TW200808907A - Composition for forming insulating films, process for production thereof, silica-base insulating films, and process for the formation of the films - Google Patents

Composition for forming insulating films, process for production thereof, silica-base insulating films, and process for the formation of the films Download PDF

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TW200808907A
TW200808907A TW096119467A TW96119467A TW200808907A TW 200808907 A TW200808907 A TW 200808907A TW 096119467 A TW096119467 A TW 096119467A TW 96119467 A TW96119467 A TW 96119467A TW 200808907 A TW200808907 A TW 200808907A
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group
component
acid
composition
insulating film
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TW096119467A
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Hisashi Nakagawa
Youhei Nobe
Masahiro Akiyama
Terukazu Kokubo
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Jsr Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Formation Of Insulating Films (AREA)
  • Silicon Polymers (AREA)
  • Paints Or Removers (AREA)
  • Organic Insulating Materials (AREA)

Abstract

A composition for forming insulating films, which comprises both a condensate prepared by the condensation through hydrolysis of (A) at least one silane selected from the group consisting of compounds represented by the general formula (1) and compounds represented by the general formula (2) with (B) a carbosilane having a structure represented by the general formula (3) and an organic solvent: R1aSi(OR2)4-a, and a general Formula (2) R3b(R4O)3-bSi-(R7)d-Si(OR5)3-cR6c; a hydrolysis-condensation product, obtained through hydrolysis-condensation in the presence of a polycarbosilane (B), having a structure whose main chain is represented by a Formula (3); and an organic solvent.

Description

200808907 九、發明說明： 【發明所屬之技術領域】 本發明係關於絕緣膜形成用組成物及其製造方法、暨二 氧化石夕系絕緣膜及其形成方法，更詳細而言，係關於可較 :佳地用於半導體元件中之層間絕緣膜等之絕緣膜形成用 •殂成物及其製造方法、暨二氧化矽系絕緣膜及其形成方 法。 【先前技術】 •習知’作為半導體元件等中之層間絕緣膜，大多使用藉 由CVD法等真空步驟而形成之二氧化矽（Si〇2)膜。並且， 近年來，以形成具有更加均勻之膜厚之層間絕緣膜為目 的，亦開始使用稱為S0G(Spin on Glass)膜之以四烷氧 基矽烧之水解生成物作為主成分之塗佈型絕緣膜。另外， $著半導體元件等之高積體化，亦開發稱為有機s〇G之以 承有機矽氧烷作為主成分之低介電係數的層間絕緣膜。 #而，奴著半導體元件等之進一步高積體化或多層化， 求更加優異之導體間之電氣絕緣性，因此，要求保存 穩定性良好、介電係數更低、機械強度更優異之層間絕緣 膜。 •另外，於半導體裝置之製造過程中，進行用以使絕緣層 •平坦化之 CMPCChemical Mechanical Planarizati〇n)步 驟、或各種清洗步驟。因此，為了應用於半導體裝置之層 間絕緣膜或保護膜等’而除了介電係數特性以外，亦要求 具有機械強度及耐化學藥品之侵韻之耐化學藥品性。 312XP/發明說明書(補件)/96-07/96119467 , 200808907 作二介電係數之材料，已提出包含如下混合物之組成 :口物係於*之存在下使烧氧基錢縮合而獲得之 ==烧氧基石夕烧之驗性部分水解物的混合物(曰本專 虎公報、特開平^ 二：、:烷乳基石夕烷之鹼性水解物於氨之存在下縮合 之㈣液（日本專利特開平11—34咖號公報、特 開平1 1 — 3 4 0 2 2 0號公耜）。妙、二 料，反應之生成物之性質不：該等方法所獲得之材 ^:機械強度、密接性等之不均亦較大，故不適應工Ϊ 佈:出有藉由混合聚碳矽烷溶液與聚矽氧烷溶液而 =丨，號公報、特開一5317號公報)，： ===在射烧與㈣氧坑之相區― 勾之狀悲分別分散於塗膜中之問題。 酸出使用有機矽酸鹽聚合物之方法，該有機石夕 物？由有機金屬石夕燒化合物製造含有碳橋之石夕 〇2/〇9γ9ΓΛ’予以水解縮合而獲得者（國際公開第 成物之穩定性較差、不適於長tr狀材料係反應生 基板之密接性較差之問題：、、子之材料’亚且存在對 低吏高分枝之聚碳矽烷進行水解縮合而獲得之 ^:糸數絕緣膜之形成方法（美國專利第6,8〇7,〇41號 »兄月書），但將聚合物塗佈於基板上後，需要氨之老化處 312XP/發明說明書(補件)/96侧6119467 ? 200808907 適=:處4,之高溫固化等步驟處理， π a只用步驟之材料。 性美之矽广人申明人提出藉由混合並加熱（A)含有水解 既基之㈣化合物與⑻含 = 昇對半導體製造步驟之耐性(曰二;，慮，而詖 觫八知、… 了改（日本專利特開2005— 350651 =丨Φ的方法。日本專利特開2005— 350651號公報之實 原"子之=不之聚合物中’存在由4個氧原子取代1個石夕 代1個Γ二如此’於聚合物構造中存在由4個氧原子取 右斜/位之情況，與並無上述部位者相比，將 有更長之加工步驟（濕式_或乾式 較差之情況。 【發明内容】 月之目的在於提供可形成如下絕緣膜之絕緣膜形 、、且成物及其製造方法，該絕緣膜可較佳地用於期望高 積體化及多層化之丰& 夕，化之牛蛉體70件等，且介電係數低，機械強 度、保存穩定性及耐化學藥品性等亦優異。 本發明之其他目的在於提供介電係數低，機械強度、保 存穩定性及耐化學藥品性等亦優異之二氧化石夕系絕緣膜 及其形成方法。 本發明一態樣之絕緣膜形成用組成物，其包含 使（A)成分與（B)成分水解縮合而獲得之水解縮合物、及 有機溶媒；該成分（A)係自以下述通式〇)所表示之化合物 以及以下述通式（2)所表示之化合物的群組選擇之至少i 種矽烷化合物，（B)成分係具有以下述通式（3)所表示之構 312XP/發明說明書(補件)/96·07/96119467 200808907 造之碳妙垸； R1aSi(〇R^)4 a ......⑴ (式中’ R1表示1價有機基，R2表示1價有機基，a表示 1〜2之整數）200808907 IX. The present invention relates to a composition for forming an insulating film, a method for producing the same, a method for forming a sulphur dioxide, and a method for forming the same, and more particularly, A method for forming an insulating film for an interlayer insulating film or the like in a semiconductor device, a method for producing the same, a cerium oxide insulating film, and a method for forming the same. [Prior Art] Conventionally, as an interlayer insulating film in a semiconductor element or the like, a cerium oxide (Si 2 ) film formed by a vacuum step such as a CVD method is often used. In addition, in recent years, in order to form an interlayer insulating film having a more uniform film thickness, a coating of a hydrolyzed product of tetraalkoxy sinter, which is called a S0G (Spin on Glass) film, has been used as a main component. Type insulating film. Further, in the case of high integration of semiconductor elements and the like, an interlayer insulating film having a low dielectric constant containing organic oxoane as a main component has been developed. #且,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, membrane. • In addition, in the manufacturing process of the semiconductor device, a CMPC Chemical Mechanical Planarz) step for planarizing the insulating layer or various cleaning steps is performed. Therefore, in addition to the dielectric constant characteristics, in order to be applied to an interlayer insulating film or a protective film of a semiconductor device, chemical resistance against mechanical strength and chemical resistance is required. 312XP/Invention Manual (Supplement)/96-07/96119467, 200808907 A material having a dielectric constant of 2, which has been proposed to contain a mixture of the following: a product obtained by condensing an alkoxy group in the presence of * = a mixture of a part of the hydrolyzate of the alkaloids of the sulphuric acid (Sui Benxihu, special Kaiping 2:,: the alkaline hydrolyzate of the alkane sulphate is condensed in the presence of ammonia (4) liquid (Japanese patent) Special Kaiping 11-34 Coffee No. Gazette, Special Kaiping 1 1 - 3 4 0 2 2 0). Wonderful, two materials, the nature of the reaction product is not: the material obtained by these methods ^: mechanical strength, The unevenness of the adhesion and the like is also large, so it is not suitable for the worksheet: a mixture of a polycarbane solution and a polyoxyalkylene solution is used. = 丨, Bulletin No. 5317, :== = In the phase zone of the firing and (4) oxygen pits - the problem of the hooks scattered in the coating film. Acidizing the method of using an organic silicate polymer, the organic stone? It is obtained by hydrolyzing and condensing a metal bridge containing a carbon bridge, which is obtained by the use of an organic metal smelting compound (the stability of the internationally disclosed first product is poor, and is not suitable for the adhesion of a long tr-shaped material reaction substrate). Poor problem: the material of the sub-substance is obtained by hydrolyzing and condensing the low-twisted and high-branched polycarbosilane. The method for forming the germanium insulating film (U.S. Patent No. 6,8,7, 〇41) No.» brothers and sisters book, but after the polymer is coated on the substrate, it needs ammonia aging 312XP / invention manual (supplement) / 96 side 6119467 ? 200808907 suitable =: at 4, high temperature curing and other steps, π a only uses the material of the step. Sexual beauty 矽 申 申 人 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申And the method of the Japanese syllabus 2005-350651 = 丨 Φ. The original Japanese version of the Japanese Patent Laid-Open No. 2005-350651 Oxygen atoms replace 1 stone eve, 1 Γ2 There are cases where the right slant/bit is taken by four oxygen atoms, and there will be a longer processing step (wet _ or dry type worse) than the case without the above. [Invention] The purpose of the month is Provided is an insulating film shape capable of forming an insulating film, and a method for producing the same, and a method for producing the same, which is preferably used for a high-volume and multi-layered shovel The dielectric constant, the storage stability, the chemical resistance, and the like are also excellent. The other object of the present invention is to provide a dielectric constant, mechanical strength, storage stability, chemical resistance, and the like. The present invention relates to a composition for forming an insulating film, which comprises a hydrolyzed condensate obtained by hydrolyzing and condensing the component (A) and the component (B), and an organic solvent; The component (A) is at least one decane compound selected from the group consisting of a compound represented by the following formula (〇) and a compound represented by the following formula (2), and the component (B) has the following formula (3) The structure represented 3 12XP/Inventive Manual (supplement)/96·07/96119467 200808907 Made of carbon wonderful; R1aSi(〇R^)4 a (1) (wherein R1 represents a monovalent organic group, and R2 represents 1 Valence organic group, a represents an integer from 1 to 2)

R3b(R40)“Si 一 (式中，R3〜R -(R7)^Si(0R5)3-〇R6c......(2) R為相同或不同’分別表示1價有機基，b ❿0或1) [化1] 以及c為相同或不同，表示〇〜2之數，RT表示伸苯基或 以（CH2)"1所表示之基（此處，m為1〜6之整數），d表示R3b(R40)"Si-(wherein R3~R-(R7)^Si(0R5)3-〇R6c...(2) R is the same or different 'is a monovalent organic group, respectively, b ❿0 or 1) [Chemical 1] and c are the same or different, indicating the number of 〇~2, RT means a phenyl group or a group represented by (CH2)"1 (here, m is an integer of 1 to 6) ), d means

[式中，R表示自氫原子、鹵素原子、羥基、烷氧基、 fe氧基、磺酸基、曱磺酸基、三氟甲磺酸基、烷基、芳基、 烯丙基、以及縮水甘油基所組成群組選擇之基，R9表示自 鹵素原子、羥基、烷氧基、醯氧基、石黃酸基、曱磺酸基、 二氟甲磺酸基、烷基、芳基、烯丙基、以及縮水甘油基所 組成群組選擇之基，為相同或不同，表示自齒素 原子、羥基、烷氧基、醯氧基、磺酸基、曱磺酸基、三氟Wherein R represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a methoxy group, a sulfonic acid group, an anthracene sulfonate group, a trifluoromethanesulfonate group, an alkyl group, an aryl group, an allyl group, and a group selected from the group consisting of glycidyl groups, and R9 represents a halogen atom, a hydroxyl group, an alkoxy group, a decyloxy group, a rhein group, an anthracenesulfonate group, a difluoromethanesulfonate group, an alkyl group, an aryl group, The groups selected from the group consisting of allyl and glycidyl groups are the same or different and represent a dentin atom, a hydroxyl group, an alkoxy group, a decyloxy group, a sulfonic acid group, an anthracene sulfonate group, and a trifluoro group.

曱磺酸基、碳數2〜6之烷基、芳基、烯丙基、以及縮水 甘油 3 UXP/發明說明書(補件)/96_〇7/96l I9467 9 200808907 代之亞μ、㈣基、料基、伸块基、伸 二 <1 §义iu，uoo之條件）。 :、=緣臈形成用組成物中’上述⑷成 上述通式（1)所表示之化合物。 於此情況下，可至少含有2種以上之上 示之化合物，且α μ、+、、s m、 、飞U>>所表 上述通式（1)所表示之化合物中，於上 广 a為1之化合物之比例為50質量％以上。 之：土=緣膜形成用組成物中’相對於換算為⑴成分 為Τ'_%合物之⑷成分100重量份’上述⑻成分可 為1〜1000重量份。 烯：d:形成用組成物中，上述⑻成分之聚苯乙 坤換异重1平均分子量為500〜10, 000。 於上述絕緣膜形成用組成物卜上述水解縮合可於鹼性 觸媒、酸性觸媒、或金屬螯合物觸媒之存在下進行。 /於此凊況下，上述水解縮合可於鹼性觸媒之存在下進 行0 、於上述絕緣膜形成用組成物中，上述鹼性觸媒可為以下 述通式（4)所表示之含氮化合物。 (X1X2X3X4N)hY ……⑷ (式中x、X、X、X為相同或不同，分別表示自氫原 子、碳數1〜2G之院基、縣烧基、芳基、以及芳基燒基 所組成群組選擇之基，γ表示_素原子或〗〜4價陰離子 性基，h表示1〜4之整數。） 312XP/發明說明書(補件)/96-07/96119467 10 200808907 上述絕緣膜形成用組成物可為實質 氧原子取代1個矽原子之部位者。、 上並不存在由Sulfonic acid group, alkyl group having 2 to 6 carbon atoms, aryl group, allyl group, and glycidol 3 UXP/Invention specification (supplement)/96_〇7/96l I9467 9 200808907 Substitute μ, (4) , material base, stretch block base, stretch two <1 § Yiu, uoo conditions). The compound represented by the above formula (1) is represented by the above (4). In this case, at least two or more of the compounds shown above may be contained, and among the compounds represented by the above formula (1), α μ, +, sm, and fly U > The ratio of the compound of 1 is 50% by mass or more. In the soil = film formation composition, the component (4) is 100 parts by weight of the component (4) in terms of the component (1), and the component (8) may be 1 to 1000 parts by weight. The olefin:d: the composition for formation, the polyphenylene exchange weight 1 of the above component (8) has an average molecular weight of 500 to 10,000. In the above-mentioned composition for forming an insulating film, the above hydrolysis and condensation can be carried out in the presence of a basic catalyst, an acidic catalyst, or a metal chelate catalyst. In this case, the hydrolytic condensation may be carried out in the presence of a basic catalyst. In the above composition for forming an insulating film, the basic catalyst may be represented by the following formula (4). Nitrogen compounds. (X1X2X3X4N)hY (4) (wherein x, X, X, and X are the same or different, and represent a radical from a hydrogen atom, a carbon number of 1 to 2 G, a calcane group, an aryl group, and an aryl group. The group that constitutes the group selection, γ represents a _ prime atom or a 〜4 valent anionic group, and h represents an integer of 1 to 4.) 312XP/Invention Manual (Supplement)/96-07/96119467 10 200808907 The above insulating film is formed The composition may be a site in which a substantial oxygen atom is substituted for one atom. Does not exist on

本發明一態樣之絕緣膜形成用 含·· 組成物之製造方法， 其包 以下、“，刀;、、成分水解縮合之步驟，該(A)成分係自 :以⑴所表示之化合物及以下述通式⑵所 物的群組選擇之至少1種錢化合物，⑻成分; 具有以下述通式⑶所表示之構造之碳石夕燒； 刀係 R1aSi(〇R2)4.a ······⑴ 表示1價有機基，a表示 (式中’ R1表示1價有機基， 1〜2之整數） R3b(R40)3-bSi-(R7)d-si(〇R5)3>cR6c ······ (2) (式中，R〜R6為相同或不同，分別表示〗價有機基，匕 以及c相同或不同，表示〇〜2之數，示伸笨基或以 -(CH〇m-所表示之基（此處，m為i〜6之整數），d表示 或1) [化2]A method for producing a composition for forming an insulating film according to an aspect of the present invention, which comprises the steps of: "a knife, a component, and a step of hydrolytic condensation, wherein the component (A) is derived from the compound represented by (1) and At least one type of money compound selected from the group of the following general formula (2), (8) component; carbon stone having a structure represented by the following general formula (3); knife system R1aSi (〇R2) 4.a ··· (1) represents a monovalent organic group, and a represents (wherein R1 represents a monovalent organic group, an integer of 1 to 2) R3b(R40)3-bSi-(R7)d-si(〇R5)3>cR6c ······ (2) (wherein R to R6 are the same or different, respectively represent the valence organic group, 匕 and c are the same or different, indicating the number of 〇~2, extending the base or taking - ( The base represented by CH〇m- (where m is an integer from i to 6), d represents or 1) [Chemical 2]

(式中’ R8表示自氫原子、鹵素原子、羥基、燒氧基、 酸氧基、石黃酸基、曱績酸基、三氟曱續酸基、烧基、芳基、 312XP/發明說明書(補件)/96-07/96119467 11 200808907 烯丙基、以及縮水甘油基所組成群組選擇之基，R9表示自 鹵素原子、羥基、烷氧基、醯氧基、磺酸基、甲磺酸基、 二氟曱磺酸基、烷基、芳基、烯丙基、以及縮水甘油基所 組成群組選擇之基，、Rn為相同或不同，表示自鹵素 原子、羥基、烷氧基、醯氧基、磺酸基、甲磺酸基、三氟 !甲磺酸基、碳數2〜6之烷基、芳基、烯丙基、以及縮水 甘油基所組成群組選擇之基，R12〜RU為相同或不同，表 不取代或非取代之亞曱基、伸烷基、伸烯基、伸炔基、伸 ⑩芳基’e、f、g分別表示〇〜1〇,〇〇〇之數，滿足1〇<e+f + g< 10, 000 之條件）。 本發明一態樣之水解縮合聚合物，係藉由上述絕緣膜形 成用組成物之製造方法而獲得。 本發明一態樣之二氧化矽系絕緣膜之形成方法，包含： 將上述絶緣膜形成用組成物塗佈於基板行而形成塗膜之 步驟； ' • 對上述塗膜實施自加熱、電子線照射、紫外線照射、以 及氧電漿中選擇之至少丨種硬化處理之步驟。 本發明-態樣之二氧化矽系絕緣膜，係藉由上述二氧化 矽系絕緣膜之形成方法而獲得。 •根據上述絕緣膜形成用組成物，含有使（A)成分與（幻 ‘成分水解縮合而獲得之水解縮合物。於該水解縮合中、，於 (A)成分產生水解而形成矽氫氧基（_Si_〇H)之同時，於（们 亦生成水解產生之錢氧基1錢氧基可引起縮 口反應而形成Si-0-Si鍵。另外，該水解縮合物具有如下 312XP/發明說明書(補件)/96-07/96119467 \〇 200808907 構造’即，（B)成分盥爽白 鍵結，而嵌人至三❹構内)成分之㈣氧絲成化學性 緣膜形成用組成物'，；=此’藉由使用本發明之絕 成機械強度高、密接性優異、且 由、LI 絕緣膜。進而，由於⑴成分並不存在 :解:W體與⑻成分之水解縮合物二=: C 性°藉此’可確保對時間更長之加工步驟 (/"、、式鍅刻或乾式姓刻）之耐性。 另外’根據上述絕緣臈形成用 包含使⑴成分與(物水解縮合之步驟:而:= 較緩和之條件獲得水解縮合物，故容易控制反/相對 =’根據上述二氧切系絕緣膜之形成^ =述絕緣膜形成用組成物塗佈於基板上而形成塗膜之 以及議中選擇之至少丨種硬 :得之:氧切系絕緣膜之介電係數小 ：此:斤 性、以及耐化學藥品性優異，且無臈中之相分離:山接 【實施方式】 以下，就本發明加以具體說明。 1 ·膜形成用組成物及其製造方法 本發明一實施形態之膜形成用組成物（ 成物)，包含使⑷成分於⑻成分之存在下進行 合之水解縮合物(以下，「稱為特定水解縮合物」)解及； 機溶媒，該（A)成分係自以下述通式Γn ’ J所表示之化合物及 312XP/發明說明書(補件)/96·07/96119467 13 ' 200808907 以下述通式（2)所表示之化合物的群組選擇之至少1種矽 烷化合物，（B)成分係具有以下述通式（3)所表示之構造之 碳矽烷。即，本發明一實施形態之絕緣膜形成用組成物之 製造方法係包含使（A)成分與（6)成分進行水解縮合之步 : 驟。以下，就各成分加以說明。 - 於本發明一實施形態之膜形成用組成物中，實質上並不 存在由4個氧原子取代1個矽原子之部位。此處，「實質 上並不存在由4個氧原子取代1個矽原子之部位」可藉由 ⑩於29S i核磁NMR測定中於-9 0〜-120 ppm未觀察到波岭而 確認。另外，此處，所謂「於29Si丽R測定中於-90〜-120 ppm未觀察到波峰」，係指於29Si丽R測定中，將存在於50 〜-80 ppm之波峰之積分值之總和設為1時，存在於-90 〜-120 ppm之波峰之積分值之總和未滿0.01。此處，50 〜-8 0 ppm之波峰相當於1個石夕原子由3個以下之氧原子 所取代之部位之成分。因此，與具有該部位之水解性矽烷 0單體與（B)成分之水解縮合物相比，藉由本發明一實施形 態之膜形成用組成物，可進一步提高耐化學藥品性。藉 此，可確保對時間更長之加工步驟（濕式蝕刻或乾式蝕刻） 之耐性。 • 1. 1. (A)成分 . (A)成分係自以下述通式（1)所表示之化合物（以下，稱 為「化合物1」）、以下述通式（2)所表示之化合物（以下， 稱為「化合物2」）的群組選擇之至少1種矽烷化合物。 (A)成分並不存在由4個氧原子取代1個秒原子之部位。 312XP/發明說明書(補件)/96-07/96119467 14 200808907 R、Si(〇R2)4—a ......⑴ (式中，R1表示1價有機基，R2表示丨價有機基，a表示 1〜2之整數。） R3b(R40)3-bSi-(R7)d-Si(0R5)3-cR6c·· •…(2) ]、U中,，R3〜R6為相同或不同’分別表示】價有機基，b ：以及C為相同或不同，表示0〜2之數，R7表示伸苯基或 以-(CH2)m-所表示之基（此處，mg i〜6之整數），d表示 0 或 1) 〇 鲁此處，於獲得加熱、電子線照射、紫外線照射、以及氧 電聚等處理中之硬化性良好之水解縮合物方面，⑴成分 較佳為包含化合@ 1。於此情況下，於使硬化性保持在一 定水準以上方面，更佳為（A)成分包含至少i種化合物i， 化合物1之中，於上述通式（1)中8為丨之化合物（化合物 1 — 1)之比例為50質量％以上，更佳為6〇質量％以上，特 佳為70質量％以上。 • 於此情況下，於包含化合物1之中上述通式（1)中a為 1之化合物（化合物1 —1)、及化合物丨之中上述通式（1) 中a為2之化合物(化合物卜。之情況下，較佳為化合 物1 —2相對於化合物1 —丨及化合物丨―2之總量為5〇質 .量％以下，更佳為30質量％以下。此處，藉由使化合物 '丄 * — 2化合物相對於丨―1及化合物1 — 2之總量為50質量％ 以下，可獲得於加熱、電子線照射、紫外線照射、以及氧 電漿等處理中硬化性良好之水解縮合物。 1 · 1 · 1.化合物1 312沿/發明說明書(補件)/96-07/96119467 15 200808907 舉^通:式二：…^所表示之“賈有機基^ 二λ、元；其笪土、，基等。此處，烷基可舉出甲基、乙基、 亦ΐ為八=’較佳為碳數1〜5，該等烧基既可為鏈狀， 二一。於上述通式⑴中，烯基可舉出乙晞基、烯 丙基等。另外，於μ、+、、s A, m(wherein R8 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an acidoxy group, a rhein group, a fluorinated acid group, a trifluorosulfonate group, a decyl group, an aryl group, 312XP/invention specification (Supplement) /96-07/96119467 11 200808907 Allyl, and glycidyl groups are selected from the group consisting of R9, which represents a halogen atom, a hydroxyl group, an alkoxy group, a decyloxy group, a sulfonic acid group, and a methyl sulfonate. a group selected from the group consisting of an acid group, a difluorosulfonium sulfonate group, an alkyl group, an aryl group, an allyl group, and a glycidyl group, and Rn is the same or different and represents a halogen atom, a hydroxyl group, an alkoxy group, a group selected from the group consisting of a decyloxy group, a sulfonic acid group, a methanesulfonic acid group, a trifluoro! methanesulfonic acid group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group, and a glycidyl group, R12 ~RU is the same or different, and the unsubstituted or unsubstituted fluorenyl, alkylene, alkenyl, alkynyl, and aryl groups 'e, f, and g represent 〇~1〇, respectively. The number satisfies 1 〇 <e+f + g < 10, 000 conditions). The hydrolyzed condensation polymer of one aspect of the present invention is obtained by the above-described method for producing a composition for forming an insulating film. A method for forming a ruthenium dioxide-based insulating film according to another aspect of the invention includes the steps of: applying the composition for forming an insulating film to a substrate row to form a coating film; ' • self-heating and electron-charging the coating film At least one of the steps of irradiation, ultraviolet irradiation, and oxygen plasma selection. The cerium oxide-based insulating film of the present invention is obtained by the above-described method for forming a cerium oxide-based insulating film. The composition for forming an insulating film contains a hydrolyzed condensate obtained by hydrolyzing and condensing the component (A) with a phantom component. In the hydrolytic condensation, the component (A) is hydrolyzed to form a hydrazine hydroxy group. (_Si_〇H), at the same time, (they also generate a hydroxyl group 1 oxy group produced by hydrolysis to cause a condensation reaction to form a Si-0-Si bond. In addition, the hydrolysis condensate has the following 312XP / invention specification (Supplement) /96-07/96119467 \〇200808907 Structure 'that is, (B) component 盥 cool white bond, and embedded in the three ❹ structure) (4) oxygen wire into a chemical film formation composition ' , by the use of the present invention, the mechanical strength is high, the adhesion is excellent, and the insulating film is made of LI. Further, since the component (1) does not exist: solution: hydrolysis condensate of the W body and the component (8) = : C property ° by this 'ensures the resistance to longer processing steps (/", 鍅, or dry type). In addition, according to the above-mentioned insulating bismuth formation, the (1) component is condensed with (the substance is hydrolyzed) Step: and: = The hydrolysis condensate is obtained under milder conditions, so it is easy to control the inverse/phase According to the formation of the above-mentioned dioxic-type insulating film, the composition for forming an insulating film is applied onto a substrate to form a coating film, and at least a hard type selected from the following: an oxygen-cut insulating film The dielectric constant is small: this is excellent in chemical properties and chemical resistance, and phase separation in the absence of bismuth: EMBODIMENT [Embodiment] Hereinafter, the present invention will be specifically described. The film forming composition (product) according to the embodiment of the present invention includes a hydrolysis condensate (hereinafter referred to as "specific hydrolysis condensate") obtained by combining the component (4) in the presence of the component (8); In the solvent, the component (A) is a compound represented by the following formula (2) and a compound represented by the following formula (2): 312XP/invention specification (supplement)/96·07/96119467 13 '200808907 At least one decane compound selected from the group, and the component (B) has a carbon decane having a structure represented by the following formula (3). That is, the method for producing the composition for forming an insulating film according to the embodiment of the present invention includes Carrying the components (A) and (6) In the film-forming composition of one embodiment of the present invention, substantially no part of the atomic group is replaced by four oxygen atoms. "There is no substantial substitution of one argon atom by four oxygen atoms". It can be confirmed by a no-observation of the -9 0 to -120 ppm in the 10 29 29S i nuclear magnetic NMR measurement. Here, "the peak is not observed at -90 to -120 ppm in the measurement of 29Si Li", which means that the sum of the integral values of the peaks present at 50 to -80 ppm is set to 1 in the measurement of 29Si Li R. At the time, the sum of the integral values of the peaks present in the range of -90 to -120 ppm is less than 0.01. Here, the peak of 50 to -8 0 ppm corresponds to a component of a portion in which one stone atom is replaced by three or less oxygen atoms. Therefore, the chemical conversion resistance can be further improved by the film-forming composition of one embodiment of the present invention, as compared with the hydrolysis-condensation product of the hydrolyzable decane 0 monomer and the component (B). This ensures long-lasting processing steps (wet or dry etching). (1) The component (A) is a compound represented by the following formula (1) (hereinafter referred to as "compound 1") and a compound represented by the following formula (2) ( Hereinafter, at least one decane compound selected from the group of "compound 2") is selected. The component (A) does not have a site in which one oxygen atom is substituted by one oxygen atom. 312XP/Invention Manual (Supplement)/96-07/96119467 14 200808907 R, Si(〇R2)4—a (1) (wherein R1 represents a monovalent organic group and R2 represents a valence organic group. , a represents an integer of 1 to 2.) R3b(R40)3-bSi-(R7)d-Si(0R5)3-cR6c·· (2) ], U, R3 to R6 are the same or different 'Respectively denotes a valence organic group, b: and C are the same or different and represent a number of 0 to 2, and R7 represents a phenyl group or a group represented by -(CH2)m- (here, mg i~6 Integer), d represents 0 or 1) In the case of obtaining a hydrolyzed condensate having good curability in a treatment such as heating, electron beam irradiation, ultraviolet irradiation, and oxygen electropolymerization, the component (1) preferably contains a compound @ 1. In this case, in order to maintain the curability at a certain level or higher, it is more preferable that the component (A) contains at least one compound i, and among the compounds 1, the compound of the formula (1) is ruthenium (compound) The ratio of 1 to 1) is 50% by mass or more, more preferably 6% by mass or more, and particularly preferably 70% by mass or more. In this case, a compound (a compound 1-1) in which the a is 1 in the above formula (1), and a compound in which the a is 2 in the above formula (1) in the compound oxime (compound) In the case of the compound 1-2, the total amount of the compound 1-2 relative to the compound 1 - hydrazine and the compound 丨 - 2 is preferably 5 〇 by mass or less, more preferably 30% by mass or less. The compound '丄*-2 compound is 50% by mass or less based on the total amount of the 丨-1 and the compound 1-2, and can be obtained by hydrolysis, electron beam irradiation, ultraviolet irradiation, and oxygen plasma treatment. Condensate. 1 · 1 · 1. Compound 1 312 along / invention specification (supplement) / 96-07/96119467 15 200808907 Lifting ^: formula 2: ... ^ said "Jia organic base ^ λ, yuan; The alumina, the base, etc. Here, the alkyl group may be a methyl group, an ethyl group, or an anthracene group of eight = ' preferably a carbon number of 1 to 5, and these alkyl groups may be chain-shaped or two. In the above formula (1), the alkenyl group may, for example, be an ethylidene group, an allyl group or the like. Further, in μ, +, s A, m

Am其L、式⑴中，芳基可舉出苯基、萘 %由:矣土】:乙基苯基、氯苯基、漠苯基、氟苯基等0 精為1價有機基’可防止產生 所取代之部位。 τ 丁 W ML1乳 之具體例，可舉出甲基三甲氧她、甲 Sr =石坑、甲基三正丙氧基石夕烧、甲基三異丙氧基 2第f夕燒、甲基三第二丁氧她、甲 —弟二丁乳基石夕烧、甲基三苯氧基石夕烧、乙基三 三乙氧基石夕燒、乙基三正丙氧基石夕炫、乙基： 異丙乳基石夕燒、乙基三正丁氧基石夕燒、乙基三第二丁氧基 Γ二ΐ三第三丁氧基石夕燒、乙基三苯氧基錢、正丙 :一甲乳基矽烷、正丙基三乙氧基矽烷、正丙基三正丙氧 基找、正丙基三異丙氧基石夕烷、正丙基三正丁氧基石夕 炫'正丙基三第二丁氧基錢、正丙基三第三二; ”丙基三苯氧基矽烷、異丙基三甲氧基矽烷、異丙基 :乙乳基石夕炫、異丙基三正丙氧基石夕燒、異丙基三異丙氧 =燒、異丙ί三正丁氧基石夕炫、異丙基三第二丁氧基石夕 凡、異丙基二弟二丁氧基石夕燒、異丙基三苯氧基石夕燒、正 丁基二甲氧基石夕燒、正丁基三乙氧基石夕炫、正丁基三正丙 氧基我、正丁基三異丙氧基石夕燒、正丁基三正丁氧基石夕 312ΧΡ/發明說明書(補件)/96·07/96119467 ^ 1〇 200808907 烷、正丁基三第二丁氧基矽烷、正丁基三第三丁氧基矽 烷、正丁基三苯氧基矽烷、第二丁基三曱氧基矽烷、第二 丁基異三乙氧基矽烷、第二丁基三正丙氧基矽烷、第二丁 基三異丙氧基矽烷、第二丁基三正丁氧基矽烷、第二丁基 1 三第二丁氧基矽烷、第二丁基三第三丁氧基矽烷、第二丁 - 基三苯氧基矽烷、第三丁基三曱氧基矽烷、第三丁基三乙 氧基矽烷、第三丁基三正丙氧基矽烷、第三丁基三異丙氧 基矽烷、第三丁基三正丁氧基矽烷、第三丁基三第二丁氧 _基矽烷、第三丁基三第三丁氧基矽烷、第三丁基三苯氧基 矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、苯基三正 丙氧基矽烷、苯基三異丙氧基矽烷、苯基三正丁氧基矽 烷、苯基三第二丁氧基矽烷、苯基三第三丁氧基矽烷、苯 基三苯氧基矽烷、乙烯基三曱氧基矽烷、乙烯基三乙氧基 矽烷、乙烯基三正丙氧基矽烷、乙烯基三異丙氧基矽烷、 乙烯基三正丁氧基矽烷、乙烯基三第二丁氧基矽烷、乙烯 0基三第三丁氧基矽烷、乙烯基三苯氧基矽烷、二曱基二曱 氧基矽烷、二曱基二乙氧基矽烷、二曱基二正丙氧基矽 烷、二曱基二異丙氧基矽烷、二曱基二正丁氧基矽烷、二 甲基二第二丁氧基矽烷、二甲基二第三丁氧基矽烷、二甲 • 基二苯氧基矽烷、二乙基二曱氧基矽烷、二乙基二乙氧基 、 矽烷、二乙基二正丙氧基矽烷、二乙基二異丙氧基矽烷、 二乙基二正丁氧基矽烷、二乙基二第二丁氧基矽烷、二乙 基二第三丁氧基矽烷、二乙基二苯氧基矽烷、二正丙基二 曱氧基矽烷、二正丙基二乙氧基矽烷、二正丙基二正丙氧 312XP/發明說明書(補件)/96-07/96119467 17 200808907 基矽烷、二正丙基二異丙氧基矽烷、二正丙基二正丁氧基 矽烷、二正丙基二第二丁氧基矽烷、二正丙基二第三丁氧 基矽烷、二正丙基二苯氧基矽烷、二異丙基二甲氧基矽 烷、二異丙基二乙氧基矽烷、二異丙基二正丙氧基矽烷、 1 二異丙基二異丙氧基矽烷、二異丙基二正丁氧基矽烷、二 : 異丙基二第二丁氧基矽烷、二異丙基二第三丁氧基矽烷、 二異丙基二苯氧基矽烷、二正丁基二曱氧基矽烷、二正丁 基二乙氧基矽烷、二正丁基二正丙氧基矽烷、二正丁基二 ⑩異丙氧基矽烷、二正丁基二正丁氧基矽烷、二正丁基二第 二丁氧基矽烷、二正丁基二第三丁氧基矽烷、二正丁基二 苯氧基矽烷、二第二丁基二甲氧基矽烷、二第二丁基二乙 氧基矽烷、二第二丁基二正丙氧基矽烷、二第二丁基二異 丙氧基矽烷、二第二丁基二正丁氧基矽烷、二第二丁基二 第二丁氧基矽烷、二第二丁基二第三丁氧基矽烷、二第二 丁基二苯氧基矽烷、二第三丁基二曱氧基矽烷、二第三丁 •基二乙氧基矽烷、二第三丁基二正丙氧基矽烷、二第三丁 基二異丙氧基矽烷、二第三丁基二正丁氧基矽烷、二第三 丁基二第二丁氧基矽烷、二第三丁基二第三丁氧基矽烷、 二第三丁基二苯氧基矽烷、二苯基二曱氧基矽烷、二苯基 . 二乙氧基矽烷、二苯基二正丙氧基矽烷、二苯基二異丙氧 、 基矽烷、二苯基二正丁氧基矽烷、二苯基二第二丁氧基矽 烷、二苯基二第三丁氧基矽烷、二苯基二苯氧基矽烷、二 乙烯基二曱氧基矽烷。該等可使用1種或同時使用2種以 上0 312XP/發明說明書(補件)/96-07/96119467 18 200808907 作為化合物卜特佳之化合物為甲基三甲氧基矽烷、甲 基二乙氧基矽烷、f基三正丙氧基矽烷、甲基三異丙氧基 矽烷、乙基三甲氧基矽烷、乙基三乙氧基 甲氧基錢、乙婦基三乙氧基我、苯基三甲氧基 苯基三乙氧基矽烷、二甲基二曱氧基矽烷、二甲基二乙氧 f矽烷、二乙基二甲氧基矽烷、二乙基二乙氧基矽烷、二 苯基一甲氧基矽烷、二苯基二乙氧基矽烷等。 1. 1· 2·化合物2Am, L, and (1), the aryl group may be phenyl, naphthalene% by: alumina: ethylphenyl, chlorophenyl, phenyl, fluorophenyl, etc. 0 is a monovalent organic group' Prevent the replacement of the parts. Specific examples of the τ-butyl W ML1 milk include methyltrimethoxazole, methyl Sr = crater, methyl tri-n-propoxylate, methyl triisopropoxy 2, and m-triazole. The second butoxy oxygen, A-di-dibutyl ketone, the methyltriphenoxylate, the ethyltritriethoxy zebra, the ethyltri-n-propoxylate, the ethyl: isopropyl Milk-based stone burning, ethyl tri-n-butoxy-oxygen, ethyl tri-n-butoxy ruthenium tridecyl tributoxylate, ethyl triphenyloxy money, n-propyl: monomethyl矽, n-propyl triethoxy decane, n-propyl tri-n-propoxy, n-propyl triisopropoxy oxa sulphate, n-propyl tri-n-butoxy sulphate Oxyl money, n-propyl tri-third, two; propyl triphenyloxydecane, isopropyl trimethoxy decane, isopropyl: ethyl lactate Xixuan, isopropyl tri-n-propoxylate, Isopropyl triisopropyloxy = calcined, isopropyl tri-n-butoxy-xanthine, isopropyl tri-n-butoxy-xanthine, isopropyl di-di-butoxide, isopropyl triphenyl Oxygen stone, n-butyl dimethoxy Shi Xizhuo, n-butyl triethoxy Shi Xi Xuan, n-butyl tri-n-propoxy, me-n-butyl triisopropoxy zebra, n-butyl tri-n-butoxy xi 312 ΧΡ / invention instructions (complement ())/96·07/96119467 ^ 1〇200808907 Alkane, n-butyl tri-butoxy decane, n-butyl tri-tert-butoxy decane, n-butyl triphenoxy decane, second butyl three a decyloxydecane, a second butyl isotriethoxy decane, a second butyl tri-n-propoxy decane, a second butyl triisopropoxy decane, a second butyl tri-n-butoxy decane, Dibutyl 1,3-tributoxy decane, second butyl tri-butoxy decane, second butyl-triphenyloxydecane, tert-butyltrimethoxy decane, tert-butyl three Ethoxy decane, tert-butyl tri-n-propoxy decane, tert-butyl triisopropoxy decane, tert-butyl tri-n-butoxy decane, tert-butyl tri-second butoxide-based decane , tert-butyltris-tert-butoxydecane, tert-butyltriphenoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, phenyltri-n-propoxydecane, phenyl trisole Propoxy decane, phenyl tri-n-butoxy decane, phenyl tri-tert-butoxy decane, phenyl tri-tert-butoxy decane, phenyltriphenyloxydecane, vinyl trimethoxy decane, Vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri-n-butoxy decane, ethylene 0-based Tributoxydecane, vinyltriphenoxydecane, dimercaptodimethoxydecane, dimercaptodiethoxydecane, dimercaptodi-n-propoxyoxydecane, dinonyldiisopropoxy Decane, dimercaptodi-n-butoxydecane, dimethyldi-butoxybutane, dimethyldi-butoxydecane, dimethyldiphenoxydecane, diethyldioxetane Base decane, diethyldiethoxy, decane, diethyldi-n-propoxy decane, diethyldiisopropoxy decane, diethyldi-n-butoxy decane, diethyldi-second Oxydecane, diethyldi-t-butoxydecane, diethyldiphenoxydecane, di-n-propyldimethoxyoxydecane, di-n-propyldiethyl Base decane, di-n-propyldi-n-propoxy 312XP/invention specification (supplement)/96-07/96119467 17 200808907 decyl, di-n-propyldisisopropoxy decane, di-n-propyldi-n-butoxy Decane, di-n-propyldi-n-butoxybutane, di-n-propyldi-butyoxybutane, di-n-propyldiphenoxydecane, diisopropyldimethoxydecane, diisopropyl Diethoxydecane, diisopropyldi-n-propoxyoxydecane, 1 diisopropyldiisopropoxydecane, diisopropyldi-n-butoxydecane, di:isopropyl propylene second butoxide Base decane, diisopropyl bis 3 butyloxy decane, diisopropyl diphenoxy decane, di-n-butyl dimethoxy decane, di-n-butyl diethoxy decane, di-n-butyl N-propoxy decane, di-n-butyl di-isopropoxy decane, di-n-butyl di-n-butoxy decane, di-n-butyl di-butoxy decane, di-n-butyl bis-butoxide Base decane, di-n-butyldiphenoxydecane, di-second butyl dimethoxy decane, di-second butyl diethoxy decane, di-second butyl di-n-propoxy decane, second Diisopropoxy decane, dibutyl butyl di-n-butoxy decane, di-second butyl di-butoxy decane, di-second butyl di-butoxy decane, two second butyl Diphenoxydecane, di-tert-butyldimethoxyoxydecane, di-tert-butyldiethoxydecane, di-tert-butyldi-n-propoxydecane, di-tert-butyldiisopropyl Oxydecane, di-tert-butyldi-n-butoxydecane, di-tert-butyldi-second-butoxydecane, di-tert-butyldi-t-butoxydecane, di-t-butyldiphenyloxide Base decane, diphenyl decyloxy decane, diphenyl. diethoxy decane, diphenyl di-n-propoxy decane, diphenyl diisopropoxide, decane, diphenyl di-n-butoxy Basear, diphenyldi-butoxybutane, diphenyldi-butoxybutane, diphenyldiphenoxydecane, divinyldimethoxyoxydecane. These may be used alone or in combination of two or more. 0 312XP/Invention Manual (Supplement)/96-07/96119467 18 200808907 The compound of the compound Bu Tejia is methyltrimethoxydecane, methyldiethoxydecane. , f-based tri-n-propoxy decane, methyl triisopropoxy decane, ethyl trimethoxy decane, ethyl triethoxy methoxy ketone, ethyl ethoxylated triethoxy I, phenyl trimethoxy Phenyltriethoxydecane, dimethyldimethoxyoxydecane, dimethyldiethoxyoxane, diethyldimethoxydecane, diethyldiethoxydecane, diphenyl-a Oxydecane, diphenyldiethoxydecane, and the like. 1. 1· 2·Compound 2

於通式⑺中，R3〜R6之1價有機基，可舉出與上述通式 (1)中作為R1、R2而例示之丨價有機基相同之基。 另外，藉由R為伸苯基或以—（CH2)m—所表示之基，而於 通式⑵中G為〇之情況下’可防止產生丨個石夕原子 由4個氧原子所取代之部位。 於通式（2)中，作為d=〇之化合物，可舉出六甲氧基二 夕烷乙氧基二矽烷、六苯氧基二矽烷、uj，2, 2一 五甲氧基-2-甲基二矽烷、i l l 2, 2一五乙氧基一2—甲基二 矽烷2 1，1，1，2, 2-五苯氧基一2一曱基二矽烷、2 一 五曱氧基-2-乙基二矽烷、l l l 2, 2一五乙氧基一2一乙基二 夕烷L L L 2, 2 —五苯氧基-2-乙基二矽烷、1，1，1，2, 2-五甲氧基—2一苯基二矽烷、1，1，1，2, 2-五乙氧基-2-苯基二 矽烷、1，1，1，2, 2-五苯氧基-2-苯基二矽烷、1，i，2, 2-四 甲氧基-1，2-二曱基二矽烷、i 2, 2一四乙氧基一l 2一二曱 基一矽烷、1.1，2, 2-四苯氧基—l 2一二曱基二矽烷、 Μ，2, 2-四甲氧基一l 2一二乙基二矽烷、l h 2, 2一四乙氧 312ΧΡ/發明說明書(補件)/96〇7/96119467 19 200808907 基-1，2-二乙基二矽烷、1，1，2, 2-四苯氧基-i，2-二乙基二 矽烷、1，1，2, 2-四曱氧基〜i，2一二苯基二矽烷、M，2, 2-四乙氧基-1，2-二苯基二矽烷、lu，2—四苯氧基—ι，2-二苯基二矽烷、1，1，2-三曱氧基一l 2, 2—三甲基二矽烷、 1，1，2-二乙氧基-1，2, 2-三甲基二矽烷、l l 2一三苯氧基 -1，2, 2-三曱基二矽烷、1，；[，2一三曱氧基〜^ 2, 2一三乙基二 石夕统、1，1，2-三乙氧基-12 2-二？"其-a 0 - —〆 —乙基一矽烷、1，1，2一二· 本虱基-1，2,2-三乙基二矽烷、112_三曱 4 2,2一 三苯基二石夕烷、U’2—三乙氧基弋2, 2〜三苯基土二石夕烷、 1’1，2-二苯氧基-i’2’2-三苯基二矽烷、】2二甲氧基 -U’2’2-四甲基二石夕烧、U-二乙氧基2;四甲基 二石浅、U-二苯氧基一四甲基二石夕烧、u一二 甲氧基-1，1，2, 2-四乙基二矽烷、L 2一二 一 四乙基二矽烷、1，2-二苯氧基-i i 2 虱土 _ ^ ,^ t四乙基二矽烷、 1，2-二曱氧基-112,2-四苯基n 氧基 -1，1，2, 2-四苯基二矽烷、i 2_二苯氧 ， 二石夕烧等。 本减、1，1，2,2-四苯基 六乙 J等之中，作為較佳例，可舉出六甲氣基二石夕烧 乳基二：烧、U’2’2-四甲氧基-1>2、二甲基二石夕烧、 匕;二氧基]，2 —二曱基二錢、1，U，2-四甲氧 :广;一广 烧、1,2 —二甲氧基―1，1，2,2-四甲基二 乙氧基―1’1，2’2-四甲基二砂烷、U-二甲 3其U 2’2—四苯基二 四苯基二矽烷等。 312XP/發明說明書(補件)/96-07/% 1194^7 20 200808907 進而，作為化合物2,作為於通式（2)中R?為以_(CH2)m— 表示之基之化合物，可舉出雙（三甲氧基矽烷基）甲烷、雙 (三乙氧基矽烷基）甲烷、雙（三正丙氧基矽烷基）曱烷、雙 (三異丙氧基矽烷基）甲烷、雙（三正丁氧基矽烷基）甲烷、 雙（三第二丁氧基矽烷基）曱烷、雙（三第三丁氧基矽烷基） 甲烷、1，2-雙（三曱氧基矽烷基）乙烷、1>2一雙（三乙氧基 矽烷基）乙烷、1,2-雙（三正丙氧基矽烷基）乙烷、丨，2一雙 (三異丙氧基矽烷基）乙烷、；[，2-雙（三正丁氧基矽烷基〉 乙烷、1，2-雙（三第二丁氧基矽烷基）乙烷、丨，2 —雙（三第 三丁氧基矽烷基）乙烷、1 -（二曱氧基甲基矽烷基）一丨一（三 甲氧基矽烧基）曱烷、1-（二乙氧基甲基矽烷基）4 一（三乙 氧基矽烷基）曱烷、1-（二正丙氧基曱基矽烷基）4 一(三正 丙氧基石夕烧基）曱烧、1 -（二異丙氧基甲基石夕烧基）一1 一（三 異丙氧基矽烷基）曱烷、1 -（二正丁氧基甲基矽烧 基）-卜（三正丁氧基矽烷基）甲烷、1 一（二第二丁氧基甲基 矽烷基）-1-(三第二丁氧基矽烷基）甲烷、1 —(二第三丁氧 基曱基矽烧基）-1 -（三第三丁氧基矽烧基）甲烷、1 —(二甲 氧基甲基矽烷基）-2-（三曱氧基矽烷基）乙烧、1一（二乙氧 基甲基矽烷基）_2-(三乙氧基矽烷基）乙烷、i-(二正丙氧 基甲基矽烷基）-2-(三正丙氧基矽烷基）乙烷、二異丙 氧基曱基石夕烧基）-2-(三異丙氧基石夕烧基）乙烧、ι —(二正 丁氧基甲基梦烧基）-2-(三正丁氧基梦烧基）乙烧、ι 二 第二丁氧基曱基矽烷基）-2-(三第二丁氧基矽烷基）乙 烷、1-(二第三丁氧基甲基矽烷基）-2-(三第三丁氧基發燒 312XP/發明說明書(補件)/96-07/96119467 21 200808907 基）乙烷、雙（二曱氧基曱基矽烷基）曱烷、雙（二乙氧基甲 基矽烷基）曱烷、雙（二正丙氧基甲基矽烷基）甲烷、雙（二 異丙氧基甲基矽烷基）甲烷、雙（二正丁氧基甲基矽烷基） 曱烷、雙（二第二丁氧基甲基矽烷基）曱烷、雙（二第三丁 氧基曱基矽烷基）甲烷、1，2-雙（二曱氧基甲基矽烷基）乙 烧、1，2-雙（二乙氧基甲基矽烷基）乙烷、；|，2一雙（二正丙 氧基曱基矽烷基）乙烷、1,2-雙（二異丙氧基甲基矽烷基） 乙烷、1，2-雙（二正丁氧基甲基矽烷基）乙烷、丨，2_雙（二 第二丁氧基曱基矽烷基）乙烷、1，2-雙（二第三丁氧基曱基 矽烷基）乙烷、1，2-雙（三甲氧基矽烷基）苯、丨，2_雙（三乙 氧基矽烷基）苯、1，2-雙（三正丙氧基矽烷基）苯、厂^雙 (二異丙氧基矽烷基）苯、1，2-雙（三正丁氧基矽烷基）苯、 1’2-雙（三第二丁氧基矽烷基）苯、12_雙（三第三丁氧基 矽烷基）苯、1，3-雙（三甲氧基矽烷基）苯、13-雙（三乙& 基石夕烷基）苯、1，3-雙（三i丙氧基錢基）苯、i 3_雙（三 =丙氧基錢基）苯、U-雙（三正丁氧基錢幻苯、^ Li弟^丁氧基石夕烧基）苯、1,3,三第三丁氧基石夕烧In the general formula (7), the monovalent organic group of R3 to R6 may be the same as the valence organic group exemplified as R1 and R2 in the above formula (1). Further, by R being a phenyl group or a group represented by -(CH2)m-, and in the case where G is 〇 in the formula (2), it is possible to prevent the generation of a cerium atom by four oxygen atoms. The part. In the formula (2), examples of the compound of d = fluorene include hexamethoxydioxane ethoxy dioxane, hexaphenoxydioxane, uj, 2, 2-pentamethoxy-2- Methyldioxane, ill 2, 2,5-ethoxy 2-methyl-dioxane 2 1,1,1,2,2-pentaphenoxy- 2,2-decyldioxane, 2,5-pentyloxy -2-ethyldioxane, lll 2, 2,5-ethoxyethoxy-2-ethylenedi-alkane LLL 2,2-pentaphenoxy-2-ethyldioxane, 1,1,1,2, 2-pentamethoxy-2-phenyldioxane, 1,1,1,2,2-pentaethoxy-2-phenyldioxane, 1,1,1,2,2-pentaphenoxy -2-phenyldioxane, 1,i,2,2-tetramethoxy-1,2-dimercaptodioxane, i 2, 2 -tetraethoxy-l 2 -dihydroxyl-decane, 1.1,2,2-Tetraphenoxy-l 2 -didecyldioxane, hydrazine, 2,2-tetramethoxy-l 2 diethyldioxane, lh 2, 2 -tetraethoxy 312 ΧΡ / BRIEF DESCRIPTION OF THE INVENTION (Spread)/96〇7/96119467 19 200808907 Base-1,2-diethyldioxane, 1,1,2,2-tetraphenoxy-i,2-diethyldioxane, 1 1,2,2-tetradecyloxy~i,2-diphenyldioxane, M 2,2-tetraethoxy-1,2-diphenyldioxane, lu, 2-tetraphenoxy-ι,2-diphenyldioxane, 1,1,2-trimethoxyl-l 2,2-trimethyldioxane, 1,1,2-diethoxy-1,2,2-trimethyldioxane, ll 2-triphenyloxy-1,2,2-trimethyl Dioxane, 1,; [, 2,3-trimethoxy-^ 2, 2,3-triethyl oxalate, 1,1,2-triethoxy-12 2-? "It-a 0 - - 〆-ethyl decane, 1,1,2 bis · Benthyl-1,2,2-triethyldioxane, 112_3曱4 2,2-triphenyl Dioxazide, U'2-triethoxy oxime 2, 2~triphenyl oxadiazepine, 1'1,2-diphenoxy-i'2'2-triphenyldioxane ,] 2 dimethoxy-U'2'2-tetramethyl bismuth, U-diethoxy 2; tetramethyl feldspar, U-diphenoxy-tetramethyl bismuth Burning, u-dimethoxy-1,1,2,2-tetraethyldioxane, L 2 -ditetraethyl dioxane, 1,2-diphenoxy-ii 2 alumina _ ^ ^ ttetraethyldioxane, 1,2-dimethoxyoxy-112,2-tetraphenylnoxy-1,1,2,2-tetraphenyldioxane, i 2 -diphenyloxy, two Shi Xizhuo and so on. Among the above-mentioned reductions, 1,1,2,2-tetraphenylhexa-J, etc., as a preferred example, a hexamethyl-based shale-sintered base 2: burned, U'2'2-fourth Oxy-1>2, dimethyl bismuth sulphate, hydrazine; dioxy], 2 -diindolyl dihydric, 1, U, 2-tetramethoxy: wide; one wide burning, 1, 2 - Dimethoxy-1,1,2,2-tetramethyldiethoxy-1'1,2'2-tetramethyldisane, U-dimethyl 3, U 2 '2-tetraphenyl Ditetraphenyl dioxane and the like. 312XP/Invention Manual (Supplement)/96-07/% 1194^7 20 200808907 Further, as the compound 2, as a compound represented by the formula (2), R? is a group represented by _(CH2)m- Illustrative of bis(trimethoxydecyl)methane, bis(triethoxydecyl)methane, bis(tri-n-propoxydecyl)decane, bis(triisopropoxydecyl)methane, bis ( Tri-n-butoxyalkylalkyl)methane, bis(tris-tert-butoxyalkyl)decane, bis(tris-tert-butoxyalkyl)methane, 1,2-bis(tridecyloxydecyl) Ethane, 1>2-bis(triethoxydecyl)ethane, 1,2-bis(tri-n-propoxydecyl)ethane, hydrazine, 2-bis(triisopropoxydecyl) Ethane, [, 2-bis(tri-n-butoxyoxyalkyl) ethane, 1,2-bis(tris(2-butoxyoxyalkyl)ethane, hydrazine, 2-bis(tris) Ethylene alkyl) ethane, 1-(dimethoxymethyl decyl) decyl (trimethoxy fluorenyl) decane, 1-(diethoxymethyl decyl) 4 (triethyl) Oxonium alkyl) decane, 1-(di-n-propoxy decyl decane ) 4 (tri-n-propoxy oxalate) oxime, 1-(diisopropoxymethyl sulphate)-l-(triisopropoxy decyl) decane, 1- (two) n-Butoxymethyl fluorenyl)-b (tri-n-butoxy decylalkyl)methane, 1 (di-second-butoxymethyl decyl)-1-(tris-2-butoxydecyl) Methane, 1-(di-t-butoxy-decyloxy)-1 -(tris-tert-butoxyalkyl)methane, 1-(dimethoxymethyldecyl)-2-(three曱 矽 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) (tri-n-propoxy-decyloxy) ethane, diisopropoxy fluorenyl ruthenium)-2-(triisopropoxy oxanthene) ethene, i-(di-n-butoxymethyl) Ethyl)-2-(tri-n-butoxymoxy) Ethylene, iodide, second butoxycarbonylalkyl)-2-(tris-2-butoxydecyl)ethane, 1-( Di-tert-butoxymethyl decyl)-2-(tris-tert-butoxy 312XP/invention specification (supplement)/96-07/96119467 21 200808907 Ethane, bis(dimethoxydecyldecylalkyl)decane, bis(diethoxymethyldecyl)decane, bis(di-n-propoxymethyldecyl)methane, bis (di) Propyloxymethyl fluorenyl methane, bis(di-n-butoxymethyl decyl) decane, bis(di-butoxymethyl decyl) decane, bis(di-t-butoxy fluorene) Base alkyl)methane, 1,2-bis(dimethoxymethyldecyl)ethlybdenum, 1,2-bis(diethoxymethyldecyl)ethane,;,2-double (two N-propoxydecylalkyl)ethane, 1,2-bis(diisopropoxymethyldecyl)ethane, 1,2-bis(di-n-butoxymethyldecyl)ethane,丨, 2_bis(di-dibutoxydecylalkyl)ethane, 1,2-bis(di-t-butoxydecylalkyl)ethane, 1,2-bis(trimethoxydecane) Benzo, hydrazine, 2_bis(triethoxydecyl)benzene, 1,2-bis(tri-n-propoxydecyl)benzene, bis(diisopropoxydecyl)benzene, 1 , 2-bis(tri-n-butoxydecyl)benzene, 1'2-bis(tri-second butoxydecane) Benzene, 12-bis(tris-tert-butoxydecyl)benzene, 1,3-bis(trimethoxydecyl)benzene, 13-bis(triethyl & sylylene)benzene, 1,3 - bis (tri-propoxy ketone) benzene, i 3 bis (tri-propoxy ketone) benzene, U-bis (tri-n-butoxy phenylene phthalate) Benzo, 1,3,3,3,butoxylate

Si苯—fi,曱氧基石夕燒基)苯、三乙氧基石夕 烷基）本、L4 —雙（三正丙氧基矽烷基）苯、丨，弘雔 (三第 苯等 η - 丁Ί氧基錢基)苯、U-雙 ‘乳基石夕炫基）苯、u-雙（三第三丁氧基石夕烧基） 該等之中，作為較佳例， 甲烧、雙（三乙氧基钱基切燒基） 沉1，2-雙（三甲氧基矽烷 312ΧΡ/#__«)/96·_6119467 200808907 基）乙烷、1，2-雙（三乙氧基矽烷基）乙烷、1 一（二曱氧基甲 基矽烷基）-1-(三甲氧基矽烷基）曱烷、1一（二乙氧基甲基 矽烷基）-1 -（三乙氧基矽烷基）曱烷、1一（二甲氧基甲基矽 烷基）-2-(三甲氧基矽烷基）乙烷、丨一（二乙氧基曱基矽烷 ‘基）一2一（三乙氧基矽烷基）乙烷、雙（二曱氧基曱基矽烷基） •甲烧、雙（一乙氧基曱基石夕烧基）甲烧、1，2-雙（二甲氧基 甲基矽烷基）乙烷、1，2-雙（二乙氧基甲基矽烷基）乙烷、 1，2-雙（三曱氧基矽烷基）苯、12—雙（三乙氧基矽烷基） ⑩苯、1，3-雙（三曱氧基矽烷基）苯、丨，3 —雙（三乙氧基矽烷 基）本、1，4雙（二甲氧基石夕烧基）苯、1，4—雙（三乙氧基發 烷基）苯等。上述化合物1〜3可使用1種或同時使用2種 以上。 使以化合物1〜2所表示之化合物水解、部分縮合時， 較佳為每1莫耳通式（1)〜（2)中以r2〇—、及所參 示之基，使用0· 1〜100莫耳之水。再者，於本發明中^ _所謂完全水解縮合物係表示縮合物成分中以R2〇—、及 R50-所表示之基100%水解，成為〇H基而完全縮合者。 1 · 2· (B)成分 其次，就（B)成分加以說明。（B)成分為具有以下述通式 ，（3)所表示之構造之聚碳矽烷（以下，稱為「化合物3」）X -成分可與上述（A)成分縮合而形成Si〜〇-Si鍵。」 312XP/發明說明書(補件)/96_〇7/96119467 23 200808907 [化3]Si benzene—fi, decyloxycarbendyl) benzene, triethoxy oxetyl), L4 — bis(tri-n-propoxy decyl) benzene, hydrazine, ruthenium (triphenyl), etc. Ί, -, U, U, ', 乳, u, u, u, u, u, u, u, u, 双, 双, 双Ethoxyl-based mercapto group) 1,2-bis(trimethoxydecane 312ΧΡ/#__«)/96·_6119467 200808907 base) ethane, 1,2-bis(triethoxydecyl)B Alkane, mono-(dimethoxymethylalkyl)-1-(trimethoxydecyl)decane, 1-(diethoxymethyldecyl)-1 -(triethoxydecyl) Decane, 1-(dimethoxymethyldecyl)-2-(trimethoxydecyl)ethane, indole (diethoxydecyldecane'yl)-2-one (triethoxydecane) Ethyl, bis(dimethoxydecyl decyl) • methyl ketone, bis(monoethoxy fluorenyl) methyl, 1,2-bis(dimethoxymethyl decyl) Ethane, 1,2-bis(diethoxymethyldecyl)ethane, 1,2-double (triterpene) Benzyl)benzene, 12-bis(triethoxydecyl) 10 benzene, 1,3-bis(trimethoxyoxyalkyl)benzene, anthracene, 3-bis(triethoxydecyl)benzyl, 1,4 bis (dimethoxy oxalate) benzene, 1,4 bis (triethoxy fluorinyl) benzene, and the like. These compounds 1 to 3 may be used alone or in combination of two or more. When the compound represented by the compound 1 to 2 is hydrolyzed and partially condensed, it is preferably used in the formula (1) to (2) in the range of r 2 〇 - and the indicated group, using 0·1~ 100 moles of water. Further, in the present invention, the term "completely hydrolyzed condensate" means that the condensate component is hydrolyzed by 100% of the groups represented by R2?- and R50-, and becomes a hydrazine H group and is completely condensed. 1 · 2· (B) Component Next, the component (B) will be described. The component (B) is a polycarbane (hereinafter referred to as "compound 3") having a structure represented by the following general formula or (3). The X-component can be condensed with the component (A) to form Si~〇-Si. key. 312XP/Invention Manual (supplement)/96_〇7/96119467 23 200808907 [Chem. 3]

(式中，R8表示自氫原子、鹵素原子、羥基、烷氧基、 醯氧基、磺酸基、曱磺酸基、三氟曱磺酸基、烷基、芳基、 ®烯丙基、以及縮水甘油基所組成群組選擇之基，R9表示自 鹵素原子、羥基、烷氧基、醯氧基、磺酸基、甲磺酸基、 二氟曱磺酸基、烷基、芳基、烯丙基、以及縮水甘油基所 組成群組選擇之基，R1D、R"為相同或不同，表示自鹵素 原子、羥基、烷氧基、醯氧基、磺酸基、曱磺酸基、三氟 甲磺酸基、碳數2〜6之烷基、芳基、烯丙基、以及縮水 甘油基所組成群組選擇之基，]^2〜RH為相同或不同，表 ⑩不取代或非取代之亞曱基、伸烷基、伸烯基、伸炔基、伸 芳基，e、f、g分別表示〇〜1〇,〇〇〇之數，滿足1〇<e+f + g< 10, 000 之條件）。 作為（A)成分與（B)成分之混合比，較佳為相對於（A)成 • ^之完全水解縮合物100重量份，（B)成分為丨〜“⑽重 ’ ，尤其更佳為5〜200重量份，進一步較佳為5〜100 重里伤。於（β)成分未滿1重量份之情況下，有時會於膜 形成後無法表現出充分之耐化學藥品性，另外若超過1 〇 〇 〇 重里份’則有時會無法實現膜之低介電係數化。 312ΧΡ/發明說明書(勝)/96·07/96119467 24 200808907 (B)成分之聚苯乙烯換算重量平均分子量較佳為500〜 10, 000，更佳為600〜5, 000，進一步較佳為600〜3, 000。 若（B)成分之聚苯乙烯換算重量平均分子量超過1 0,000， 則有時會引起與（A)成分之層分離，無法形成均勻之膜。 " 於製造上述膜形成用組成物中所含有之水解縮合物 : 時，係使用化合物3作為（B)成分，於（C)觸媒及（B)成分 之存在下，使（A)成分水解縮合，藉此，不僅可使（A)成分 彼此水解縮合，並且可使（B)成分與來自（A)成分之聚梦氧 ⑩烷進行水解縮合。藉此，可使獲得之水解縮合物具有如下 構造，即’以（B)成分（聚碳秒烧）為核之聚合物嵌入至來 自（A)成分（含有水解基之矽烷單體）之聚矽氧烷之三級結 構内的構造。本發明之絕緣膜形成用組成物含有上述水解 縮合物，藉此，可獲得介電係數更小，機械強度、密接性 及耐化學藥品性非常優異，且無膜中之相分離之絕緣膜。 1. 3. (C)觸媒 Φ 此處，上述水解縮合較佳為於鹼性觸媒、酸性觸媒、或 金屬螯合物觸媒等（C)觸媒之存在下進行。 1. 3. 1.鹼性觸媒 製造上述膜形成用組成物中所含有之水解縮合物時，藉 • 由使用鹼性觸媒作為（C)觸媒，可提高所獲得之水解縮合 - 物之分子構造中存在的分子鏈之分枝度，且進一步增大其 分子量。 藉此，可獲得具有上述構造之水解縮合物。 作為鹼性觸媒，例如可舉出曱醇胺、乙醇胺、丙醇胺、 312XP/發明說明書(補件)/96-07/96119467 25 200808907 丁醇胺、N-甲基甲醇脸、M 7甘 N-丁基甲醇胺、":乙=：基甲醇胺、Μ-丙基甲醇胺、 r 土 ％月女、N-乙基乙醇胺、N-丙基乙 坪妝、JN 丁基乙醉胺、 丙基丙醇胺4丁義而矿 醇私、卜乙基丙醇胺、N- 胺、N而其丁 r· IN—甲基丁醇胺、N-乙基丁醇 取、N-丙基丁醇胺、N— 装 N，N-二乙基曱醇胺、N : : I』-二甲基甲醇胺、 吁妝N，N-一丙基甲醇胺、N N_二 二曱基乙醇胺、„_二乙基乙醇胺，N，心= =督二丁基乙醇胺、二甲基丙醇胺、N，N_ ;二：丙醇胺：N，N'二丙基丙醇胺、N，N-二丁基丙醇胺、 :一甲基丁醇胺、N，N-二乙基丁醇胺、N，N-二丙基丁醇 胺、N，N一二丁基丁醇胺、N-曱基二甲醇胺、N-乙基二甲醇 胺、N-丙基二甲醇胺、n一丁基二甲醇胺、N_?基二乙醇胺、 N—乙基二乙，胺、N-丙基二乙醇胺、N-丁基二乙醇胺、N_ 曱土丙醇胺、N-乙基二丙醇胺、N—丙基二丙醇胺、n_ 丁基二丙醇胺、N—曱基二丁醇胺、卜乙基二丁醇胺、N- 丙基>二丁醇胺、N_丁基二丁醇胺、N_(胺基甲基）甲醇胺、 N (月女基甲基）乙醇胺、N_ (胺基曱基）丙醇胺、(胺基甲 基）丁醇胺、N_(胺基乙基）甲醇胺、N_(胺基乙基）乙醇胺、 N-(胺基乙基）丙醇胺、N_(胺基乙基）丁醇胺、N_(胺基丙 基）甲醇胺、N-(胺基丙基）乙醇胺、N_(胺基丙基）丙醇胺、 N-(胺基丙基）丁醇胺、N_(胺基丁基）甲醇胺、N_(胺基丁 基）乙醇胺、N-(胺基丁基）丙醇胺、N_(胺基丁基）丁醇胺、 甲氧基甲基胺、甲氧基乙基胺、甲氧基丙基胺、甲氧基丁 基胺、乙氧基甲基胺、乙氧基乙基胺、乙氧基丙基胺、乙 312XP/發明說明書(補件)/96-〇7/96119467 26 200808907 氧基丁基胺、丙氧基曱基胺、丙氧基乙基胺、丙氧基丙基 胺、丙氧基丁基胺、丁氧基曱基胺、丁氧基乙基胺、丁氧 基丙基胺、丁氧基丁基胺、曱基胺、乙基胺、丙基胺、丁 基胺、N，N-二曱基胺、N，N-二乙基胺、N，N-二丙基胺、N，N-一丁基胺、二甲基胺、三乙基胺、三丙基胺、三丁基胺、 ：氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫 氧化四丁基銨、四曱基伸乙基二胺、四乙基伸乙基二胺、 四丙基伸乙基二胺、四丁基伸乙基二胺、甲基胺基甲基 •胺、曱基胺基乙基胺、曱基胺基丙基胺、曱基胺基丁基胺、 乙基胺基甲基胺、乙基胺基乙基胺、乙基胺基丙基胺、乙 基胺基丁基胺、丙基胺基甲基胺、丙基胺基乙基胺、丙基 胺基丙基胺、丙基胺基丁基胺、丁基胺基甲基胺、丁基胺 基乙基胺、丁基胺基丙基胺、丁基胺基丁基胺、吡啶、吼 咯、哌讲、吡咯啶、哌啶、甲基吡啶、咮啉、曱基咪啉、 二氮雜雙環辛烷、二氮雜雙環壬烷、二氮雜雙環十一烯、 _氨、氫氧化鈉、氫氧化鉀、氫氧化鋇、氫氧化鈣等。 作為鹼性觸媒，特佳為以下述通式（4)所表示之含氮化 合物（以下亦稱為化合物4)。 (X!X2X3X4)hY······(4) "於上述通式⑷中，^乂2、^4相同或不同，分別表 -示氫原子、碳數1〜20之烷基（較佳為甲基、乙基、丙基、 丁基、己基等）' 羥基烷基（較佳為羥基乙基等）、芳基（較 佳為苯基等）、芳基烷基（較佳為苯基甲基等），γ表示鹵 素原子（較么為氟原子、氯原子、溴原子、碟原子等）、1 312ΧΡ/發明說明書(補件)/96-〇7/96119467 27 200808907 〜4價之陰離子性基（較佳為羥基等），e表示1〜4之整數。 作為化合物4之具體例，作為較佳例，可舉出氫氧化四 曱基錢、氫氧化四乙基錄、氳氧化四正丙基銨、氫氧化四 異丙基銨、氫氧化四正丁基銨、氳氧化四異丁基銨、氫氧 : 化四第三丁基銨、氳氧化四戊基銨、氳氧化四己基銨、氫 - 氧化四庚基銨、氫氧化四辛基銨、氫氧化四壬基銨、氫氧 化四癸基銨、氫氧化四（十一烷基）銨、氫氧化四（十二烷 基）銨、溴化四甲基銨、氯化四甲基銨、溴化四乙基銨、 ⑩氯化四乙基銨、溴化四正丙基銨、氯化四正丙基銨、溴化 四正丁基銨、氯化四正丁基銨、氫氧化六癸基三曱基銨、 溴化正六癸基三甲基銨、氫氧化正十八烷基三曱基銨、溴 化正十八烧基三甲基銨、氯化十六烧基三曱基銨、氯化十 八烷基三甲基銨、氯化节基三甲基銨、氯化二癸基二甲基 銨、氯化二（十八烷基）二曱基銨、氯化三癸基曱基銨、氫 硫酸四丁基銨、溴化三丁基甲基銨、氯化三辛基曱基銨、 _氯化三月桂基甲基銨、氫氧化苄基三甲基銨、溴化苄基三 乙基銨、溴化苄基三丁基銨、溴化苯基三曱基銨、膽鹼等。 該等之中，特佳為氳氧化四曱基銨、氫氧化四乙基銨、氫 氧化四正丙基銨、氫氧化四正丁基銨、溴化四曱基銨、氯 - 化四曱基銨、溴化四乙基銨、氯化四乙基銨、溴化四正丙 . 基銨、氯化四正丙基銨。上述化合物4可使用1種或同時 使用2種以上。 驗性觸媒之使用量，係相對於（A)成分與（B )成分之合計 矽原子（化合物1〜3之總量）1莫耳，通常為0.0001〜1 312XP/發明說明書(補件)/96-07/96119467 28 200808907 莫耳，較佳為0. 001〜〇. 1莫耳。 1· 3· 2·酸性觸媒 可用作⑹觸媒之酸性觸媒，例如可舉出鹽酸、石肖酸、 硫酸、氫氟酸、磷酸、硼酸等無機酸； 乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、 癸酸、草酸、順丁烯二酸、甲基 、 χ 丫丞内一酸、己二酸、癸二酸、 沒食子酸、赂酸、苯六羧酴、允 不、羧馱化生四烯酸、莽草酸、2一 =基己酸、油酸、硬脂酸、亞油酉曼、亞麻油酸、水揚酸、 本:酸、對胺基苯曱酸、對甲苯俩、苯續酸、單氯乙酸、 二^酸：三氯乙酸、三氟乙酸、甲酸、丙二酸、績酸、 丁κ偷 ‘彳豕酸、酒石酸、琥珀酸、反 丁烯一酸、伊康酸、甲基反- # 一放 f 埤一馱、檸康酸、蘋果酸、 戊一 之水解物、順丁烯二酸 之水解物等有機酸，作為更佳之例，可舉：：：二酸酐 等酸性觸媒可使用1種或同時使用2種以上。’、夂酉夂°亥 酸性觸媒之使用量，係相對 矽原早Γ各人札，〇 對於（A)成分與（B)成分之合計 夕原子（化合物1〜3之總量h莫 社甘^ 夫斗通常為0.0001〜1 莫耳’較佳為0·001〜〇1莫耳。 1 · 3 · 3 ·金屬螯合物觸媒 可用作（C )觸媒之金屬螯合物貞 逵口物觸媒，例如可舉出二乙Λ 基•早（乙醯丙酮）鈦、三正氧 牛出一乙虱 異丙虱基•早（乙醯丙酮）鈦、三 一 鈦、二第一丁气茸 氧土 •單（乙醯丙g同） 一弟一丁乳基·早(乙醯丙，)鈦 ’ (乙醯丙酮）鈦、二乙氧基.雔^ # 乐一丁乳基•早 基雙（乙醯丙㈤鈦、二正丙氧基·(wherein R8 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a decyloxy group, a sulfonic acid group, an anthracenesulfonic acid group, a trifluorosulfonium sulfonate group, an alkyl group, an aryl group, an allyl group, And a group selected from the group consisting of glycidyl groups, and R9 represents a halogen atom, a hydroxyl group, an alkoxy group, a decyloxy group, a sulfonic acid group, a methanesulfonic acid group, a difluoroantimonysulfonyl group, an alkyl group, an aryl group, a group selected from the group consisting of allyl groups and glycidyl groups, R1D, R" are the same or different and represent a halogen atom, a hydroxyl group, an alkoxy group, a decyloxy group, a sulfonic acid group, an anthracene sulfonate group, and a third group. a group selected from the group consisting of a fluoromethanesulfonic acid group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group, and a glycidyl group, wherein ^2 to RH are the same or different, and Table 10 is not substituted or non-substituted. Substituted fluorenylene, alkylene, alkenyl, alkynyl, and aryl groups, and e, f, and g represent 〇~1〇, respectively, and satisfy the number of 〇<e+f + g<; 10, 000 conditions). The mixing ratio of the component (A) and the component (B) is preferably 100 parts by weight based on the total hydrolyzed condensate of (A), and the component (B) is 丨~"(10) heavy', particularly preferably 5 to 200 parts by weight, more preferably 5 to 100 parts by weight. When the (β) component is less than 1 part by weight, sufficient chemical resistance may not be exhibited after film formation, and if it exceeds 1 〇〇〇重份', sometimes the low dielectric constant of the film may not be achieved. 312ΧΡ/Invention Manual (Win)/96·07/96119467 24 200808907 The polystyrene-equivalent weight average molecular weight of the component (B) is preferably It is 500 to 10,000, more preferably 600 to 5,000, further preferably 600 to 3,000. If the polystyrene-equivalent weight average molecular weight of the component (B) exceeds 10,000, it sometimes causes ( A) The layer of the component is separated, and a uniform film cannot be formed. " When the hydrolysis-condensation product contained in the film-forming composition is produced: Compound 3 is used as the component (B), and (C) catalyst and In the presence of the component (B), the component (A) is hydrolyzed and condensed, whereby not only (A) can be formed. Hydrolytically condensed with each other, and the component (B) can be hydrolytically condensed with the polyoxyloxyl from the component (A). Thereby, the obtained hydrolysis condensate can have the following structure, that is, the component (B) Carbon calcination is a structure in which a polymer of a core is embedded in a tertiary structure of a polyoxyalkylene derived from a component (a hydrocarbyl group containing a hydrolyzable group). The composition for forming an insulating film of the present invention contains the above hydrolysis. By using the condensate, an insulating film having a smaller dielectric constant, excellent mechanical strength, adhesion, and chemical resistance, and no phase separation in the film can be obtained. 1. 3. (C) Catalyst Φ Here The hydrolysis condensation is preferably carried out in the presence of a (C) catalyst such as a basic catalyst, an acid catalyst, or a metal chelate catalyst. 1. 3. 1. Basic catalyst production for the above film formation In the case of the hydrolysis condensate contained in the composition, the use of the alkaline catalyst as the (C) catalyst can increase the branching degree of the molecular chain existing in the molecular structure of the obtained hydrolysis condensation product, and further Increasing the molecular weight thereof, whereby water having the above configuration can be obtained The condensate. Examples of the basic catalyst include decylamine, ethanolamine, propanolamine, 312XP/invention specification (supplement)/96-07/96119467 25 200808907 butanolamine, N-methylmethanol face, M 7 G-N-butylmethanolamine, ": B =: benzylamine, hydrazine-propylmethanolamine, r soil % month female, N-ethylethanolamine, N-propyl propyl makeup, JN butyl Ethanol, propylpropanolamine 4 butyl and oleyl alcohol, acetopropanolamine, N-amine, N and its butyl r-IN-methylbutanolamine, N-ethylbutanol, N- Propyl butanolamine, N-loaded N,N-diethyl sterolamine, N: : I』-dimethylmethanolamine, N, N-monopropylmethanolamine, N N_dioxene Ethanolamine, „_diethylethanolamine, N, heart = = dibutylethanolamine, dimethylpropanolamine, N, N_; di: propanolamine: N, N' dipropylpropanolamine, N , N-Dibutylpropanolamine, :Methylbutanolamine, N,N-diethylbutanolamine, N,N-dipropylbutanolamine, N,N-dibutylbutanolamine , N-decyl dimethanolamine, N-ethyl dimethanolamine, N-propyl dimethanolamine, n-butyl dimethanolamine, N-? diethanolamine, N Ethyldiethylamine, amine, N-propyldiethanolamine, N-butyldiethanolamine, N-alumina, N-ethyldipropanolamine, N-propyldipropanolamine, n-butyl Propylamine, N-decyldibutanolamine, ethylidene dibutanolamine, N-propyl>dibutanolamine, N-butylbutanolamine, N-(aminomethyl)methanolamine, N (Monthyl methyl)ethanolamine, N_(aminomercapto)propanolamine, (aminomethyl)butanolamine, N_(aminoethyl)methanolamine, N_(aminoethyl)ethanolamine, N -(Aminoethyl)propanolamine, N_(Aminoethyl)butanolamine, N_(Aminopropyl)methanolamine, N-(Aminopropyl)ethanolamine, N_(Aminopropyl)propyl Alcoholamine, N-(aminopropyl)butanolamine, N-(aminobutyl)methanolamine, N-(aminobutyl)ethanolamine, N-(aminobutyl)propanolamine, N_(amine group Butyl)butanolamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, B Oxypropylamine, B 312XP / invention specification (supplement) / 96-〇7/96119467 26 200808907 oxybutylamine, propoxydecylamine Propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxydecylamine, butoxyethylamine, butoxypropylamine, butoxybutylamine, hydrazine Amine, ethylamine, propylamine, butylamine, N,N-didecylamine, N,N-diethylamine, N,N-dipropylamine, N,N-butylamine , dimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, Tetramethyl stilbene ethyl diamine, tetraethyl ethylene diamine, tetrapropyl ethylene diamine, tetrabutyl ethylene diamine, methyl amino methyl amine, mercapto aminoethyl amine, hydrazine Aminopropylamine, mercaptoaminobutylamine, ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, ethylaminobutylamine, propylamine Methylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine, butylaminopropyl Amine, butylaminobutylamine, pyridine, pyrrole, piperidin, pyrrolidine, piperidine, Pyridine, porphyrin, decyl morpholine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, _ ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide Wait. The basic catalyst is particularly preferably a nitrogen-containing compound represented by the following formula (4) (hereinafter also referred to as compound 4). (X!X2X3X4)hY······(4) " In the above formula (4), ^2, ^4 are the same or different, and each represents a hydrogen atom and an alkyl group having 1 to 20 carbon atoms ( Preferred is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or the like) a hydroxyalkyl group (preferably a hydroxyethyl group or the like), an aryl group (preferably a phenyl group or the like), or an arylalkyl group (preferably). Is a phenylmethyl group, etc., γ represents a halogen atom (relatively a fluorine atom, a chlorine atom, a bromine atom, a dish atom, etc.), 1 312 ΧΡ / invention specification (supplement) / 96-〇7/96119467 27 200808907 ～4 An anionic group of a valence (preferably a hydroxyl group or the like), and e represents an integer of 1 to 4. Specific examples of the compound 4 include, as a preferred example, tetradecyl hydroxide, tetraethyl hydroxide, tetra-n-propylammonium oxide, tetraisopropylammonium hydroxide, and tetra-n-butyl hydroxide. Ammonium, ruthenium tetraisobutylammonium, hydrogen and oxygen: tetrabutylammonium hydride, tetraamylammonium oxyhydroxide, tetrahexylammonium hydride, hydrogen tetrahydroheptyl ammonium oxide, tetraoctyl ammonium hydroxide, Tetramethylammonium hydroxide, tetradecylammonium hydroxide, tetrakis(undecyl)ammonium hydroxide, tetrakis(dodecyl)ammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, Tetraethylammonium bromide, tetraethylammonium chloride, tetra-n-propylammonium bromide, tetra-n-propylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, hydrogen hydroxide Mercaptotrimethylammonium bromide, n-hexyltrimethylammonium bromide, n-octadecyltrimethylammonium hydroxide, n-octadecyltrimethylammonium bromide, hexadecanoyl tridecyl chloride Ammonium, octadecyltrimethylammonium chloride, benzyltrimethylammonium chloride, dimercaptodimethylammonium chloride, dioctadecylphosphonium chloride, triterpene chloride Base amide, hydrogen sulphur Tetrabutylammonium, tributylmethylammonium bromide, trioctyldecylammonium chloride, trilaurylmethylammonium chloride, benzyltrimethylammonium hydroxide, benzyltriethylammonium bromide, bromine Benzyltributylammonium bromide, phenyltriammonium bromide, choline, and the like. Among these, particularly preferred are ruthenium tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetradecylammonium bromide, and tetrachloroammonium chloride. Ammonium, tetraethylammonium bromide, tetraethylammonium chloride, tetra-n-propylammonium bromide, tetra-n-propylammonium chloride. The above compound 4 may be used alone or in combination of two or more. The amount of the test catalyst used is 1 mole of the atom (the total amount of the compound 1 to 3) relative to the total of the components (A) and (B), usually 0.0001 to 1 312 XP / invention specification (supplement) /96-07/96119467 28 200808907 Moor, preferably 0. 001~〇. 1 mole. 1·3· 2·2. The acidic catalyst can be used as the acidic catalyst of (6) catalyst, and examples thereof include inorganic acids such as hydrochloric acid, succinic acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and boric acid; acetic acid, propionic acid, and butyric acid; , valeric acid, caproic acid, heptanoic acid, caprylic acid, citric acid, citric acid, oxalic acid, maleic acid, methyl, guanidine, adipic acid, azelaic acid, gallic acid, Acid, benzene hexacarboxylate, ban, carboxyformated retinoic acid, shikimic acid, phthalic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, Acid, p-aminobenzoic acid, p-toluene, benzoic acid, monochloroacetic acid, diacid: trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, acid, Ding ke, 'tannic acid, Tartaric acid, succinic acid, thiobutyric acid, itaconic acid, methyl anti-# one put f 埤 驮, citraconic acid, malic acid, hydrolysate of pentyl, hydrolyzate of maleic acid, etc. As a more preferable example, an acid catalyst such as a dianhydride may be used alone or in combination of two or more. ', 夂酉夂 ° Hai's acid catalyst usage is based on the combination of (A) and (B) ingredients (the total amount of compounds 1 to 3) The glycerin is usually 0.0001 to 1 mol. It is preferably 0·001 to 〇1 mol. 1 · 3 · 3 · The metal chelate catalyst can be used as the metal chelate of the (C) catalyst. The mouthwash catalyst may, for example, be diethyl hydrazide, early (acetyl acetonide) titanium, trioxane oxol, ethyl isopropyl hydrazide, early (acetyl acetonide) titanium, tri-titanium, and second一丁气茸氧土•单(乙醯丙g同) 一弟一丁乳基·早(乙醯丙,)钛' (乙醯酮) Titanium, diethoxy.雔^ #乐一丁乳Base · early base double (acetylidene (five) titanium, di-n-propoxy group

312XP/發明說明書(補件)/96-07/96119467 JQ 200808907 雙（乙醯丙酮）鈦、二異丙氧基•雙（乙醯丙酮）鈦、二正丁 氧基•雙（乙醯丙酮）鈦、二第二丁氧基•雙（乙醯丙酮） 鈦、二第三丁氧基•雙（乙醯丙酮）鈦、單乙氧基•三（乙 醯丙酮）鈦、單正丙氧基•三（乙醯丙酮）鈦、單異丙氧基· •三（乙醯丙酮）鈦、單正丁氧基•三（乙醯丙酮）鈦、單第二 ：丁氧基•三（乙醯丙酮）鈦、單第三丁氧基•三（乙醯丙酮） 鈦、四（乙醯丙酮）鈦、三乙氧基•單（乙基乙醯乙酸）鈦、 三正丙氧基•單（乙基乙醯乙酸）鈦、三異丙氧基•單（乙 馨基乙醯乙酸）鈦、三正丁氧基•單（乙基乙醯乙酸）鈦、三 第二丁氧基•單（乙基乙醯乙酸）鈦、三第三丁氧基•單（乙 基乙醯乙酸）鈦、二乙氧基•雙（乙基乙醯乙酸）鈦、二正 丙氧基•雙（乙基乙醯乙酸）鈦、二異丙氧基•雙（乙基乙 醯乙酸）鈦、二正丁氧基•雙（乙基乙醯乙酸）鈦、二第二 丁氧基•雙（乙基乙醯乙酸）鈦、二第三丁氧基•雙（乙基 乙醯乙酸）鈦、單乙氧基•三（乙基乙酿乙酸）鈦、單正丙 籲氧基•三（乙基乙醯乙酸）鈦、單異丙氧基•三（乙基乙醯 乙酸）鈦、單正丁氧基•三（乙基乙酿乙酸）鈦、單第二丁 氧基•三（乙基乙醯乙酸）鈦、單第三丁氧基•三（乙基乙 醯乙酸）鈦、四（乙基乙醯乙酸）鈦、單（乙醯丙酮）三（乙基 •乙醯乙酸）鈦、雙（乙醯丙酮）雙（乙基乙醯乙酸）鈦、三（乙 -醯丙酮）單（乙基乙醯乙酸）鈦等鈦螯合物化合物； 三乙氧基•單（乙醢丙酮）锆、三正丙氧基•單（乙醯丙 酮）锆、三異丙氧基•單（乙醯丙酮）錯、三正丁氧基•單（乙 醯丙酮）鍅、三第二丁氧基•單（乙醯丙酮）锆、三第三 312XP/發明說明書(補件)/96-07/96119467 30 200808907 氧基•單（乙醯丙酮）錯、- -P ^ ^ . 一乙乳基•雙（乙醯丙酮）钞、一 正丙乳基·雙(乙醯丙酮)錯、吼、- 錯、二正丁氧某•雔&妒—異丙虱基•雙（乙醯丙酉同） 土 又（乙fe丙酉同）錯、第—]負其德广 醯丙酮)錯、二第 丁减·雙(乙 一, 乐一丁虱基•雙（乙醯丙酮）鍅、單乙氧其· —(乙丙酮）錯、單正丙氧—土 _ 基二（乙酏丙酮）鍅、單異丙 乳I 二（乙丙酉同）錯、罩 早丁乳基•二（乙醯丙酮）锆、 早弟一丁乳基•三（乙酸丙酮）錯、單第三丁氧基·312XP/Invention Manual (supplement)/96-07/96119467 JQ 200808907 Bis(acetonitrile) titanium, diisopropoxy bis(acetonitrile) titanium, di-n-butoxy bis (acetamidine) Titanium, di-butoxide, bis(acetamidine) titanium, di-t-butoxy-bis(acetonitrile) titanium, monoethoxy-3 (acetonitrile) titanium, mono-n-propoxy • Tris(acetonitrile) titanium, monoisopropoxy • tris(acetonitrile) titanium, mono-n-butoxy•tris(acetonitrile) titanium, single second: butoxy•three (acetamidine) Acetone) Titanium, mono-tert-butoxy-tris(acetonitrile) Titanium, tetrakis(acetonitrile)titanium, triethoxyl-mono(ethylacetamidineacetic acid) titanium, tri-n-propoxy-single (single) Ethylacetamidineacetic acid) Titanium, triisopropoxy oxy-mono(ethylacetic acid) titanium, tri-n-butoxy-single (ethyl acetoacetate) titanium, three second butoxy-single ( Ethylacetamidineacetic acid) Titanium, tri-tert-butoxy-mono(ethylacetamidineacetic acid) titanium, diethoxy bis(ethylethanoacetic acid) titanium, di-n-propoxy-bis (ethyl) Acetylacetate) titanium, Isopropoxy bis(ethylacetamidineacetic acid) titanium, di-n-butoxy bis (ethyl acetonitrile) titanium, two second butoxy bis (ethyl acetonitrile) titanium, two Tributyloxy•bis(ethylacetamidineacetic acid) titanium, monoethoxy-3 (ethyl ethyl acetate) titanium, mono-n-propenyloxy-tris(ethylacetamidineacetic acid) titanium, monoisopropyl Oxyl-tris(ethylacetamidineacetic acid) titanium, mono-n-butoxy-tris(ethylethanoacetic acid) titanium, single second butoxy-tris(ethylethanoacetic acid) titanium, single third Oxyl-tris(ethylacetamidineacetic acid) titanium, tetrakis(ethylacetamidineacetic acid) titanium, mono(acetamidineacetone) tris(ethyl•acetamidineacetic acid) titanium, bis(acetamidineacetone) bis(ethyl Acetylacetate) Titanium chelate compound such as titanium, tris(ethyl-fluoreneacetone) mono(ethylacetamidineacetic acid) titanium; triethoxyl mono(acetonitrile)zirconium, tri-n-propoxyl Ethyl acetonide) zirconium, triisopropoxy oxy-mono(acetamidine acetonide), tri-n-butoxy-single (acetyl acetonide) oxime, three second butoxy-single (acetyl acetonide) zirconium, three Third 312XP / hair Instruction manual (supplement)/96-07/96119467 30 200808907 Oxygen • Single (acetamidine) wrong, - -P ^ ^ . One ethyl lactyl • double (acetamidine) banknote, one n-propyl lactate · double (acetamidine) wrong, 吼, - 错, 二正丁氧, 雔 amp amp 虱 虱 虱 双 双 双 双 双 双 双 双 双 双 双 双 双 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 土 ] Negative 醯 醯 醯 醯 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) 2 (acetamidine) hydrazine, monoisopropyl acrylate I bis (ethylene propylene acrylate) wrong, hood early butyl ketone • bis (acetyl acetonide) zirconium, early butyl butyl ketone • tris (acetic acid acetone) wrong, Single third butoxy

==同）錯、四（乙醯丙酮）結、三乙氧基•單（乙基乙酿乙 二正丙氧基•單（乙基乙醯乙酸）锆、三異丙氧基· 早^ ^乙酉^乙酸）錯、二正丁氧基•單（乙基乙醯乙酸） ，一第一 丁氧基•單（乙基乙醯乙酸）鍅、三第三丁氧基· 單（乙基乙乙酸）錯、二乙氧基•雙（乙基乙酿乙酸）錐、 一正丙氧基•雙（乙基乙醯乙酸）锆、二異丙氧基•雙（乙 基乙醯乙酸）鍅、二正丁氧基•雙（乙基乙醯乙酸）銼、二==同), wrong, tetrakis (acetonitrile), triethoxy, mono (ethyl ethyl bromide), zirconium monoethyl ethoxide, triisopropoxy, early ^ ^ 酉 酉 ^ acetic acid) wrong, di-n-butoxy • mono (ethyl acetonitrile), a first butoxy • mono (ethyl acetonitrile) hydrazine, three third butoxy · mono (ethyl Acetic acid) s, diethoxy bis (ethyl ethyl styrene) cone, mono-n-propoxy bis (ethyl acetonitrile) zirconium, diisopropoxy bis (ethyl acetonitrile)鍅, di-n-butoxy bis (ethyl acetonitrile) hydrazine, two

第二丁氧基•雙（乙基乙醯乙酸）锆、二第三丁氧基•雙（乙 基乙醯乙酸）鍅、單乙氧基•三（乙基乙醯乙酸）锆、單正 丙氧基•二（乙基乙醯乙酸）鍅、單異丙氧基•三（乙基乙 酿乙酸）鍅、單正丁氧基•三（乙基乙醯乙酸）锆、單第二 丁氧基•三（乙基乙醯乙酸）鍅、單第三丁氧基•三（乙基 乙醯乙酸）鍅、四（乙基乙醯乙酸）鍅、單（乙醯丙酮）三（乙 基乙酸乙酸）錘、雙（乙醯丙酮）雙（乙基乙醯乙酸）锆、三 (乙醯丙酮）單（乙基乙醯乙酸）錘等錘螯合物化合物； 三（乙醯丙酮）鋁、三（乙基乙醯乙酸）鋁等鋁螯合物化合 物； 31 312XP/發明說明書(補件)/96-07/96119467 200808907 Γ二可Μ舉出鈦或銘之聲合物，特佳可舉出鈦之聲合 物名荨孟屬螯合物觸媒可使们種或同時使 J屬螯合物觸媒之使用量，係相對於(A)成分與(二上分 之^十:夕原子（化合物1〜3之總量）1莫耳，通常為〇 ooi 〜Ϊ莫耳，較佳為〇· 〇〇1〜〇· 1莫耳。 1 · 4 ·知*疋水解縮合物之製造方法 如上所述’特定水解縮合物可藉由使上 述（Β)成分水解縮合而獲得。 ）成刀與上 此處，可於使⑴成分及⑻成分溶解於有機溶媒之狀能 二=棒於此情況下可使用之有機溶媒，例= Ζ舉出甲醇、乙醇、正丙醇、異丙醇、正丁醇、卜 第二丁醇、第三丁醇等醇系溶媒；乙二醇、U-丙二醇、 1，3-丁二醇、2’4_戊二醇、2_甲基_2,4—戊二醇、2 二醇、2’4-庚二醇、2_乙基]，3_己二醇、二乙二醇、二 丙二醇、三乙二醇、三丙二醇等多元醇系溶媒；乙二醇^ 甲齡、乙二醇單乙縫、乙二醇單丙醚、乙二醇單丁鱗等多 兀醇部分醚系溶媒；乙醚、異丙醚、正丁醚、正己醚、 乙^己醚、二氧戊環、4_甲基二氧戊環、二〇号烧、二甲基 二哼烷、乙二醇單曱醚、乙二醇二甲醚、乙二醇單乙醚: 乙二醇二乙喊㈣系溶媒；丙酉同、甲基乙基_、甲基正丙 基酮、甲基正丁基酮、二乙基酮、曱基]一丁基酮、曱基 正戊基酮、乙基正丁基酮、f基正己基_、二異丁基嗣土、 三曱基壬嗣、環戊酮、環己酮、環庚_、環辛酮、2_己酮、 曱基環己目、2’4_戊二酉同、丙酮基丙嗣、二丙嗣醇、等酮 312XP/發明說明書(補件)/96-07/96119467 32 200808907 系溶媒。 有機溶媒中之（A)成分及B)成分之合計量之濃度為1〜 30重量％。 。私解、、很σ蚪之反應溫度為0〜loot：，較佳為20〜80 夂反應日守間為3〇〜1 〇〇〇分鐘，較佳為3〇〜18〇分鐘。 α成77之从、加順序並無特別限定，例如較好的是於將驗 =觸媒^加於有機溶媒之液中，逐次添加分別將（Α)成分 及成为添加於有機溶媒者。 :獲得之特定水解縮合物之聚苯乙稀換算重量 2〇0$〇t〇T^ 2,000 ^ ，000，進—步較佳為2,0〇〇〜15〇 〇〇 合物之聚苯乙烯拖瞀舌旦τ 右知疋水％縮 獲得目的之介電‘，==分子量未滿i’500’則無法 易生成異物，而且存j —方面1超過啊咖，則容 1.5.有機溶媒 -膜之面内均勾性惡劣之情況。 作為上述絕緣膜形成 舉出自醇系溶媒、網ί、;：成：中所含有之有機溶媒，可 系溶媒、脂肪族煙系媒:：胺系_、醚系溶媒、顆 的群組選擇之至少！種Υ *日H容媒以及含鹵素溶媒 作為醇系溶媒，可舉出 正丁醇、異丁醇、第二丁出醇甲f、正丙醇、異内醇、 "基丁醇、第二戊醇、第三弟戊二醇丁正戍醇、異戊醇、 醇、2-甲基戊醇、第 以基丁醇、正已 庚醇、正辛醇、2—知2-乙基丁醇、第二庚醇、3、 土已醇、第二辛醇、正壬醇、 312Xp/發明說明書(補件)/96-07/96119467 33 200808907 :甲基+庚醇、正癸醇、第二(十一)醇、三甲基壬醇、 m 、第二（十七）醇、糠醇、苯盼、環己醇、甲 醇系溶媒； 甲基展己醇、苯甲醇、二丙酉同醇等單 醇 1，2~ 丙二醇、1，3-丁二醇、2 4-戊-醇、？ 曱基_2,4~戊-萨9 ς 口 哔ζ’4戍一知、2_ 戍一知、2, 5-己二酵、2, 4-庚二醇、2-乙基 一.一乙二醇、二丙二醇、：__ 一 兀醇系溶媒； 哔寻夕 單t醇單甲越、乙二醇單乙_、乙二醇單㈣、乙二醇 喊、_乙二醇單㈣、乙二醇單㈣、乙二醇單2 一乙 二-乙—乙二醇單甲驗、二乙二醇單乙醚、二乙二醇單 :秘-乙二醇單丁醚、二乙 丙二醇單乙8申 并早T _、 單甲峻ΙΓ二早丙趟、丙二醇單丁驗、二丙二醇 鱗系溶媒.箄—醇Γ乙醚、二丙二醇單㈣等多元醇部分 以上。、該等醇系溶媒可使用1種或同時使用2種 作為_系溶媒，可舉出丙 酮、甲基正丁基_、二乙基綱、甲==甲基正丙基 基酮、乙基正丁基，、甲基正己基；:二：丁二基正戊 基壬酮、環戊酉同、環己酉同、環庚啊 西同土己同、二甲 基環己酮、2 4-A - w工 ^§Π 2一己酮、甲 小菌香鋼等酮季料^等=丙酉同、二丙_、苯乙酉同、 用2種以上 相糸溶媒可使用1種或同時使 作為酿胺系溶媒，可舉出二甲基咪唾琳酉同、N-甲 312XP/發明說明書(補件)/96-07/96119467 34 200808907Second butoxy bis(ethylacetamidineacetic acid) zirconium, di-t-butoxy-bis(ethylacetamidineacetic acid) ruthenium, monoethoxyl-tris(ethylacetamidineacetic acid) zirconium, single positive Propyloxybis(ethylacetamidineacetic acid) hydrazine, monoisopropoxy oxy-tris(ethylethanoacetic acid) ruthenium, mono-n-butoxy-tris(ethylethanoacetic acid) zirconium, single second Oxyl-tris(ethylacetamidineacetic acid) hydrazine, mono-tert-butoxy-tris(ethylethanoacetic acid) hydrazine, tetrakis(ethylacetamidineacetic acid) hydrazine, mono(acetamidineacetone)tris(ethyl) Hammer chelate compound such as acetic acid acetic acid) hammer, bis(acetonitrile) bis(ethylacetamidineacetic acid) zirconium, tris(acetylacetone) mono(ethylacetamethyleneacetic acid) hammer; tris(acetonitrile)aluminum Aluminum chelate compound such as tris(ethylacetamethyleneacetate)aluminum; 31 312XP/invention specification (supplement)/96-07/96119467 200808907 Γ二Μ Μ 钛 钛 或 或 或 或 或 或 或 或 或The name of the titanium sulphate, the genus chelating agent, can be used or the amount of the J chelate catalyst can be used in relation to the (A) component and Atomic atom The total amount of the substances 1 to 3) 1 mol, usually 〇ooi~Ϊ莫耳, preferably 〇· 〇〇1~〇·1 mol. 1 · 4 · know * 疋 hydrolysis condensate manufacturing method as above The 'specific hydrolysis condensate can be obtained by hydrolyzing and condensing the above (Β) component.) The above-mentioned sizing and the above-mentioned component can dissolve the component (1) and the component (8) in the form of an organic solvent. An organic solvent that can be used, for example, an alcohol-based solvent such as methanol, ethanol, n-propanol, isopropanol, n-butanol, dibutanol or tert-butanol; ethylene glycol, U-propylene glycol , 1,3-butanediol, 2'4-pentanediol, 2-methyl-2,4-pentanediol, 2diol, 2'4-heptanediol, 2-ethylidene, 3_ Polyol-based solvent such as hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol or tripropylene glycol; ethylene glycol; methyl age, ethylene glycol monoethyl sulphide, ethylene glycol monopropyl ether, ethylene glycol single Part of ethers of polyterpene alcohol such as butyl scale; ether, diisopropyl ether, n-butyl ether, n-hexyl ether, hexyl ether, dioxolane, 4-methyldioxolane, bismuth, dimethyl Dioxane, ethylene glycol monoterpene ether, ethylene glycol Methyl Ether, Ethylene Glycol Monoethyl Ether: Ethylene Glycol and Ethyl (4) Solvent; Propionate, Methyl Ethyl, Methyl N-propyl Ketone, Methyl-N-Butyl Ketone, Diethyl Ketone, Mercapto ] monobutyl ketone, decyl n-pentyl ketone, ethyl n-butyl ketone, f-based n-hexyl _, diisobutyl silicate, trimethyl hydrazine, cyclopentanone, cyclohexanone, cycloheptane _, Cyclooctanone, 2-hexanone, fluorenylcycloheximide, 2'4-pentadienyl, acetonylpropionate, dipropanol, ketone 312XP/invention specification (supplement)/96-07/96119467 32 200808907 is a solvent. The concentration of the total amount of the component (A) and the component B) in the organic solvent is from 1 to 30% by weight. . The private solution, the reaction temperature of σ蚪 is 0~loot:, preferably 20~80 夂, the reaction time is 3〇~1 〇〇〇 minutes, preferably 3〇~18〇 minutes. The order of addition and the addition of α to 77 is not particularly limited. For example, it is preferred to add the test agent to the liquid of the organic solvent, and to add the (Α) component and the organic solvent to each other. : Polyphenylene oxide obtained by the specific hydrolysis condensate has a weight of 2〇0$〇t〇T^ 2,000 ^ ,000, and preferably is a polystyrene of 2,0〇〇15 Dragging the tongue τ 右 knows that the water is reduced to obtain the purpose of the dielectric ', = = molecular weight is less than i'500' can not easily generate foreign matter, and save j - aspect 1 exceeds ah, then 1.5. organic solvent - The surface of the membrane is inferior in hooking. The formation of the above-mentioned insulating film is exemplified by an organic solvent contained in an alcohol-based solvent, a network, a solvent, or an aliphatic-based medium: an amine-based, an ether-based solvent, and a group. At least! Υ 日 日 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H Dipentanol, third pentanediol butyl sterol, isoamyl alcohol, alcohol, 2-methylpentanol, butylbutanol, n-heptanol, n-octanol, 2-known 2-ethyl Butanol, second heptanol, 3, hexanol, second octanol, n-decyl alcohol, 312Xp/invention specification (supplement)/96-07/96119467 33 200808907: methyl + heptanol, n-nonanol, Second (11) alcohol, trimethyl decyl alcohol, m, second (seventeen) alcohol, decyl alcohol, benzene, cyclohexanol, methanol solvent; methyl hexanol, benzyl alcohol, dipropylene Monools such as alcohol 1,2~ propanediol, 1,3-butanediol, 2 4-pentanol, ?曱基_2,4~戊-萨9 ς 口哔ζ'4戍一知, 2_ 戍一知, 2, 5-hexane diprotein, 2, 4-heptanediol, 2-ethyl one. Glycol, dipropylene glycol,: __ sterol-based solvent; 哔 单 单 mono t-alcohol monomethyl, ethylene glycol monoethyl _, ethylene glycol single (four), ethylene glycol shout, _ ethylene glycol single (four), B Glycol mono (tetra), ethylene glycol mono 2 - ethylene di-ethylene glycol monomethyl test, diethylene glycol monoethyl ether, diethylene glycol mono: secret - ethylene glycol monobutyl ether, diethylene glycol monoethylene 8 Shen and early T _, single 甲 ΙΓ ΙΓ ΙΓ ΙΓ 趟 趟 趟 趟 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二These alcohol-based solvents may be used alone or in combination as two types of solvents, and examples thereof include acetone, methyl n-butyl group, diethyl group, methyl group = methyl propyl ketone, and ethyl group. n-Butyl, methyl-n-hexyl;: 2: butyldiyl-n-pentyl fluorenone, cyclopentanyl, cyclohexyl amide, cycloglycol, hexamidine, dimethylcyclohexanone, 2 4 -A - w work ^§Π 2 ketone, a small bacterium, etc., such as ketone quaternary material ^, etc. = propyl hydrazine, dipropyl _, phenethyl hydrazine, use two or more kinds of hydrazine solvent, one type or both Examples of the brewing amine-based solvent include dimethyl hydrazine, N-A 312XP/invention specification (supplement)/96-07/96119467 34 200808907

二严甲醯胺、Μ—二乙基甲醯胺、乙 N—甲美,卜二1胺、N，N一二甲基乙醯胺，N一甲基丙醯胺 種二疋酮等含氮系溶媒。該等醯胺系溶媒可使用 種或同時使用2種以上。严 醯 醯 Μ Μ 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二A nitrogen-based solvent. These amide-based solvents may be used singly or in combination of two or more kinds.

—作為鍵溶媒系，可舉出乙醚、異丙醚、正丁_、正己醚、 2 ”己醚、二氧戊環、4一甲基二氧戊環、二噚烷、二曱 基二哼烷、乙二醇單甲醚、乙二醇二曱醚、乙二醇單乙醚、 乙一醇一乙瞇、乙二醇單正丁醚、乙二醇單正己醚、乙二 醇單、乙二醇| 2—乙基丁醚、乙二醇二丁鍵、二乙 一酉予單甲醚、二乙二醇二曱醚、二乙二醇單乙醚、二乙二 酉予一乙醚、二乙二醇單正丁醚、二乙二醇二正丁醚、二乙 一醇單正己醚、乙氧基三甘醇、四乙二醇二正丁醚、丙二 酉予單曱醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、 二丙二醇單甲醚、二丙二醇單乙醚、三丙二醇單甲醚、四 氫呋喃、2-甲基四氫呋喃、二苯醚、苯甲醚等醚系溶媒。 該等醚系溶媒可使用1種或同時使用2種以上。 作為酯系溶媒，可舉出碳酸二乙酯、碳酸丙二酯、乙酸 甲酯、乙酸乙酯、丨—丁内酯、^ —戊内酯、乙酸正丙酯、 乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸第二丁酯、 乙酸正戊酯、乙酸第二戊酯、乙酸3-甲氧基丁酯、乙酸 曱基戊酯、乙酸2-乙基丁酯、乙酸2-乙基己酯、乙酸苄 酯、乙酸環己酯、乙酸甲基環己基、乙酸正壬酯、乙醯乙 酸甲酯、乙醯乙酸乙酯、乙二醇單甲醚乙酸酯、乙二醇單 乙峻乙酸酯、二乙二醇單曱醚乙酸酯、二乙二醇單乙醚乙 312ΧΡ/發明說明書(補件)/96-07/96119467 35 200808907 酸酯、二乙二醇單正丁醚乙酸酯、丙二醇單甲醚乙酸酯、 丙一醇單乙it乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁 喊乙酸酯、二丙二醇單甲醚乙酸酯、二丙二醇單乙醚乙酸 酉曰、乙二醇二乙酸酯、甲氧基三乙二醇乙酸酯、丙酸乙酯、 丙酸正丁醋、丙酸異戊酯、草酸二乙酯、草酸二正丁酯、 礼酸曱酯、乳酸乙酯、乳酸正丁酯、乳酸正戊酯、丙二酸 一乙自曰、鄰苯二甲酸二甲酯、鄰苯二曱酸二乙酯等酯系溶 媒。忒等酯系溶媒可使用丨種或同時使用2種以上。 作為脂肪族烴系溶媒，可舉出正戊烧、異戊烧、正己烧、 異己烷、正庚烷、異庚烷、2, 2, 4-三甲基戊烷、正辛烷、 異辛烧、壞己烧、甲基環己烧等脂肪族煙系溶媒。該等脂 肪族煙系溶媒可使用！種或同時使用2種以上。 作為方香族烴系溶媒，可列舉苯 甲苯、乙基苯、二甲、田I ^ ^ 丫本均二 二乙基苯〜苯本_二基乙基苯、正丙苯、異丙苯、 菩夭- 土 —乙基笨、二異丙苯、正戊基萃等 方曰無烴糸溶媒。該等芳香族 、^ ^ 、 使用2種以上。作為含㈣^系/合媒可使用1種或同時 〆尸 局_素洛媒，可列舉二氯曱拉、备分 氟氣碳化物、氯苯、-負！ 、 虱仿、 ^ 一虱本、等含鹵素溶媒。 於本發明中，期望使用沸點 為溶劑種類，較俨# i w x 之有機溶媒，作 貝車“土係醇糸溶劑、酮系溶 了 =係同時使用該等之1種或2種以上，進 5亥#有機溶媒既可為與牿 用者相同者，亦可於特定水解縮:物縮：物之合成中所使 置換為預期之有機溶媒。 V 〇之&咸結束後將溶劑 咖/發明說明書(補件)/9_6119467 36 200808907 曰❶上述臈形成用組成物之總固形分濃度較佳為2〜30重 量％、’可視使用目的進行適當調整。藉由使上述膜形成用 組成物之總固形分濃度為2〜30重量％，可使塗膜之膜厚 為適當範圍’而形成具有更優異之保存穩定性者。再者二 δ亥總固形分遭度之調整係視需要藉由丨農縮及有機溶媒之 稀釋而進行。 1 · 6 ·其他添加物 物Γί述絕緣膜形成用組成物中’進而亦可添加有機聚合 解性劑等成分。另外’該等添加物亦可添加於溶 解或刀放有混合（Α)成分及⑻成分前之各成分的 1· 6· 1·有機聚合物 作為有機聚合物’例如可舉出具有糖 乙晞基酿胺系聚合物、(甲基)丙稀酸系聚合物、；乙 物系聚合物、樹枝狀聚合物、聚醯胺、聚酸胺酸、 醯胺、聚物、聚，二唾、氣系聚合物、 具有♦伸烷基氧化物構造之聚合物等。 作為聚㈣基氧化物構造之聚合物，可舉 化物構造、聚環氧乙烷構造、 甲基虱 亞甲基鱗構造、聚環氧丁㈣=乳丙燒構造、聚氧化四， 具體而§ ’可舉出聚氧乙 ^ 聚氧乙烯烷基苯醚、聚氧乙/t、、承乳乙婦炫基鍵、 “ 知固軸、聚氧乙婦羊毛脂衍 =貌基讀福馬林縮合物之環氧乙⑽生物 烯♦氧丙烯嵌段共聚物、聚 虱乙 化合物、聚氧乙稀丙三醇：=聚氧丙稀炫基州型 醉月曰肪酸酯、聚氧乙烯山梨糖醇酐 3_發明說明書_/96·_19467 37 200808907 脂肪酸_、聚氧乙烯山梨醇脂肪酸酉旨… 醇醯胺硫酸鹽等醚酯型化合物、尹 來氧乙婦脂肪酸烷 醇脂肪酸酯、脂肪酸單甘油酯、铲乙〜醇脂肪酸酯、乙二 糖醇酐脂肪酸酯、丙_酶p=丙二醇脂肪酸酯、山梨 ' 型化合物等。 “、、搪脂肪酸酯等醚酯 •-作為聚氧乙烯聚氧丙稀嵌段共 段構造之化合物。 物可舉出具有如下巍 -(X，V(y， • -(X，)1-(Y，v(x，)n— (式中，X，表示以—CH2CH2〇一所 -ch2CH(CH3)0-表示之基，i表示心：之基，Y，表示以 表示0〜90之數）。 m表不10〜99，η 口亥等之中，作為更佳之例，可舉取& 氧乙烯平#i兩搡山队u甘 印♦乳乙稀烷基醚、聚 手L 〇佈聚虱丙烯肷段共聚物、聚氧 聚童ί r、膝$ n 礼己埽聚氧丙烯烷基醚、 承虱乙烯丙二醇脂肪酸酯、聚氧乙 醋、臂盡7降ϊ木糖醇酐脂肪酸 合物可傕用1锸$ F1味& 1化己物。上述有機聚 便用1種或同時使用2種以上。 1 · 6 · 2 ·界面活性劑 作為界面活㈣，壯可舉出非 離子系界面活性劑、陽離子李只而、=糸界面/舌性劑、陰 ㈣，* μ ~離子系界面活性劑、兩性界面活性 ;、乂由、而可舉出氟系界面活性劑、聚矽氧系界面活性 2承伸院基氧化物系界面活性劑、聚（甲基）丙婦酸酿系 ，活性劑等，較佳可列舉氟系界面活性劑、聚 面活性劑。 L系界 312ΧΡ/發明說明書(補件)/96·〇7/96ι ^ 9467 38 200808907 1 〇 〇重量份所獲得之聚 。該等可使用1種或同 界面活性劑之使用量，係相對於 合物，通常為0·00001〜1重量份 時使用2種以上。 2·膜之形成方法 /發明一實施形態之膜（絕緣骐）之形成方法包含：將膜 形成用組成物塗佈於基材上而开j 夕 、 π每^ & 成塗膜之步驟；對上述塗 胰貝施自加熱、電子線照射、紫外 ^ i 1 ^ ^ 系外線知射、以及氧電漿選 擇之至少1種硬化處理之步驟。 ^為塗佈膜形成用組成物之基材，可舉出心仙2、 :二 =CN等含有Si2之層。作為將膜形成用組成 之方法’可使用旋塗法、浸潰法、輥塗法、 二:=“衣手段。於基材上塗佈膜形成用組成物後，去 ^谷·形成塗膜。此時之膜厚，作為乾燥 卜 佈可形成厚度〇·〇5〜2.5 /zm之泠臌0 u 乂 ^ Λ 1 之塗膜，2次塗佈可形成厚 又· 5· 0 # m之塗膜。其後，藉由對所獲得之塗膜實 施硬化處理，可形成二氧化矽系膜。 猎由加熱進打硬化之情況下’係將該塗膜於惰性環境氣 體下或減屢下加熱至8(rc〜45(rc。作為此時之加熱方 法，可使用加熱板、烘箱、爐子等，作為加熱環境氣體， 可於惰性環境氣體下或減愿下進行。另外，亦可藉由於加 熱條件下照射紫外線而進行塗膜之硬化處理。 另外為彳工制上述塗膜之硬化速度，視需要可階段性加 熱’或選擇氮、空氣m等環境氣體。藉由此種步 驟，可進行二氧化矽系膜之製造。 312XP/發明說明書(補件)/9心〇7/96119467 200808907 3. 二氧化矽系膜（二氧化矽系絕緣膜） 本舍明-實加形恶之二氧化梦系膜，其介電係數低，且 表面平坦性優異，故作為LSI、系统LSI、_、觀m、 _ΑΜ、請等半導體元件用層間絕緣膜特別優里， 且可較佳地用於餘刻終止膜、半導體元件之表面塗膜等保 濩膜、使用多層抗钕劑之半導體製作步驟之中間層、多層 1布線基板之層間絕緣膜、液晶顯示元件用保護膜或絕緣膜 等本毛月貝知形恶之二氧化石夕系膜之介電係數通常為 3 · 5以下，較佳為1. 8〜3. 〇。 4. 實施例 乂下歹j舉貝加例進-步具體說明本發明。本發明不為 限定於以下實施例者。再#，實施例以及比較例中之「份 及「％」，只要無特別標記，則分別表示重量份及重量％。 4· 1.評估方法 各種膜之評估如下進行。 々英寸夕曰曰圓上，使用旋塗法塗佈膜形成用組成物， 於加熱板上以9 0 °C #、經qα ^ ^ 。 季秌3刀1里，接者於氮環境氣體下以 200 C乾燥3分鐘。進而，利用 ⑴用以下之任一方法實施硬化 處理。 (i )僅以加熱進行硬化處理之情況 於50 mT〇rr之減壓下（真空環境氣體）以42〇ι之立 爐锻燒1小時。 (ii)於加熱條件下藉由紫外線照射進行硬化處理之情況 一邊於加熱板上將塗臈加熱至綱。C ’―邊照射3分鐘 312XP/發明說明書(補件)/96-〇7/96119467 4〇 200808907 包含波長250 nm以下之波長之白色紫外線。此時，使氧 分壓為0· 01 kPa以下。 4. 1. 1.介電係數測定 於所獲得之膜上藉由蒸鍍法形成鋁電極圖案，製成介電 • 係數測定用樣品。對該樣品以頻率100 kHz之頻率，使用 :Yokogawa Hewlett Packard(股）製、HP16451B 電極以及 HP4284A Precision LCR Mater，藉由電容電壓法（CV 法， Capacitance Voltage)測定該膜之介電係數。 ⑩4· 1· 2·絕緣膜之硬度以及彈性率（揚氏模量）評估 於MTS公司製造之超微小硬度計（NanoindentatorXP) 上安裝Berkovich型壓頭，求得所獲得之絕緣膜之萬能硬 度。另外，藉由連續硬度測定法測定彈性率。 4. 1. 3.保存穩定性 使用旋塗法將於40°C保存30天之膜形成用組成物塗佈 於基材上，將基板於加熱板上以90°C乾燥3分鐘，接著 •於氮環境氣體下以200°C乾燥3分鐘，進而於50 mTorr 之減壓下以420°C之立式爐鍛燒1分鐘。使用光學膜厚計 (Rudolph Technologies 公司製造、Spectra Laser200) 對如此獲得之塗膜之膜厚於塗膜面内進行50點測定。測 •定所獲得之膜之膜厚，根據藉由下式而求得之膜厚增加 、率，評估保存穩定性。 膜厚增加率（％)=((保存後之膜厚）一（保存前之膜 厚））·Κ保存前之膜厚）χ100 A :膜厚增加率為4%以下。 312XP/發明說明書(補件)/96-07/96119467 41 200808907 B ·膜厚增加率超過4%。 • 14·耐化學藥品性 拉 夕糸版之8央吋晶圓於室溫下於0· 2%之 稀氫氟酸水溶液中芦、、主q 么从 夜T /又/貝3分鐘，觀察浸潰前後之二氧化矽 系膜之膜厚變化。婪， 化右下述疋義之殘膜率為99%以上，則判 断耐化學藥品性良好。 殘膜率（％)=：(浸潰後 厚）χ100 之膜之膜厚）+ (浸潰前 之膜之膜- Examples of the key solvent system include diethyl ether, diisopropyl ether, n-butyl ketone, n-hexyl ether, 2 hexyl ether, dioxolane, 4-methyldioxolane, dioxane, and dinonyl ruthenium. Alkane, ethylene glycol monomethyl ether, ethylene glycol dioxime ether, ethylene glycol monoethyl ether, ethyl alcohol monoethyl hydrazine, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol single, ethylene two Alcohol | 2-ethyl butyl ether, ethylene glycol dibutyl bond, diethyl hydrazine monomethyl ether, diethylene glycol dioxime ether, diethylene glycol monoethyl ether, diethyl hydrazine to diethyl ether, diethylene Alcohol mono-n-butyl ether, diethylene glycol di-n-butyl ether, di-n-ol mono-n-hexyl ether, ethoxy triethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monoterpene ether, propylene glycol monoethyl ether, An ether-based solvent such as propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diphenyl ether or anisole. The solvent may be used alone or in combination of two or more. Examples of the ester-based solvent include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, and hydrazine. Butyrolactone, valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, acetic acid 3- Methoxybutyl ester, decyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, acetamidine Methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, diethylene glycol monoterpene ether acetate, diethylene glycol monoethyl ether 312 ΧΡ / Description of the invention (supplement)/96-07/96119467 35 200808907 Acid ester, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propanol monoethyl acetate, propylene glycol monopropyl Ether acetate, propylene glycol monobutyl acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxy triethylene glycol acetate, C Ethyl acetate, n-butyl vinate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, decyl phthalate, ethyl lactate, n-butyl lactate, lactic acid An ester-based solvent such as ester, malonate-ethyl phthalate, dimethyl phthalate or diethyl phthalate. The ester-based solvent such as hydrazine may be used in combination or in combination of two or more kinds. Examples of the hydrocarbon-based solvent include n-pentyl, iso-pentyl, n-hexan, isohexane, n-heptane, isoheptane, 2, 2, 4-trimethylpentane, n-octane, isooctane, and An aliphatic tobacco-based solvent such as hexane or methylcyclohexanone. The aliphatic tobacco-based solvent can be used in combination or in combination of two or more kinds. Examples of the sulphur-based hydrocarbon-based solvent include phenyltoluene and ethylbenzene. Dimethyl, field I ^ ^ 丫 均 di-diethyl benzene ~ Benzene _ diethyl ethyl benzene, n-propyl benzene, cumene, Bodhisattva - soil - ethyl stupid, diisopropyl benzene, n-pentyl There is no hydrocarbon oxime solvent in the extraction, etc. These aromatics, ^^, and two or more kinds can be used. As the (4)-system/combination medium, one type or the same corpse sulphate can be used, and diclosan can be cited. , prepared for fluorine gas carbide, chlorobenzene, - negative! , imitation, ^ a transcript, and other halogen-containing solvents. In the present invention, it is desirable to use an organic solvent having a boiling point of a solvent type, which is more than i# iwx, and a "vehicle alcoholic solvent, a ketone-based solvent, a system of one or more types, and a The organic solvent can be replaced by the same organic solvent as in the synthesis of the specific hydrolyzed product. V 〇之 & salt after the end of the solvent coffee / invention (Description) / 9_6119467 36 200808907 The total solid content concentration of the above-mentioned composition for forming a crucible is preferably 2 to 30% by weight, which is appropriately adjusted depending on the intended use. The total composition of the above film formation is obtained. The solid content concentration is 2 to 30% by weight, and the film thickness of the coating film can be set to an appropriate range' to form a more excellent storage stability. Further, the adjustment of the total solid content of the second δ is determined by the need of 丨It is carried out by diluting agricultural shrinkage and organic solvent. 1 · 6 · Other additives Γ In the composition for forming an insulating film, a component such as an organic polymerizable agent may be added. Further, these additives may be added to Dissolve or mix with knife (Α) 1. The organic polymer as the organic polymer of the component before the component (8) is, for example, a glycidyl-based amine-based polymer or a (meth)acrylic acid-based polymer; Ethylene polymer, dendritic polymer, polyamine, polyamic acid, guanamine, polymer, poly, disa, gas polymer, polymer with ♦ alkyl oxide structure, etc. Polymer of poly(tetra)-based oxide structure, can be described as a structure, a polyethylene oxide structure, a methyl fluorene methylene scale structure, a polybutylene (tetra) = a milk-fired structure, a poly-oxidation IV, and specifically § ' Examples thereof include polyoxyethylene polyoxyethylene alkyl phenyl ether, polyoxyethylene/t, and lactulose ethyl thiol bond, "knot solid axis, polyoxymethylene lanolin derivative = appearance base read fumarin condensate" Epoxy B (10) bioolefin ♦ oxypropylene block copolymer, polyethylidene bromide, polyoxyethylene propylene glycol: = polyoxypropylene stiletto state drunk acid ester, polyoxyethylene sorbitol Anhydride 3_Invention Manual_/96·_19467 37 200808907 Fatty acid _, polyoxyethylene sorbitol fatty acid 酉 ... ether ester such as melamine sulphate Compound, Yinlai Oxygen Fatty Acid Alkanol Fatty Acid Ester, Fatty Acid Monoglyceride, Shovel B-Alcohol Fatty Acid Ester, Ethylene Glycol Alcohol Fatty Acid Ester, Pro-Enzyme p= Propylene Glycol Fatty Acid Ester, Yamanashi Type Compound Wait. ", an ether ester such as a fatty acid ester, a compound of a polyoxyethylene polyoxypropylene block." The compound has the following structure: (X, V(y, • -(X,)1) -(Y,v(x,)n- (wherein, X represents the base represented by -CH2CH2〇-ch2CH(CH3)0-, i represents the base of the heart: Y, represents 0 to 90 The number of meters is not 10~99, η mouth Hai, etc. As a better example, it can be mentioned & oxyethylene flat #i two 搡山队u 甘印♦ 乳乙乙alkyl ether, gather hands L 〇 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚The alcoholic anhydride fatty acid compound can be used in an amount of 1 锸$F1 味1. The above organic concentrating agent can be used alone or in combination of two or more kinds. 1 · 6 · 2 · surfactant as interface (4), strong Examples of nonionic surfactants, cationic Li, 糸 interface/tongue, yin (4), * μ ~ ionic surfactant, amphoteric interfacial activity; Agent, polyoxane system interface 2, the extension of the base oxide surfactant, the poly(methyl) propylene glycol acid brewing system, the active agent, etc., preferably include a fluorine-based surfactant and a surfactant. L system boundary 312 ΧΡ / invention specification ( Replenishment) / 96 · 〇 7 / 96 ι ^ 9467 38 200808907 1 〇〇 by weight of the obtained poly. The use of one or the same surfactant can be used, relative to the compound, usually 0·00001 In the case of the method of forming a film (insulating crucible) according to the embodiment of the present invention, the method for forming a film (insulating crucible) according to the embodiment of the present invention comprises: applying a film forming composition to a substrate to open a π, π a step of forming a film per ^ & a step of applying at least one kind of hardening treatment of the above-mentioned coated pan-stained self-heating, electron beam irradiation, ultraviolet ^ i 1 ^ ^ external line detection, and oxygen plasma selection. The substrate containing the composition for forming a film may be a layer containing Si 2 such as two or two = CN. The method for forming a film may be a spin coating method, a dipping method, or a roll coating method. , 2: = "clothing means. After coating the composition for film formation on the substrate, go to the valley to form a coating film. The film thickness can be used as a dry cloth to form a coating film having a thickness of 〇·〇5 to 2.5 /zm 泠臌0 u 乂^ Λ 1, and a coating film of a thickness of 5·0 #m can be formed by two coatings. Thereafter, the ruthenium dioxide film can be formed by subjecting the obtained coating film to a hardening treatment. When the stalk is heated and hardened, the coating film is heated to 8 under an inert atmosphere or under repeated conditions. (rc to 45 (rc.) As a heating method at this time, a heating plate, an oven, a furnace, or the like can be used as the heating ambient gas, and it can be carried out under an inert atmosphere or under reduced pressure. Further, the coating film may be hardened by irradiation of ultraviolet rays under heating conditions. Further, the curing speed of the coating film is completed by the completion of the coating, and if necessary, the heating may be performed stepwise, or an environmental gas such as nitrogen or air m may be selected. By such a procedure, the production of a ruthenium dioxide film can be carried out. 312XP/Invention Manual (supplement)/9 heart 〇7/96119467 200808907 3. cerium dioxide film (cerium oxide-based insulating film) Benximin-solid oxidized oxidized dream film, its dielectric coefficient Since it is low in surface flatness, it is excellent as an interlayer insulating film for semiconductor elements, such as LSI, system LSI, _, m, _ ΑΜ, etc., and can be preferably used for the surface coating of a residual stopper film or a semiconductor element. A protective film such as a film, an intermediate layer of a semiconductor fabrication step using a multilayer anti-caries agent, an interlayer insulating film of a multilayer 1 wiring substrate, a protective film for a liquid crystal display element, or an insulating film, etc. 5〜3. 〇。 The dielectric film of the cerium film is usually 3 · 5 or less, preferably 1. 8~3. 4. EXAMPLES The present invention is specifically described in the following section. The present invention is not limited to the following examples. In the examples and the comparative examples, "parts and "%" are used to indicate the parts by weight and % by weight, unless otherwise specified. 4. Evaluation methods Evaluation of various membranes was carried out as follows. On the 曰曰 inch 曰曰 circle, the composition for film formation was applied by spin coating, and was applied to the hot plate at 90 ° C #, via qα ^ ^ . In the 3 knives of the raft, the receiver was dried at 200 C for 3 minutes under a nitrogen atmosphere. Further, the curing treatment is carried out by any one of the following methods (1). (i) In the case of hardening treatment by heating, it was calcined in a 42 〇 vertical furnace under reduced pressure of 50 mT Torr (vacuum atmosphere) for 1 hour. (ii) When the curing treatment is carried out by ultraviolet irradiation under heating, the coating is heated to the surface on the hot plate. C ─ ― 3 minutes of irradiation 312XP / invention manual (supplement) / 96-〇 7/96119467 4〇 200808907 Contains white ultraviolet light with a wavelength of 250 nm or less. At this time, the partial pressure of oxygen is made 0 to 01 kPa or less. 4. 1. 1. Measurement of Dielectric Coefficient An aluminum electrode pattern was formed by vapor deposition on the obtained film to prepare a sample for dielectric constant measurement. The film was measured for the dielectric constant of the film by a capacitor voltage method (CV method, Capacitance Voltage) using a frequency of 100 kHz using a Yokogawa Hewlett Packard (manufactured), an HP16451B electrode, and an HP4284A Precision LCR Mater. 104· 1· 2· Hardness and elastic modulus (Young's modulus) of the insulating film were evaluated by installing a Berkovich type indenter on a nanometer hardness tester (Nanoindentator XP) manufactured by MTS, and the hardness of the obtained insulating film was obtained. . Further, the modulus of elasticity was measured by a continuous hardness measurement method. 4. 1. 3. Storage stability The film-forming composition was applied to the substrate by spin coating at 40 ° C for 30 days, and the substrate was dried on a hot plate at 90 ° C for 3 minutes, and then • The mixture was dried at 200 ° C for 3 minutes under a nitrogen atmosphere, and further calcined in a vertical furnace at 420 ° C for 1 minute under a reduced pressure of 50 mTorr. The film thickness of the coating film thus obtained was measured at 50 points in the surface of the coating film using an optical film thickness meter (manufactured by Rudolph Technologies, Spectra Laser 200). The film thickness of the obtained film was measured, and the storage stability was evaluated based on the increase and the film thickness obtained by the following formula. Film thickness increase rate (%) = ((film thickness after storage) - (film thickness before storage)) - film thickness before storage) χ 100 A: The film thickness increase rate was 4% or less. 312XP/Invention Manual (supplement)/96-07/96119467 41 200808907 B · The film thickness increase rate exceeds 4%. • 14·Chemical-resistant Lahu 糸 version of the 8 吋 吋 wafer at room temperature in 0. 2% dilute hydrofluoric acid aqueous solution, the main q from the night T / / / shell 3 minutes, observe The film thickness of the cerium oxide film before and after the immersion was changed. In other words, if the residual film ratio of the following meaning is 99% or more, it is judged that the chemical resistance is good. Residual film rate (%) =: (thickness after immersion) film thickness of χ100) + (film of film before immersion)

殘膜率為99%以上。 B=殘膜率未滿99%。 4 · 1 · 5 ·確認有無膜之相分離 1絕緣膜之剖面以集束離子束法進行加工用於觀察，使 用牙透式電子顯微鏡（Tem，Transmission Electron Microscope)以18000倍調查外觀。判斷結果如下所示。 A :剖面之形狀觀察中獲得均勻之塗膜。 φ B ·塗膜中確認海導島狀相區相分離。 4 · 1 · 6 · S i NMR光譜測定 膜形成用組成物之29SiNMR光譜（100 MHz)，使用BRUKER AVMCE500型進行測定。 4· 2·膜形成用組成物之製造 、4· 2· 1.實施例1 於具備冷凝器之石英製燒瓶中，稱取2· 32 g之40%甲 基胺水溶液、159.96 g超純水、以及464.97 g乙醇，於 60°C進行攪拌。接著，添加56· 83 g曱基三曱氧基矽烷、 312XP/發明說明書(補件)/96-07/96119467 42 200808907 以及15.93 g具有以下述通式（5)所表示之構造之聚碳矽 烷（Mw=l，300)後，於60°C攪拌6小時，獲得含有聚苯乙 烯換算重量平均分子量為39, 000之水解縮合物之反應 液。將反應液冷卻至室溫後，添加613.24 g丙二醇單丙 、 醚及20. 65 g | 20%乙酸水溶液。於減壓下使該反應液濃 * 縮直至固形分濃度達到10%，獲得膜形成用組成物1。該 膜形成用組成物之 S i丽R光譜（10 0 Μ Η z )之光譜貢料（稀 釋溶媒：無）如下所述。再者，於本實施例及後述之實施 ❿例2〜4中，於29SiNMR測定中，將存在於50〜-80 ppm之 波峰之積分值之總和設為1時，存在於-90〜-120 ppm之 波峰之積分值之總和未滿0. 01。 -75〜-45 ppm (Broad)， -30〜-10 ppm (Broad)， 0〜 20 ppm (Broad) [化4] 息 Γ och2ch3 • -4·- OCH2CH3 _n ··.··⑸ 4. 2. 2.實施例2 於具備冷凝器之石英製燒瓶中，稱取38. 21 g之20%氫 氧化四丙基銨水溶液、5 9 · 7 g超純水、以及5 4 2. 5 4 g異 丙醇，於60°C進行攪拌。接著，添加49.72 2甲基三曱 氧基矽烷、以及9. 80 g具有以下述通式（6)所表示之構造 312XP/發明說明書(補件)/96-07/96119467 43 200808907 之市售聚碳秒烧（「NIPUSIType—L」、可自日本炭素股份 有限公司獲得之聚二曱基矽烷之碳矽烷化聚合物）（Mw = 910)後，於60 C攪拌4小時，獲得含有聚苯乙烯換算重 1平均分子篁為48, 000之水解縮合物之反應液。將反應 液冷卻至室溫後，添加552· 03 g丙二醇單丙醚及25· 95 g 之20%乙酸水溶液。於減壓下使該反應液濃縮直至固形分 濃度達到10%，獲得膜形成用組成物2。該膜形成用組成 物之29SiNMR光譜（1〇〇 mHz)之光譜資料（稀釋溶媒：無） 如下所述。 75 45 ppm (Broad)，-40〜-30 ppm (Broad)，-20 〜10 ppm (Broad)， 10〜30 ppm (Broad) [化5] ch3 Si-CH2—The residual film ratio is 99% or more. B = residual film rate is less than 99%. 4 · 1 · 5 · Confirmation of phase separation of the film 1 The cross section of the insulating film was processed by the cluster ion beam method for observation, and the appearance was investigated by a transmission electron microscope (Tem, Transmission Electron Microscope) at 18,000 times. The judgment result is as follows. A: A uniform coating film was obtained in the shape observation of the cross section. φ B · Confirmation of phase separation of the sea-island island phase in the coating film. 4 · 1 · 6 · S i NMR spectrum measurement The 29Si NMR spectrum (100 MHz) of the film-forming composition was measured using a BRUKER AVMCE500 type. 4·2·Production of a film-forming composition, 4. 2· 1. Example 1 In a quartz flask equipped with a condenser, 2·32 g of a 40% aqueous solution of methylamine and 159.96 g of ultrapure water were weighed. And 464.97 g of ethanol were stirred at 60 °C. Next, 56·83 g of decyltrimethoxy decane, 312XP/invention specification (supplement)/96-07/96119467 42 200808907 and 15.93 g of polycarbodecane having a structure represented by the following formula (5) were added. After (Mw = 1,300), the mixture was stirred at 60 ° C for 6 hours to obtain a reaction liquid containing a hydrolyzed condensate having a weight average molecular weight of 39 000 in terms of polystyrene. After cooling the reaction mixture to room temperature, 613.24 g of propylene glycol monopropane, ether and 20.65 g of a 20% aqueous acetic acid solution were added. The reaction liquid was concentrated under reduced pressure until the solid content concentration reached 10%, and the film formation composition 1 was obtained. The spectral scent (dilute solvent: none) of the S i Li R spectrum (10 0 Μ Η z ) of the composition for film formation is as follows. Further, in the present examples and the examples 2 to 4 which will be described later, in the 29Si NMR measurement, when the sum of the integral values of the peaks present in the range of 50 to 80 ppm is set to 1, it exists in -90 to -120. The sum of the integral values of the peaks of the ppm is less than 0.01. -75 to -45 ppm (Broad), -30 to -10 ppm (Broad), 0 to 20 ppm (Broad) [Chemical 4] Information Γ och2ch3 • -4·- OCH2CH3 _n ······(5) 4. 2 2. Example 2 In a quartz flask equipped with a condenser, 38.21 g of 20% aqueous solution of tetrapropylammonium hydroxide, 5 9 · 7 g of ultrapure water, and 5 4 2. 5 4 g were weighed. Isopropanol was stirred at 60 °C. Next, 49.72 2 methyltrimethoxy decane and 9.80 g of a commercially available polymer having the structure 312XP/invention specification (supplement)/96-07/96119467 43 200808907 represented by the following general formula (6) were added. After carbon calcination ("NIPUSI Type-L", a carbon decylated polymer of polydimethyl decane available from Nippon Carbon Co., Ltd.) (Mw = 910), it was stirred at 60 C for 4 hours to obtain polystyrene. The reaction liquid of the hydrolyzed condensate having a weight average molecular weight of 4, 000 was converted. After cooling the reaction mixture to room temperature, 552·03 g of propylene glycol monopropyl ether and 25·95 g of a 20% aqueous acetic acid solution were added. The reaction liquid was concentrated under reduced pressure until the solid concentration reached 10% to obtain a composition 2 for film formation. The spectral data (diluted solvent: none) of the 29Si NMR spectrum (1 〇〇 mHz) of the film-forming composition was as follows. 75 45 ppm (Broad), -40 to -30 ppm (Broad), -20 to 10 ppm (Broad), 10 to 30 ppm (Broad) [Chemical 5] ch3 Si-CH2—

⑹(6)

4· 2. 3.實施例3 斤於具備冷凝器之石英製燒瓶中，稱取4·92 g之25%氫 氧化四曱基銨水溶液、93. 5 g超純水、以及568. 51轻乙 醇，於60 C進行授拌。接著，花費i小時連續添加8, 21运 二甲基二曱氧基矽烷、21·59 g曱基三曱氧基矽烷、以及 3.14 g具有以下述通式所表示之構造之聚碳矽烷 (MW=1，05G)後，進而於6代_ 2小時，獲得含有聚笨 312XP/發明說明書(補件)/96-〇7/96119467 44 200808907 乙烯換异重篁平均分子量為34,〇〇〇之水解縮合物之反應 液。將反應液冷卻至室溫後，添加658· 76 g丙二醇單丙 醚及9· 31 g之20%乙酸水溶液。於減壓下使該反應液濃 a細直至固形分濃度達到10%，獲得膜形成用組成物3。該 膜形成用組成物之29Si丽R光譜（1〇〇 MHz)之光譜資料（稀 1 釋溶媒：無）如下所述。 -75〜-45 ppm (Broad)，-30〜1〇 ppm (Br〇ad)，〇〜2〇 ppm (Broad) •[化 6] -CHo ?CH3 s\—— OCH3 •⑺ 4 · 2 · 4 ·實施例4 φ 於具備冷凝器之石英製燒瓶中，稱取13· 44 g之10%草 酸水溶液、41· 72 g超純水、以及571· 53 g丙二醇單丙 _ ’接著添加56· 83 g曱基三甲氧基矽烷、以及15. 93 g 實施例1中所使用之聚碳矽烷（Mw = 1，300)後，於60°C攪 •拌2小時，獲得含有聚苯乙烯換算重量平均分子量為 ‘ 3，5 0 0之水解縮合物之反應液。將反應液冷卻至室溫後， 添加700.31 g丙二醇單丙醚。於減壓下使該反應液濃縮 直至固开> 分濃度達到1 〇%，獲得膜形成用組成物4。該膜 形成用組成物之29Si丽R光譜（1〇〇 MHz)之光譜資料（稀釋 312XP/發明說明書(補件)/96-07/96119467 45 200808907 溶媒：無）如下所述。 -70〜-60 ppm (Broad)， -60〜-50 ppm (Broad)， -50 〜-40 ppm (Broad)，-30〜-10 ppm (Broad), 5〜10 ppm (Broad) ~ . 4. 2. 5.比較例1 ' 於具備冷凝器之石英製燒瓶中，稱取2. 58 g 40%之曱 基胺水溶液、17 8. 16 g超純水、以及4 3 5 · 3 4 g乙醇，於 60°C進行攪拌。接著，添加41. 07 g曱基三甲氧基矽烷、 ⑩26. 92 g四乙氧基矽烷、以及15. 93 g具有以下述通式（8) 所表示之構造之聚碳矽烷（Mw=l，300)後，於60°C攪拌6 時間，獲得含有聚苯乙烯換算重量平均分子量為45, 000 之水解縮合物之反應液。將反應液冷卻至室溫後，添加 613. 50 g丙二醇單丙醚及22. 96 g之20%乙酸水溶液。於 減壓下使該反應液濃縮直至固形分濃度達到10%，獲得膜 形成用組成物5。該膜形成用組成物之29Si丽R光譜（100 0 MHz )之光譜資料（稀釋溶媒：無）如下所述。再者，於本比 較例及後述之比較例2〜4中，於29SiNMR測定中，將存在 於50〜-80 ppm之波峰之積分值之總和設為1時，存在於 -9 0〜-1 2 0 ppm之波峰之積分值之總和大於0. 01。 第 -115〜-90 ppm (Broad)， -75〜-45 ppm (Broad)，-30 .〜-10 ppm (Broad), 0〜20 ppm (Broad) 312XP/發明說明書(補件)/96-07/96119467 46 200808907 [化7] och2ch3 CH2--4 。 568 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Ethanol was mixed at 60 C. Next, 8, 21 dimethyl dimethoxy decane, 21·59 g decyl decyloxy decane, and 3.14 g of polycarbane having a structure represented by the following formula (MW) were continuously added for 1 hour. =1,05G), and then in the 6th generation _ 2 hours, obtained the polystyrene 312XP / invention manual (supplement) / 96-〇7/96119467 44 200808907 ethylene exchange weight weight average molecular weight of 34, 〇〇〇 A reaction solution for hydrolyzing a condensate. After the reaction solution was cooled to room temperature, 658.76 g of propylene glycol monopropyl ether and 9·31 g of a 20% aqueous acetic acid solution were added. The reaction liquid was concentrated to a concentration of 10% under reduced pressure to obtain a film-forming composition 3. The spectral data of the 29Si Li R spectrum (1 〇〇 MHz) of the film-forming composition (diluted solvent: none) is as follows. -75~-45 ppm (Broad), -30~1〇ppm (Br〇ad), 〇~2〇ppm (Broad) •[化6] -CHo ?CH3 s\—— OCH3 •(7) 4 · 2 · 4 · Example 4 φ In a quartz flask equipped with a condenser, weighed 13.44 g of 10% aqueous oxalic acid solution, 41.72 g of ultrapure water, and 571·53 g of propylene glycol monopropyl _ 'and then added 56· 83 g of decyltrimethoxydecane, and 15.93 g of the polycarbane (Mw = 1,300) used in Example 1, and then stirred at 60 ° C for 2 hours to obtain a polystyrene-converted weight. A reaction liquid of a hydrolysis condensate having an average molecular weight of '3,500. After the reaction solution was cooled to room temperature, 700.31 g of propylene glycol monopropyl ether was added. The reaction liquid was concentrated under reduced pressure until the concentration was maintained at a concentration of 1% by weight to obtain a film-forming composition 4. The spectral data of the 29Si Li R spectrum (1 〇〇 MHz) of the film-forming composition (diluted 312XP/invention specification (supplement)/96-07/96119467 45 200808907 solvent: none) is as follows. -70~-60 ppm (Broad), -60~-50 ppm (Broad), -50 to -40 ppm (Broad), -30~-10 ppm (Broad), 5~10 ppm (Broad) ~ . 4 2. Comparative Example 1 'In a quartz flask equipped with a condenser, 2.58 g of 40% aqueous solution of mercaptoamine, 17 8. 16 g of ultrapure water, and 4 3 5 · 3 4 g were weighed. Ethanol was stirred at 60 °C. Next, 41.07 g of decyltrimethoxydecane, 1026.92 g of tetraethoxydecane, and 15.93 g of polycarbane having a structure represented by the following formula (8) (Mw=l, After 300), the mixture was stirred at 60 ° C for 6 hours to obtain a reaction liquid containing a hydrolyzed condensate having a weight average molecular weight of 45,000 in terms of polystyrene. After cooling the reaction mixture to room temperature, 613.50 g of propylene glycol monopropyl ether and 22.96 g of a 20% aqueous acetic acid solution were added. The reaction liquid was concentrated under reduced pressure until the solid content concentration reached 10% to obtain a film forming composition 5. The spectral data (diluted solvent: none) of the 29Si Li R spectrum (100 0 MHz) of the film-forming composition is as follows. Further, in the comparative examples and Comparative Examples 2 to 4 to be described later, in the 29Si NMR measurement, when the total of the integrated values of the peaks of 50 to 80 ppm is set to 1, it exists in -9 0 to -1. The sum of the integral values of the peaks of 2 0 ppm is greater than 0.01. -115~-90 ppm (Broad), -75~-45 ppm (Broad), -30.~-10 ppm (Broad), 0~20 ppm (Broad) 312XP/Invention Manual (supplement)/96- 07/96119467 46 200808907 [化7] och2ch3 CH2--

I •Si- 0CH2CH3 ⑻ 4. 2. 6.比較例2 於具備冷凝器之石英製燒瓶中，稱取45.93 g之20%氫 _氧化四丙基銨水溶液、71. 8 g超純水、以及4 9 5 · 31 g異 丙醇，於60°C進行攪拌。接著，添加26. 24 g曱基三曱 氧基矽烷、50. 93 g四丙氧基矽烷、以及9. 80 g具有以 下述通式（9)所表示之構造之市售聚碳矽烷（「NIPUSI Type-L」、可自日本炭素股份有限公司獲得之聚二曱基矽 烷之碳矽烷化聚合物）（Mw=910)後，於60°C攪拌4小時， 獲得含有聚苯乙烯換算重量平均分子量為55, 000之水解 0縮合物之反應液。將反應液冷卻至室溫後，添加5 51. 8 6 g 丙二醇單丙醚及31. 20 g之20%乙酸水溶液。於減壓下使 該反應液濃縮直至固形分濃度達到10%，獲得膜形成用組 成物6。該膜形成用組成物之29Si丽R光譜（100 MHz)之光 ^ 譜資料（稀釋溶媒：無）如下所述。 ' -115〜-90 ppm (Broad)， -75〜-45 ppm (Broad)， -40 〜-30 ppm (Broad)，-20 〜10 ppm (Broad)，10 〜30 ppm (Broad) 312XP/發明說明書(補件)/96-07/96119467 47 200808907 [化8]I. Si- 0CH2CH3 (8) 4. 2. 6. Comparative Example 2 In a quartz flask equipped with a condenser, 45.93 g of a 20% hydrogen tetramethylammonium hydroxide aqueous solution, 71.8 g of ultrapure water, and 4 9 5 · 31 g of isopropanol, stirred at 60 ° C. Next, 26.24 g of decyltrimethoxy decane, 50.93 g of tetrapropoxy decane, and 9.80 g of commercially available polycarbon decane having a structure represented by the following formula (9) were added (" NIPUSI Type-L", a carbon-alkylated polymer of polydimethyl decane available from Nippon Carbon Co., Ltd.) (Mw = 910), and then stirred at 60 ° C for 4 hours to obtain a weight average in terms of polystyrene A reaction solution of a hydrolyzed 0 condensate having a molecular weight of 55,000. After cooling the reaction mixture to room temperature, 5 51.86 g of propylene glycol monopropyl ether and 31.20 g of a 20% aqueous acetic acid solution were added. The reaction liquid was concentrated under reduced pressure until the solid content concentration reached 10%, and the composition for film formation 6 was obtained. The photo-spectrum data (diluted solvent: none) of the 29Si Li R spectrum (100 MHz) of the film-forming composition was as follows. '-115~-90 ppm (Broad), -75~-45 ppm (Broad), -40 to -30 ppm (Broad), -20 to 10 ppm (Broad), 10 to 30 ppm (Broad) 312XP/Invention Manual (supplement)/96-07/96119467 47 200808907 [Chem. 8]

' 4· 2· 7.比較例3 於具備冷凝器之石英製燒瓶中，稱取5· 80 g之25%气 氧化四曱基銨水溶液、11〇· 3〇 g超純水、以及548. _乙醇，於6(TC進行攪拌。接著，花費}小時連續添加5 j g二甲基二曱氧基矽烷、16.15g曱基三甲氧基矽烷、1〇83 g四甲氧基矽烷、以及3· 14 g具有以下述通式（1〇)所表 示之構造之聚碳矽烷（Mw=l，〇50)後，進而於6(TC攪拌2 小時，獲得含有聚苯乙烯換算重量平均分子量為4〇, 〇〇〇 之水解縮合物之反應液。將反應液冷卻至室溫後，添加 658· 38 g丙二醇單丙醚及1〇· 98 g之20%乙酸水溶液。於 φ減壓下使該反應液濃縮直至固形分濃度達到丨〇%，獲得膜 形成用組成物7。該膜形成用組成物之29Si丽R光譜（100 MHz)之光譜資料（稀釋溶媒：無）如下所述。 -115〜-90 ppm (Broad)， -75〜-45 ppm (Broad)， -30 .〜—10 ppm (Broad)， 0〜20 ppm (Broad) ^ [化 9] 312XP/發明說明書(補件)/96-07/96119467 48 200808907 och3 I 3'4·2· 7. Comparative Example 3 In a quartz flask equipped with a condenser, 5·80 g of 25% oxidized tetradecyl ammonium aqueous solution, 11〇·3〇g of ultrapure water, and 548. _ Ethanol, stirring at 6 (TC). Next, it took 5 hours to continuously add 5 jg of dimethyldimethoxy decane, 16.15 g of decyltrimethoxydecane, 1 〇83 g of tetramethoxynonane, and 3· 14 g of polycarbane (Mw=l, 〇50) having a structure represented by the following formula (1〇), and further stirred at 6 (TC for 2 hours to obtain a weight average molecular weight of 4 聚苯乙烯 in terms of polystyrene) , the reaction solution of the hydrolysis condensate of hydrazine. After cooling the reaction solution to room temperature, 658·38 g of propylene glycol monopropyl ether and 1 〇 98 g of a 20% aqueous acetic acid solution were added. The reaction was carried out under reduced pressure of φ. The liquid was concentrated until the solid content concentration reached 丨〇%, and the film-forming composition 7 was obtained. The spectrum data of the 29Si Li R spectrum (100 MHz) of the film-forming composition (diluted solvent: none) was as follows. -90 ppm (Broad), -75 to -45 ppm (Broad), -30 .~-10 ppm (Broad), 0 to 20 ppm (Broad) ^ [Chem. 9] 312XP/Invention Manual ( Supplement)/96-07/96119467 48 200808907 och3 I 3

Si-CH2 L〇ch3 (10) 4 · 2 · 8 ·比較例4 於具備冷凝器之石英製燒瓶中，稱取14· 97 g之10〇/〇草 酸水溶液、46.44 g超純水、以及554.25 g丙二醇單丙 醚’接著添加41.07 g甲基三甲氧基矽烷、26. 92 g四乙 氧基石夕烷、以及15· 93 g與實施例1中所使用者相同之聚 碳矽烷（Mw = 1，300)後，於6(TC攪拌2小時，獲得包含聚 苯乙烯換算重量平均分子量為3, 7〇〇之水解縮合物。將反 應液冷卻至室溫後，添加7〇〇· 16g丙二醇單丙醚。於減 壓下使該反應液濃縮直至固形分濃度達到10%，獲得膜形 成用組成物8。該膜形成用組成物之29S]^Mr光譜〇〇〇 MHz) 之光譜資料（稀釋溶媒：無）如下所述。 -110〜-95 ppm (Broad)， -95〜-90 ppm (Broad)， -90 〜一80 ppm (Broad), -70〜-60 ppm (Broad)，-60〜-50 ppm (Broad)，-50 〜-40 ppm (Broad)， -30 〜-1〇 ppm (Broad)， 5〜10 ppm (Broad) 4· 3·評估結果 使用實施例1〜4及比較例1〜4中所獲得之膜形成用組 成物1〜8，就介電係數、彈性率、硬度、耐化學藥品性、 保存穩定性及剖面觀察結果加以評估。再者，此時所應用 之硬化處理方法如表中所示。評估結果示於表1。 312XP/發明說明書(補件)/抓〇7/96119467 49 200808907 [表1]Si-CH2 L〇ch3 (10) 4 · 2 · 8 · Comparative Example 4 In a quartz flask equipped with a condenser, 14·97 g of 10 〇/shikiic acid aqueous solution, 46.44 g of ultrapure water, and 554.25 were weighed. g propylene glycol monopropyl ether' followed by 41.07 g of methyltrimethoxydecane, 26.92 g of tetraethoxy oxane, and 15.93 g of the same polycarbodecane as the user of Example 1 (Mw = 1 After 300), the mixture was stirred for 6 hours at TC to obtain a hydrolysis condensate having a weight average molecular weight of 3,7 Å in terms of polystyrene. After cooling the reaction solution to room temperature, 7 〇〇·16 g of propylene glycol was added. The reaction mixture was concentrated under reduced pressure until the solid content concentration reached 10% to obtain a film-forming composition 8. The spectrum of the film-forming composition of 29S]^Mr spectrum 〇〇〇MHz) (diluted) Solvent: none) as described below. -110~-95 ppm (Broad), -95 to -90 ppm (Broad), -90 to 80 ppm (Broad), -70 to -60 ppm (Broad), -60 to -50 ppm (Broad), -50 to -40 ppm (Broad), -30 to -1 〇 ppm (Broad), 5 to 10 ppm (Broad) 4·3· Evaluation results were obtained using Examples 1 to 4 and Comparative Examples 1 to 4. The film-forming compositions 1 to 8 were evaluated for dielectric constant, modulus of elasticity, hardness, chemical resistance, storage stability, and cross-sectional observation results. Further, the hardening treatment method applied at this time is as shown in the table. The evaluation results are shown in Table 1. 312XP / invention manual (supplement) / grab 7/96119467 49 200808907 [Table 1]

由表1可確認，與比較例i〜4相比較， 〜4，可形成具有與耐化學藥品性提昇同等 藉由實施例 之介電係數、 臈之均勻性亦 彈性率及硬度之膜。另外可知保存穩定性、 無問題。 根據以上情況，由本發明所獲得之二氧化矽 強度優異，介電係數低，進而耐化學藥品性及f膜之機械 亦優異，故可較佳地用作半導體元件等 f存穩定性 卞寻之層間絕緣膜。 312XP/發明說明書(補件)/96-07/96119467 50As can be seen from Table 1, in comparison with Comparative Examples i to 4, a film having a dielectric constant, a uniformity of enthalpy, an elastic modulus, and a hardness equivalent to the chemical resistance improvement can be formed. In addition, it is known that the storage stability is stable. According to the above, the cerium oxide obtained by the present invention is excellent in strength, low in dielectric constant, and excellent in chemical resistance and mechanical properties of the f film, so that it can be preferably used as a semiconductor element and the like. Interlayer insulating film. 312XP/Invention Manual (supplement)/96-07/96119467 50

Claims (1)

200808907 十、申請專利範園： /· 一種絕緣膜形成用組成物，其包含使（A)成分與（B) 成分水解縮合而獲得之水解縮合物、及有機溶媒，該（A) 成勿係自以下述通式（1)所表示之化合物及以下述通式（2) 所表不之化合物的群組選擇之至少1種矽烷化合物， 成分係具有以下述通式（3)所表示之構造之碳矽烷； R1aSi(〇R2)4.a ......⑴ (式中’ R1表示1價有機基，R2表示1價有機基，a表示 1〜2之整數） R3b(R40)3-bSi~(R7)d^Si(0R5)3.cR6c......(2) (式中’ R3〜R6為相同或不同，分別表示1價有機基，b 以及c為相同或不同，表示0〜2之數，R7表示伸苯基或 以-（CH2)m-所表示之基（此處，瓜為1〜6之整數），d表示 0或1) [化 10]200808907 X. Patent application: /· A composition for forming an insulating film, comprising a hydrolysis condensate obtained by hydrolyzing and condensing the component (A) and the component (B), and an organic solvent, and the (A) At least one decane compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), wherein the component has a structure represented by the following formula (3) Carbonza; R1aSi(〇R2)4.a (1) (wherein R1 represents a monovalent organic group, R2 represents a monovalent organic group, and a represents an integer of 1 to 2) R3b(R40)3 -bSi~(R7)d^Si(0R5)3.cR6c (2) (wherein R3 to R6 are the same or different, respectively representing a monovalent organic group, and b and c are the same or different , represents a number from 0 to 2, R7 represents a phenyl group or a group represented by -(CH2)m- (here, the melon is an integer of 1 to 6), and d represents 0 or 1) [Chemical 10] (式中，R8表示自氫原子、鹵素原子、羥基、烧氧基、 醯氧基、磺酸基、甲磺酸基、三氟甲磺酸基、烷基、芳基、 烯丙基、以及縮水甘油基所組成群組選擇之基，R9表示自 鹵素原子、羥基、烷氧基、醯氧基、磺酸基、曱磺酸基、 312XP/發明說明書(補件)/96-07/96119467 51 200808907 = 芳基'烯㈣、以及縮水甘油基所 組成群組選擇之基，R1°、RU為相同或不同，表示自函素 原子、經基、貌氧基、酿氧基、石黃酸基'甲石黃酸基、三氣 甲石黃酸基、碳數2〜6之絲、芳基、烯丙基、以及縮水 甘油基所組成群組選擇之基，R12〜R14相同或不同，表示 取代或非取代之亞甲基、伸烧基、伸烯基、伸快基、伸芳 基，e、f、g分別表示0〜10，_之數，滿足1〇<e+f + g< 10, 000 之條件）。 2. 如申請專利範圍第i項之絕緣膜形成用組成物，其 中’上述(A)成分包含以上述通式⑴所表示之化合物。 3. 如申請專利範圍第2項之絕緣膜形成用組成物，其 中，至少含有1種以上述通式（1)所表示之化合物， 以上述通式⑴所表示之化合物中，於上述通式⑴中& 為1之化合物之比例為50質量％以上。 4. 如中請專利範圍第！項之絕緣膜形成用組成物，其 ’相對於換算為（A)成分之完全水解縮合物之⑽重量 份，上述（B)成分為1〜1〇〇〇重量份。 5·如中請專利_第！項之絕賴形成用組成物，其 上述（B)成分之聚苯乙烯換算重量平均分子量為5⑽ 〜10, 000 〇 6. 如中請專利範圍第i項之絕緣卿成用組成物，其 中’上述水解縮合係於鹼性觸媒、酸性觸媒、或金屬螯合 物觸媒之存在下進行。 7. 如申請專利範圍第6項之絕緣臈形成用組成物，其 312XP/發明說明書(補件)/96_〇7/96119467 52 200808907 中’上述水解縮合係於驗性 8如申嗜衷剎，m μ 呆之存在下違仃。 • #專心圍弟7項之絕緣 中，上述鹼性觸媒係以下述 風用、、且成物- (X-X2XYN)hY ......⑷、通式⑷所表示之含氮化合物， 子Γ X、x、χ4為相同或不同，分別表示自氫原 數1〜2(3之烧基1錢基、芳基、以及芳基烧基 所、、且成群組選擇之其，γ本- _ 土 Υ表不齒素原子或1〜4價陰離子 性基，h表示1〜4之整數）。 9·如申晴專利範圍第1項之絕緣膜形成用組成物，其 中’實質上並不存在由4個氧原子取代i個發原子之部位。 、i〇. 一種絕緣膜形成用組成物之製造方法，其包含使（A) 成分與（B)成分水解縮合之步驟，該（A)成分係自以下述通 式（1)所表示之化合物及以下述通式（2)所表示之化合物 的群組選擇之至少丨種矽烷化合物，（趵成分係具有以下 述通式（3 )所表示之構造之碳石夕烧； RlaSi(〇R2)4.a ······⑴ (式中’ R表示1價有機基，R2表示1價有機基，a表示 1〜2之整數） R3b(R40)3-bSi-(R7)d-Si(0R5)3-〇R6c ……（2) (式中’R3〜R6為相同或不同，分別表示1價有機基，b 以及c為相同或不同，表示〇〜2之數，R7表示伸苯基或 以-（CH2),-所表示之基（此處，m為1〜6之整數），d表示 0或1) [化 11] 312XP/發明說明書(補件)/96_〇7/96119467 53 200808907(wherein R8 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a decyloxy group, a sulfonic acid group, a methanesulfonate group, a trifluoromethanesulfonate group, an alkyl group, an aryl group, an allyl group, and a group selected from the group consisting of glycidyl groups, R9 represents a halogen atom, a hydroxyl group, an alkoxy group, a decyloxy group, a sulfonic acid group, an anthracene sulfonate group, 312XP/invention specification (supplement)/96-07/96119467 51 200808907 = aryl 'ene (tetra), and glycidyl group consisting of groups selected, R1 °, RU are the same or different, indicating the self-capacity atom, the thiol, the oxy group, the ethoxylate, the tartaric acid a group selected from the group consisting of a 'methionine group, a trisole, a carbon number of 2 to 6, a aryl group, an allyl group, and a glycidyl group, and R12 to R14 are the same or different. Represents a substituted or unsubstituted methylene group, a stretching group, an alkenyl group, a stretching group, an extended aryl group, and e, f, and g represent 0 to 10, respectively, and satisfy the number 1 〇 <e+f + g<10, 000 conditions). 2. The composition for forming an insulating film according to the item i of the patent application, wherein the component (A) contains the compound represented by the above formula (1). 3. The composition for forming an insulating film according to the second aspect of the invention, wherein at least one compound represented by the above formula (1) is contained, and the compound represented by the above formula (1) is in the above formula (1) The ratio of the compound of &1 is 1% by mass or more. 4. Please ask for the scope of patents! The composition for forming an insulating film is (10) by weight based on the total hydrolyzed condensate of the component (A), and the component (B) is 1 to 1 part by weight. 5. Please ask for a patent _ the first! The composition for the formation of the above-mentioned (B) component has a polystyrene-equivalent weight average molecular weight of 5 (10) to 10, 000 〇 6. The insulating composition of the item i of the patent scope, wherein The hydrolysis condensation is carried out in the presence of a basic catalyst, an acidic catalyst, or a metal chelate catalyst. 7. In the case of the insulating bismuth forming composition of claim 6 of the patent scope, 312XP/invention specification (supplement)/96_〇7/96119467 52 200808907, the above-mentioned hydrolysis condensation is based on the testability 8 , m μ is in violation of the existence of staying. • In the insulation of the 7 items of the Concentration, the above-mentioned basic catalyst is a nitrogen-containing compound represented by the following wind-type, (--X-X2XYN)hY (4), and (4). X, x, and χ4 are the same or different, and each represents a hydrogen atom number of 1 to 2 (3, a ketone group, an aryl group, and an aryl group, and is selected in groups, Γ-- _ Υ Υ 不 不 不 不 不 或 或 或 或 或 不 不 不 不 不 不 不 不 不 。 。 。 。 。 。 9. The composition for forming an insulating film according to item 1 of the Shenqing patent range, wherein 'there is substantially no portion in which one of the atomic atoms is replaced by four oxygen atoms. And a method for producing a composition for forming an insulating film, comprising the step of hydrolyzing and condensing the component (A) and the component (B), wherein the component (A) is a compound represented by the following formula (1) And at least a decane compound selected from the group consisting of the compounds represented by the following formula (2), wherein the oxime component has a carbonaceous structure of a structure represented by the following formula (3); RlaSi (〇R2) 4.a ·······(1) (wherein R represents a monovalent organic group, R2 represents a monovalent organic group, and a represents an integer of 1 to 2) R3b(R40)3-bSi-(R7)d-Si (0R5)3-〇R6c (2) (wherein R3 to R6 are the same or different, respectively represent a monovalent organic group, b and c are the same or different, indicating the number of 〇~2, and R7 is a benzene extending The base or the base represented by -(CH2),- (where m is an integer of 1 to 6), and d represents 0 or 1) [Chem. 11] 312XP/Invention Manual (Supplement)/96_〇7/ 96119467 53 200808907 .....(3) (式中，R8表示自氫原子、鹵素原子、羥基、烷氧基、 醯氧基、磺酸基、甲磺酸基、三氟甲磺酸基、烷基、芳基、 浠丙基、以及縮水甘油基所組成群組選擇之基，r9表示自 鹵素原子、羥基、烷氧基、醯氧基、磺酸基、曱磺酸基、 二氟曱姐基、烧基、芳基、烯丙基、以及縮水甘油基所 組成群組選擇之基，m相同或不同，表示自齒素 原子羥基、烷氧基、醯氧基、續酸基、曱磺酸基、三氟 曱石黃酸基、破數2〜6之烧基、芳基、稀丙基、以及縮水 甘油基所組成群組選擇之基，Rl2〜Rl4為相同或不同，表 不取代或非取代之亞甲基、伸院基、伸稀基、伸快基、伸 芳基’ e、f、g分別表示〇〜1〇，_之數，滿足i〇<e+f + g< 10, 000 之條件）。 U· 一種水解縮合聚合物，係藉由申請專利範圍第10項 之製造方法而獲得。 12. —種二氡化矽系絕緣膜之形成方法，其包含： 將申請專利範圍第i至10項中任一項之絕緣膜形成用 、、且成物塗佈於基板上而形成塗膜之步驟； ^上述塗膜實施自加熱、電子線照射、紫外線照射、以 及乳電漿中選擇之至少1種硬化處理之步驟。 312XP/發明說明書(補件)抓07/96119467 200808907 13. —種二氧化矽系絕緣膜，係藉由申請專利範圍第12 項之二氧化矽系絕緣膜之形成方法而獲得。(3) (wherein R8 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a decyloxy group, a sulfonic acid group, a methanesulfonic acid group, a trifluoromethanesulfonate group, an alkyl group, a group selected from the group consisting of an aryl group, a propyl group, and a glycidyl group, and r9 represents a halogen atom, a hydroxyl group, an alkoxy group, a decyloxy group, a sulfonic acid group, an anthracene sulfonate group, a difluoro fluorenyl group, a group selected from the group consisting of an alkyl group, an aryl group, an allyl group, and a glycidyl group, wherein m is the same or different, and represents a hydroxyl group, an alkoxy group, a decyloxy group, a repeating acid group, an anthracene sulfonate group from a dentate atom. , a group selected from the group consisting of trifluoroanthenic acid, agglomerated 2 to 6 alkyl, aryl, propyl, and glycidyl groups, and R1 to R14 are the same or different, and the table is not substituted or Substituted methylene, stretching base, stretching base, stretching fast base, and extending aryl 'e, f, g respectively represent 〇~1〇, _ number, satisfying i〇<e+f + g<10 , 000 conditions). U. A hydrolytic condensation polymer obtained by the production method of claim 10 of the patent application. 12. A method for forming a bismuth-based lanthanide-based insulating film, comprising: forming an insulating film for forming any one of claims 1-4 to 10, and applying the composition to a substrate to form a coating film Step; The above coating film is subjected to at least one hardening treatment selected from the group consisting of heating, electron beam irradiation, ultraviolet irradiation, and milk plasma. 312XP/Invention Manual (Repair) Grab 07/96119467 200808907 13. A cerium oxide-based insulating film is obtained by a method for forming a cerium oxide-based insulating film of claim 12 of the patent application. 312XP/發明說明書(補件)/96-07/96119467 55 200808907 七、指定代表圖： (一） 本案指定代表圖為：無 (二) 本代表圖之元件符號簡單說明: 無312XP/Invention Manual (supplement)/96-07/96119467 55 200808907 VII. Designation of representative drawings: (1) The representative representative of the case is: None (2) Simple description of the symbol of the representative figure: None 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： R^SiCOR2)^ ……（1) R3b(R40)3-bSi-(R7)d-Si(0R5)3-cR6〇 ……（2)8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: R^SiCOR2)^ (1) R3b(R40)3-bSi-(R7)d-Si(0R5)3-cR6〇... …(2) • 312XP/發明說明書(補件)/96-07/96119467 5• 312XP/Invention Manual (supplement)/96-07/96119467 5
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