TWI766919B

TWI766919B - Manufacturing method of polysilane compound, polysilane compound, cyclic polysilane compound, polysilane composition, polysilane film, and substrate of agglomerated silane film

Info

Publication number: TWI766919B
Application number: TW106144971A
Authority: TW
Inventors: 千坂博樹; 野田国宏; 塩田大
Original assignee: 日商東京應化工業股份有限公司
Priority date: 2016-12-28
Filing date: 2017-12-21
Publication date: 2022-06-11
Also published as: JPWO2018123658A1; WO2018123658A1; TW201835168A; JP6989525B2

Abstract

本發明提供一種殘存金屬(例如Zn、Cu、Fe)較少之聚矽烷化合物之製造方法、包含該聚矽烷化合物之組合物、膜及基板。 The present invention provides a method for producing a polysilane compound with less residual metals (eg, Zn, Cu, Fe), a composition, a film and a substrate comprising the polysilane compound.

本發明之質量平均分子量5000以下之聚矽烷化合物之製造方法包括於下述通式(A1)所表示之有機金屬錯合物及鎂之存在下使鹵矽烷化合物反應。 The method for producing a polysilane compound having a mass average molecular weight of 5000 or less of the present invention includes reacting a halosilane compound in the presence of an organometallic complex represented by the following general formula (A1) and magnesium.

M^pL_p/q (A1) M ^p L _p/q (A1)

(上述通式(A1)中，M^p表示p價之金屬陽離子，L表示q價之有機配位基，p及q分別獨立地表示1以上之整數) (In the above general formula (A1), M ^p represents a p-valent metal cation, L represents a q-valent organic ligand, and p and q each independently represent an integer of 1 or more)

Description

聚矽烷化合物之製造方法、聚矽烷化合物、環狀聚矽烷化合物、聚矽烷組合物、聚矽烷膜、及附聚矽烷膜之基板 Manufacturing method of polysilane compound, polysilane compound, cyclic polysilane compound, polysilane composition, polysilane film, and substrate of agglomerated silane film

本發明係關於一種聚矽烷化合物之製造方法、包含該聚矽烷化合物之組合物、膜及基板。 The present invention relates to a method for producing a polysilane compound, a composition, a film and a substrate comprising the polysilane compound.

聚矽烷化合物係於陶瓷前驅物、光電子材料(例如光阻劑、有機感光體等光電子照相材料、光波導等光傳輸材料、光記憶體等光記錄材料、電致發光元件用材料)、各種元件中之層間絕緣膜、如LED(Light Emitting Diode，發光二極體)元件或有機EL(Electroluminescence，電致發光)元件之類的發光元件之密封材料、向半導體基板之雜質擴散用之塗佈膜、及半導體製程用之間隙填充材料等用途中使用，於該等尖端材料領域中，對於去除原料中之金屬成分，要求較高。又，於包括微細加工或多層製程之製造步驟中，要求填埋基板上之凹凸之間隙填充特性，或者要求耐化學品性或加工性之容易性。 Polysilane compounds are used in ceramic precursors, optoelectronic materials (such as photoresist, photoelectronphotographic materials such as organic photoreceptors, optical transmission materials such as optical waveguides, optical recording materials such as optical memory, materials for electroluminescence elements), various elements Interlayer insulating film, sealing material for light-emitting elements such as LED (Light Emitting Diode) elements or organic EL (Electroluminescence, electroluminescence) elements, coating films for impurity diffusion to semiconductor substrates , and gap filling materials for semiconductor processes. In the field of these cutting-edge materials, there is a high requirement for removing metal components from raw materials. In addition, in the manufacturing steps including microfabrication or multi-layer processes, gap-filling properties for filling the unevenness on the substrate, chemical resistance or ease of processability are required.

作為此種聚矽烷化合物之製造方法，例如於專利文獻1中揭示有一種於氯化鋅等金屬鹵化物之存在下使金屬鎂與鹵矽烷化合物反應而製造聚矽烷之方法。 As a method for producing such a polysilane compound, for example, Patent Document 1 discloses a method for producing a polysilane by reacting metal magnesium and a halosilane compound in the presence of a metal halide such as zinc chloride.

於使用氯化鋅等金屬鹵化物之製造方法中，於製造後之聚矽烷中，因矽-金屬鍵導致鋅等金屬殘存而難以減少殘存金屬。存在上述殘存金屬可能會損害作為包含上述聚矽烷之膜等光電子材料之性能之問題。 In the production method using a metal halide such as zinc chloride, in the polysilane after production, metals such as zinc remain due to the silicon-metal bond, and it is difficult to reduce the remaining metal. There is a problem that the above-mentioned residual metal may impair performance as an optoelectronic material such as a film containing the above-mentioned polysilane.

又，若謀求以減少殘存金屬為目的而製造之聚矽烷之高分子量化，則存在間隙填充特性劣化之困擾。 In addition, when the high molecular weight of the polysilane produced for the purpose of reducing the residual metal is sought, there is a problem that the gap-filling property deteriorates.

又，於專利文獻2中記載有一種於製造聚矽烷後使用氯化銅等金屬化合物將殘存金屬去除之精製方法。 In addition, Patent Document 2 describes a purification method for removing residual metals using a metal compound such as copper chloride after the production of polysilane.

然而，於使用氯化銅等金屬化合物之精製中，存在聚矽烷中之末端因水解而矽烷醇(Si-OH)化，從而導致聚矽烷發生矽氧烷化之問題。又，已知聚矽烷中之矽烷醇化亦可能會導致包含上述聚矽烷之膜之性能降低(例如產生龜裂)。 However, in the purification using metal compounds such as copper chloride, there is a problem that the terminal in the polysilane is hydrolyzed to silanol (Si-OH), thereby causing the polysilane to be siloxaneated. Also, it is known that silylation in polysilanes may also result in reduced performance (eg, cracking) of films comprising the above-mentioned polysilanes.

[先前技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利第5571992號公報 [Patent Document 1] Japanese Patent No. 5571992

[專利文獻2]日本專利第5658608號公報 [Patent Document 2] Japanese Patent No. 5658608

本發明係鑒於上述先前技術之問題，其目的在於提供一種殘存金屬(例如Zn、Cu、Fe)較少之聚矽烷化合物之製造方法、包含該聚矽烷化合物之組合物、膜及基板。 In view of the above-mentioned problems of the prior art, the present invention aims to provide a method for producing a polysilane compound with less residual metals (eg, Zn, Cu, Fe), a composition, a film and a substrate comprising the polysilane compound.

本發明者等人發現，於聚矽烷化合物之製造方法中，藉由使用特定之有機金屬錯合物，而抑制所製造之聚矽烷化合物之矽氧烷化及達成5000以下之質量平均分子量，可減少殘存金屬，從而完成了本發明。 The inventors of the present invention have found that, in the method for producing a polysilane compound, by using a specific organometallic complex, the siloxanization of the produced polysilane compound can be suppressed and the mass average molecular weight of 5000 or less can be achieved. The residual metal was reduced, and the present invention was completed.

本發明之第1態樣係一種質量平均分子量5000以下之聚矽烷化合物之製造方法，其包括於下述通式(A1)所表示之有機金屬錯合物及鎂之存在下使鹵矽烷化合物反應。 A first aspect of the present invention is a method for producing a polysilane compound having a mass average molecular weight of 5,000 or less, which comprises reacting a halosilane compound in the presence of an organometallic complex represented by the following general formula (A1) and magnesium .

M^pL_p/q (A1) M ^p L _p/q (A1)

本發明之第2態樣係一種質量平均分子量5000以下之聚矽烷化合物，其中下述(2X)相對於下述(1X)及(2X)之波峰之面積之和的比即下述式(3X)所表示之比率為0.4以下，上述波峰之面積係將聚矽烷化合物中藉由X射線光電子光譜法測定之於99eV以上且104eV以下之鍵結能量範圍內具有最大檢測波峰高度之光譜進行波峰分離而求出，並且上述聚矽烷化合物中之金屬之含量為500ppb以下。 The second aspect of the present invention is a polysilane compound having a mass average molecular weight of 5,000 or less, wherein the ratio of the following (2X) to the sum of the areas of the peaks of the following (1X) and (2X) is the following formula (3X ) is less than or equal to 0.4, and the area of the above-mentioned peaks is determined by X-ray photoelectron spectroscopy in the polysilane compound with the maximum detection peak height within the range of 99eV or more and 104eV or less. Then, the content of the metal in the above-mentioned polysilane compound was found to be 500 ppb or less.

(1X)‧‧‧於鍵結能量為99.0eV以上且99.5eV以下之範圍內具有最大檢測波峰高度之波峰之面積 (1X)‧‧‧The area of the peak with the maximum detection peak height in the range of bonding energy of 99.0eV or more and 99.5eV or less

(2X)‧‧‧於鍵結能量為100eV以上且104eV以下之範圍內具有最大檢測波峰高度之波峰之面積 (2X)‧‧‧The area of the peak with the maximum detection peak height in the range of bonding energy of 100eV or more and 104eV or less

(3X)‧‧‧(2X)/[(1X)+(2X)] (3X)‧‧‧(2X)/[(1X)+(2X)]

本發明之第3態樣係一種組合物，其包含第2態樣之聚矽烷化合物。 A third aspect of the present invention is a composition comprising the polysilane compound of the second aspect.

本發明之第4態樣係一種膜，其包含第2態樣之聚矽烷化合物。 A fourth aspect of the present invention is a film comprising the polysilane compound of the second aspect.

本發明之第5態樣係一種基板，其具備包含第2態樣之聚矽烷化合物之膜。 The 5th aspect of this invention is a board|substrate provided with the film containing the polysilane compound of 2nd aspect.

根據本發明，可提供一種殘存金屬(例如Zn、Cu、Fe)較少之聚矽烷化合物之製造方法、包含該聚矽烷化合物之組合物、膜及基板。 According to the present invention, a method for producing a polysilane compound with less residual metals (eg, Zn, Cu, Fe), a composition, a film and a substrate comprising the polysilane compound can be provided.

以下，對本發明之實施態樣詳細地進行說明，但本發明並不受以下之實施態樣任何限定，可於本發明之目的之範圍內適當添加變更而實施。 Hereinafter, the embodiment of the present invention will be described in detail, but the present invention is not limited to the following embodiment at all, and can be implemented with appropriate additions and modifications within the scope of the object of the present invention.

又，於本說明書中，若無特別說明，則「~」表示以上至以下。 In addition, in this specification, unless otherwise specified, "~" represents the above to the following.

<聚矽烷化合物之製造方法> <Method for producing polysilane compound>

第1態樣之聚矽烷化合物之製造方法係包括於上述通式(A1)所表示之有機金屬錯合物及鎂之存在下使鹵矽烷化合物反應之聚矽烷化合物之製造方法。 The method for producing a polysilane compound of the first aspect includes a method for producing a polysilane compound in which a halosilane compound is reacted in the presence of the organometallic complex represented by the general formula (A1) and magnesium.

根據第1態樣之聚矽烷化合物之製造方法，藉由使用上述通式(A1)所表示之有機金屬錯合物，可減少殘存金屬。 According to the manufacturing method of the polysilane compound of the 1st aspect, by using the organometallic complex represented by the said general formula (A1), residual metal can be reduced.

又，所製造之聚矽烷化合物之質量平均分子量達成5000以下，亦可改善間隙填充特性。 In addition, when the mass average molecular weight of the produced polysilane compound is 5000 or less, the gap filling properties can also be improved.

(有機金屬錯合物) (Organometallic Complex)

第1態樣之聚矽烷化合物之製造方法中，鹵矽烷化合物之反應係於下述通式(A1)所表示之有機金屬錯合物之存在下進行。 In the method for producing the polysilane compound of the first aspect, the reaction of the halosilane compound is performed in the presence of the organometallic complex represented by the following general formula (A1).

M^pL_p/q (A1) M ^p L _p/q (A1)

作為構成p價之金屬陽離子M^p之金屬原子，可列舉選自由鐵、銀、鋁、鉍、鈰、鈷、銅、鏑、鉺、銪、鎵、釓、鉿、鈥、銦、銥、鑭、鎦、錳、鉬、釹、鎳、鋨、鈀、鉕、鐠、鉑、錸、銠、釕、釤、鈧、錫、鋱、鈦、銩、釩、鉻、鉭、鐿、金、水銀、鎢、釔、鋅及鋯所組成之群中之金屬。 Examples of the metal atom constituting the ^p -valent metal cation Mp include iron, silver, aluminum, bismuth, cerium, cobalt, copper, dysprosium, erbium, europium, gallium, gadolinium, hafnium, ∥, indium, iridium, and lanthanum. , tungsten, manganese, molybdenum, neodymium, nickel, osmium, palladium, strontium, strontium, platinum, rhenium, rhodium, ruthenium, samarium, scandium, tin, tantalum, titanium, strontium, vanadium, chromium, tantalum, ytterbium, gold, mercury , a metal in the group consisting of tungsten, yttrium, zinc and zirconium.

作為p，較佳為1~4之整數，更佳為1~3之整數，進而較佳為2或3。 As p, an integer of 1 to 4 is preferable, an integer of 1 to 3 is more preferable, and 2 or 3 is still more preferable.

作為q，較佳為1~4之整數，更佳為1~3之整數，進而較佳為1或2。 As q, an integer of 1 to 4 is preferable, an integer of 1 to 3 is more preferable, and 1 or 2 is still more preferable.

作為q價之有機配位基L，可列舉：乙醯丙酮等β-二酮酸鹽配位基、烯烴、共軛酮、腈、胺、羧酸鹽配位基、一氧化碳、膦、亞膦酸鹽、膦酸鹽、亞磷酸鹽等有機配位基。q價之有機配位基L亦可為螯合物配位基。 Examples of the q-valent organic ligand L include β-diketonate ligands such as acetone acetone, Organic ligands such as alkenes, conjugated ketones, nitriles, amines, carboxylate ligands, carbon monoxide, phosphines, phosphites, phosphonates, phosphites, etc. The q-valent organic ligand L may also be a chelate ligand.

作為上述有機金屬錯合物，較佳為下述通式(A2)所表示之有機金屬錯合物。 As said organometallic complex, the organometallic complex represented by following general formula (A2) is preferable.

(上述通式(A2)中，M表示選自由鐵、銀、鋁、鉍、鈰、鈷、銅、鏑、鉺、銪、鎵、釓、鉿、鈥、銦、銥、鑭、鎦、錳、鉬、釹、鎳、鋨、鈀、鉕、鐠、鉑、錸、銠、釕、釤、鈧、錫、鋱、鈦、銩、釩、鉻、鉭、鐿、金、水銀、鎢、釔、鋅及鋯所組成之群中之金屬，R^a1分別獨立地表示飽和烴基、不飽和烴基、芳香族烴基、芳烷基、烷氧基、芳氧基、芳烷氧基或芳氧基烷基，R^a2表示氫原子、飽和烴基、不飽和烴基、芳香族烴基或芳烷基；p表示1以上之整數) (In the above-mentioned general formula (A2), M represents selected from iron, silver, aluminum, bismuth, cerium, cobalt, copper, dysprosium, erbium, europium, gallium, gadolinium, hafnium, ∥, indium, iridium, lanthanum, tungsten, manganese , Molybdenum, Neodymium, Nickel, Osmium, Palladium, Ni, Fe, Pt, Rhenium, Rhodium, Ruthenium, Samarium, Scandium, Tin, Tb, Titanium, V, Vanadium, Chromium, Tantalum, Ytterbium, Gold, Mercury, Tungsten, Yttrium , a metal in the group consisting of zinc and zirconium, R ^a1 independently represents a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkoxy group or an aryloxyalkane group group, R ^a2 represents a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or an aralkyl group; p represents an integer of 1 or more)

作為R^a1及R^a2所表示之飽和烴基，可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十四烷基、十六烷基、十八烷基、二十烷基、二十二烷基、2-十二烷基十六烷基、三十烷基、三十二烷基、四十烷基等碳數1~40之直鏈狀或支鏈狀烷基；進而該等經鹵素原子(氟原子、氯原子、溴原子、碘原子)、烷氧基(下述所記載者等)、矽烷基(下述所記載者等)等取代基之1種或2種以上取代而成之烷基，例如氯丙基、3,3,3-三氟丙基、3,3,4,4,5,5,6,6,6-九氟己基、十三氟-1,1,2,2-四氫辛基、十七氟-1,1,2,2-四氫癸基、3-(七氟異丙氧基)丙基、三甲基矽烷基甲基等；環丙基、環丁基、環戊基、環己基、雙環庚基、環辛基、金剛烷基等碳數3~18之單環或2環以上之多環之環狀飽和烴基；進而該等環狀飽和烴基經烷基(上述者等)、芳基(上述者等)等取代基之1種或2種以上取代而成者，例如4-第三丁基環己基、4-苯基環己基等；或者具有上述環狀飽和烴基之烷基(上述者等)，例如環己基甲基、金剛烷基乙基等。 Examples of the saturated hydrocarbon group represented by R ^a1 and R ^a2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, behenyl, 2- Dodecylhexadecyl, tridecyl, tridodecyl, tetradecyl and other linear or branched alkyl groups with 1 to 40 carbon atoms; , chlorine atom, bromine atom, iodine atom), alkoxy group (described below, etc.), silyl group (described below, etc.) and other substituents, an alkyl group substituted by one or two or more kinds, For example, chloropropyl, 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2- Tetrahydrooctyl, heptafluoro-1,1,2,2-tetrahydrodecyl, 3-(heptafluoroisopropoxy)propyl, trimethylsilylmethyl, etc.; cyclopropyl, cyclobutyl Monocyclic or polycyclic cyclic saturated hydrocarbon groups with carbon number of 3 to 18 such as base, cyclopentyl, cyclohexyl, bicycloheptyl, cyclooctyl, adamantyl, etc.; and these cyclic saturated hydrocarbon groups are One or more of substituents such as alkyl (the above), aryl (the above, etc.), substituted by one or more, such as 4-tert-butylcyclohexyl, 4-phenylcyclohexyl, etc.; or The alkyl group of the above-mentioned cyclic saturated hydrocarbon group (the above-mentioned, etc.), for example, cyclohexylmethyl, adamantylethyl and the like.

作為R^a1及R^a2所表示之不飽和烴基，可列舉：乙烯基、乙炔基、烯丙基、1-丙烯基、炔丙基、丁烯基、戊烯基、己烯基、辛烯基、癸烯基、十二烯基、十八烯基等碳數2~18之直鏈狀或支鏈狀烯基、炔基；進而該等不飽和烴基經鹵素原子(上述者等)、烷氧基(下述所記載者等)、矽烷基(下述所記載者等)、芳基(下述所記載者等)之取代基之1種或2種以上取代而成者，例如2-三氟甲基乙烯基、2-三氟甲基乙炔基、3-甲氧基-1-丙烯基、3-甲氧基-1-丙炔基、2-三甲基矽烷基乙烯基、2-三甲基矽烷基乙炔基、2-苯基乙烯基、2-苯基乙炔基等；環丙烯基、環己烯基、環辛烯基等碳數3~18之環狀不飽和烴基；具有上述環狀不飽和烴基之烷基(上述者等)，例如環己烯基乙基等。 Examples of the unsaturated hydrocarbon group represented by R ^a1 and R ^a2 include vinyl, ethynyl, allyl, 1-propenyl, propargyl, butenyl, pentenyl, hexenyl, and octenyl , decenyl, dodecenyl, octadecenyl and other linear or branched alkenyl and alkynyl groups with 2 to 18 carbon atoms; One or two or more of substituents of oxy (described below, etc.), silyl group (described below, etc.), aryl (described below, etc.) are substituted, for example, 2- Trifluoromethylvinyl, 2-trifluoromethylethynyl, 3-methoxy-1-propenyl, 3-methoxy-1-propynyl, 2-trimethylsilylvinyl, 2 -Trimethylsilylethynyl, 2-phenylethynyl, 2-phenylethynyl, etc; The alkyl group having the above-mentioned cyclic unsaturated hydrocarbon group (the above-mentioned, etc.), for example, cyclohexenylethyl and the like.

作為R^a1及R^a2所表示之芳香族烴基，可列舉：苯基、及甲苯基、丁基苯基、丁氧基苯基等經烷基、烷氧基、胺基等1種或2種以上取代而成之取代苯基等。 Examples of the aromatic hydrocarbon group represented by R ^a1 and R ^a2 include one or two types of phenyl groups, alkyl groups such as tolyl groups, butylphenyl groups, butoxyphenyl groups, alkoxy groups, and amino groups, etc. Substituted phenyl and the like formed by the above substitution.

作為R^a1及R^a2所表示之芳烷基，可列舉：苄基、苯乙基、甲基苯乙基、丁基苯乙基、苯基丙基、甲氧基苯基丙基等，作為雜芳烷基，可列舉：吡啶基甲基、吡啶基乙基等。 Examples of the aralkyl group represented by R ^a1 and R ^a2 include benzyl, phenethyl, methylphenethyl, butylphenethyl, phenylpropyl, methoxyphenylpropyl, and the like. As a heteroaralkyl group, a pyridylmethyl group, a pyridylethyl group, etc. are mentioned.

作為R^a1所表示之烷氧基，可列舉：甲氧基、乙氧基、丙氧基、丁氧基、己氧基、辛氧基等碳數1~18之烷氧基，作為芳氧基，可列舉：苯氧基、及甲苯氧基、丁基苯氧基等經烷基等取代基取代而成之取代苯氧基等。 Examples of the alkoxy group represented by R ^a1 include alkoxy groups having 1 to 18 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, and octyloxy, and aryloxy groups. Examples of the group include a phenoxy group, a substituted phenoxy group such as a tolyloxy group and a butylphenoxy group substituted with a substituent such as an alkyl group.

作為R^a1所表示之芳烷氧基，可列舉：苄氧基、苯乙氧基等，作為芳氧基烷基，可列舉：苯氧基丙基、苯氧基丁基等。 As an aralkoxy group represented by R ^a1 , a benzyloxy group, a phenethoxy group, etc. are mentioned, and a phenoxypropyl group, a phenoxybutyl group, etc. are mentioned as an aryloxyalkyl group.

作為R^a1，較佳為碳數為1~30之飽和烴基、芳香族烴基等，進而較佳為碳數為1~15之烷基、苯基等，尤佳為甲基。 R ^a1 is preferably a saturated hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group, or the like, more preferably an alkyl group having 1 to 15 carbon atoms, a phenyl group, or the like, and particularly preferably a methyl group.

作為R^a2，較佳為氫原子、碳數為1~18之飽和烴基、芳香族烴基等，進而較佳為氫原子、碳數為1~10之烷基、苯基、苯基乙基等，尤佳為氫原子。 R ^a2 is preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 18 carbon atoms, an aromatic hydrocarbon group, or the like, and more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, a phenylethyl group, or the like , preferably a hydrogen atom.

較佳為R^a1表示甲基，R^a2表示氫原子。 Preferably, R ^a1 represents a methyl group, and R ^a2 represents a hydrogen atom.

p之較佳例如上所述。 Preferred examples of p are as described above.

作為金屬錯合物，可根據上述金屬M與R^a1及R^a2之組合而列舉各種金屬錯合物。若例示具體例，則可列舉：乙醯丙酮銀(I)、三(乙醯丙酮)鋁(III)、三(2,2,6,6-四甲基-3,5-庚二酮)鋁(III)、三(2,2,6,6-四甲基-3,5-庚二酮)鉍(III)、三(乙醯丙酮)鈰(III)、雙(乙醯丙酮)鈷(II)、三(乙醯丙酮)鈷(III)、三(1,3-二苯基-1,3-丙二酮)鈷(III)、三(3-甲基-2,4-戊二酮)鈷(III)、三(3-苯基-2,4-戊二酮)鈷(III)、三(3-(1-苯基乙基)-2,4-戊二酮)鈷(III)、雙(苯甲醯丙酮)鈷(II)雙(六氟乙醯丙酮)鈷(II)、三(2,2,6,6-四甲基-3,5-庚二酮)鈷(III)、雙(乙醯丙酮)銅(II)、雙(2,2,6,6-四甲基-3,5-庚二酮)銅(II)、三(2,2,4,6,6-五甲基-3,5-庚二酮)鈷(III)、三(2,2,6,6-四甲基-4-(1-苯基乙基)-3,5-庚二酮)鈷(III)、三(2,2,6,6-四甲基-4-苯基-3,5-庚二酮)鈷(III)、雙(六氟乙醯丙酮)銅(II)、雙(三氟乙醯丙酮)銅(II)、三(乙醯丙酮)鏑(III)、三(乙醯丙酮)鉺(III)、三(2,2,6,6-四甲基-3,5-庚二酮)鉺(III)、三(乙醯丙酮)銪(III)、雙(乙醯丙酮)鐵(II)、三(乙醯丙酮)鐵(III)、三(1,3-二苯基-1,3-丙二酮)鐵(III)、三(3-甲基-2,4-戊二酮)鐵(III)、三(3-苯基-2,4-戊二酮)鐵(III)、三(3-(1-苯基乙基)-2,4-戊二酮)鐵(III)、三(2,2,6,6-四甲基-3,5-庚二酮)鐵(III)、三(2,2,4,6,6-五甲基-3,5-庚二酮)鐵(III)、三(2,2,6,6-四甲基-4-(1-苯基乙基)-3,5-庚二酮)鐵(III)、三(2,2,6,6-四甲基-4-苯基-3,5-庚二酮)鐵(III)、四(乙醯丙酮)鉿(IV)、三(乙醯丙酮)鎵(III)、三(乙醯丙酮)釓(III)、三(乙醯丙酮)鈥(III)、三(乙醯丙酮)銦(III)、三(乙醯丙酮)銥(III)、三(乙醯丙酮)鑭(III)、三(乙醯丙酮)鎦(III)、雙(乙醯丙酮)錳(II)、三(乙醯丙酮)錳(III)、雙(六氟乙醯丙酮)錳(II)、雙(乙醯丙酮)二氧化鉬(IV)、三(乙醯丙酮)釹(III)、三(2,2,6,6-四甲基-3,5-庚二酮)釹(III)、雙(乙醯丙酮)鎳(II)、雙(2,2,6,6-四甲基-3,5-庚二酮)鎳(II)、雙(六氟乙醯丙酮)鎳(II)、雙(1,3-二苯基-1,3-丙二酮)鎳(II)、雙(3-甲基-2,4-戊二酮)鎳(II)、雙(3-苯基-2,4-戊二酮)鎳(II)、雙(3-(1-苯基乙基)-2,4-戊二酮)鎳(II)、雙(2,2,4,6,6-五甲基-3,5-庚二酮)鎳(II)、雙(2,2,6,6-四甲基-4-(1-苯基乙基)-3,5-庚二酮)鎳(II)、雙(2,2,6,6-四甲基-4-苯基-3,5-庚二酮)鎳(II)、雙(乙醯丙酮)鈀(II)、雙(六氟乙醯丙酮)鈀(II)、雙(1,3-二苯基-1,3-丙二酮)鈀(II)、雙(3-甲基-2,4-戊二酮)鈀(II)、雙(3-苯基-2,4-戊二酮)鈀(II)、雙(3-(1-苯基乙基)-2,4-戊二酮)鈀(II)、雙(2,2,4,6,6-五甲基-3,5-庚二酮)鈀(II)、雙(2,2,6,6-四甲基-4-(1-苯基乙基)-3,5-庚二酮)鈀(II)、雙 (2,2,6,6-四甲基-4-苯基-3,5-庚二酮)鈀(II)、三(乙醯丙酮)鉕(III)、三(乙醯丙酮)鐠(III)、三(六氟乙醯丙酮)鐠(III)、雙(乙醯丙酮)鉑(II)、三(乙醯丙酮)銠(III)、三(乙醯丙酮)釕(III)、三(乙醯丙酮)鈧(III)、三(六氟乙醯丙酮)鈧(III)、三(2,2,6,6-四甲基-3,5-庚二酮)鈧(III)、三(乙醯丙酮)釤(III)、三(2,2,6,6-四甲基-3,5-庚二酮)釤(III)、雙(乙醯丙酮)錫(II)、三(乙醯丙酮)鋱(III)、三(2,2,6,6-四甲基-3,5-庚二酮)鋱(III)、三(2,2,6,6-四甲基-3,5-庚二酮)銩(III)、三(乙醯丙酮)釩(III)、三(乙醯丙酮)釔(III)、三(六氟乙醯丙酮)釔(III)、三(2,2,6,6-四甲基-3,5-庚二酮)釔(III)、雙(乙醯丙酮)鋅(II)、雙(六氟乙醯丙酮)鋅(II)、雙(2,2,6,6-四甲基-3,5-庚二酮)鋅(II)、四(乙醯丙酮)鋯(IV)、四(2,2,6,6-四甲基-3,5-庚二酮)鋯(IV)、四(三氟乙醯丙酮)鋯(IV)等。 As a metal complex, various metal complexes can be mentioned according to the combination of the said metal M, R ^a1 , and R ^a2 . Specific examples include silver (I) acetylacetonate, aluminum (III) tris(acetylacetonate), tris(2,2,6,6-tetramethyl-3,5-heptanedione) Aluminum(III), Tris(2,2,6,6-tetramethyl-3,5-heptanedione)bismuth(III), Tris(acetylacetonate)cerium(III), bis(acetylacetone)cobalt (II), Tris(acetylacetone)cobalt(III), Tris(1,3-diphenyl-1,3-propanedione)cobalt(III), Tris(3-methyl-2,4-pentane) Diketone) cobalt(III), tris(3-phenyl-2,4-pentanedione)cobalt(III), tris(3-(1-phenylethyl)-2,4-pentanedione)cobalt (III), bis(benzylacetone)cobalt(II) bis(hexafluoroacetone)cobalt(II), tris(2,2,6,6-tetramethyl-3,5-heptanedione) Cobalt(III), Bis(acetylacetone)copper(II), Bis(2,2,6,6-tetramethyl-3,5-heptanedione)copper(II), Tris(2,2,4 ,6,6-pentamethyl-3,5-heptanedione) cobalt(III), tris(2,2,6,6-tetramethyl-4-(1-phenylethyl)-3,5 -Heptanedione)cobalt(III), tris(2,2,6,6-tetramethyl-4-phenyl-3,5-heptanedione)cobalt(III), bis(hexafluoroacetone) Copper(II), Bis(trifluoroacetone acetone)copper(II), Tris(acetylacetone)dysprosium(III), Tris(acetylacetone)erbium(III), Tris(2,2,6,6- Tetramethyl-3,5-heptanedione) Erbium(III), Tris(acetoacetone)Europium(III), Bis(acetoacetone)iron(II), Tris(acetoacetone)iron(III), Tris(1,3-diphenyl-1,3-propanedione)iron(III), tris(3-methyl-2,4-pentanedione)iron(III), tris(3-phenyl- 2,4-Pentanedione)iron(III), tris(3-(1-phenylethyl)-2,4-pentanedione)iron(III), tris(2,2,6,6-tetrakis) Methyl-3,5-heptanedione)iron(III), tris(2,2,4,6,6-pentamethyl-3,5-heptanedione)iron(III), tris(2,2 ,6,6-Tetramethyl-4-(1-phenylethyl)-3,5-heptanedione)iron(III), tris(2,2,6,6-tetramethyl-4-benzene) yl-3,5-heptanedione)iron(III), tetrakis(acetoacetone)hafnium(IV), tris(acetoacetone)gallium(III), tris(acetoacetone)glium(III), tris(acetone) Acetylacetone)—(III), Tris(Acetylacetone)Indium(III), Tris(Acetylacetone)Iridium(III), Tris(Acetylacetone)Lanthanum(III), Tris(Acetylacetone)Li(III) III), bis(acetylacetone)manganese(II), tris(acetylacetone)manganese(III), bis(hexafluoroacetone)manganese(II), bis(acetylacetone)molybdenum(IV) dioxide , tris (acetone acetone) neodymium (III), tris (2,2,6,6-tetramethyl-3,5-heptanedione) neodymium (III), bis(acetylacetone)nickel(II), bis(2,2,6,6-tetramethyl-3,5-heptanedione)nickel(II), bis(hexafluoroacetone) Nickel(II), Bis(1,3-diphenyl-1,3-propanedione)nickel(II), Bis(3-methyl-2,4-pentanedione)nickel(II), Bis( 3-Phenyl-2,4-pentanedione)nickel(II), bis(3-(1-phenylethyl)-2,4-pentanedione)nickel(II), bis(2,2, 4,6,6-Pentamethyl-3,5-heptanedione)nickel(II), bis(2,2,6,6-tetramethyl-4-(1-phenylethyl)-3, 5-Heptanedione)nickel(II), bis(2,2,6,6-tetramethyl-4-phenyl-3,5-heptanedione)nickel(II), bis(acetoacetone)palladium (II), bis(hexafluoroacetone)palladium(II), bis(1,3-diphenyl-1,3-propanedione)palladium(II), bis(3-methyl-2,4 -Pentanedione)palladium(II), bis(3-phenyl-2,4-pentanedione)palladium(II), bis(3-(1-phenylethyl)-2,4-pentanedione ) palladium(II), bis(2,2,4,6,6-pentamethyl-3,5-heptanedione)palladium(II), bis(2,2,6,6-tetramethyl-4 -(1-Phenylethyl)-3,5-heptanedione)palladium(II), bis(2,2,6,6-tetramethyl-4-phenyl-3,5-heptanedione) Palladium(II), Tris(acetylacetone)(III), Tris(acetylacetone)(III), Tris(hexafluoroacetone)(III), bis(acetylacetone)platinum(II) , Tris (acetylacetone) rhodium (III), tris (acetylacetone) ruthenium (III), tris (acetylacetone) scandium (III), tris (hexafluoroacetone) scandium (III), tris (2 ,2,6,6-Tetramethyl-3,5-heptanedione)scandium(III), tris(acetylacetone)samarium(III), tris(2,2,6,6-tetramethyl-3 ,5-heptanedione) samarium(III), bis(acetylacetone)tin(II), tris(acetylacetone)samarium(III), tris(2,2,6,6-tetramethyl-3, 5-Heptanedione) abium (III), tris (2,2,6,6-tetramethyl-3,5-heptanedione) quinone (III), tris (acetone acetone) vanadium (III), tris (acetylacetone)yttrium(III), tris(hexafluoroacetylacetone)yttrium(III), tris(2,2,6,6-tetramethyl-3,5-heptanedione)yttrium(III), Bis(acetylacetone)zinc(II), bis(hexafluoroacetylacetone)zinc(II), bis(2,2,6,6-tetramethyl-3,5-heptanedione)zinc(II) , Tetrakis (acetylacetonate) zirconium (IV), tetrakis (2,2,6,6-tetramethyl-3,5-heptanedione) zirconium (IV), tetrakis (trifluoroacetone acetone) zirconium (IV) )Wait.

該等有機金屬錯合物可單獨使用或將2種以上組合使用。作為有機金屬錯合物，可使用預先合成之金屬錯合物，亦可使用於體系中製造者。 These organometallic complexes can be used alone or in combination of two or more. As the organometallic complex, a pre-synthesized metal complex can be used, or one produced in a system can also be used.

上述有機金屬錯合物之使用量相對於鹵矽烷化合物，較佳為0.0001~10莫耳倍之範圍，更佳為0.0005~1莫耳倍之範圍，尤佳為0.001~0.1莫耳倍之範圍。 The usage amount of the above-mentioned organometallic complex is preferably in the range of 0.0001 to 10 mol times, more preferably 0.0005 to 1 mol times, and particularly preferably 0.001 to 0.1 mol times, relative to the halosilane compound. .

(鎂) (magnesium)

於第1態樣之聚矽烷化合物之製造方法中，鹵矽烷化合物之反應係於鎂之存在下進行。 In the method for producing the polysilane compound of the first aspect, the reaction of the halosilane compound is performed in the presence of magnesium.

鎂可作為使鹵矽烷化合物脫鹵素縮聚合之還原劑發揮功能(「鎂還原法」、WO98/29476號公報、日本專利特開2003-277507號公報所記載之方法等)。 Magnesium can function as a reducing agent for dehalogenation polycondensation of halosilane compounds (“magnesium reduction method”, methods described in WO98/29476, Japanese Patent Laid-Open No. 2003-277507, etc.).

作為鎂，可為金屬鎂(鎂單質)之形態、鎂合金之形態，亦可為該等之混合物等(以下，亦簡稱為「鎂成分」)。 Magnesium may be in the form of metallic magnesium (magnesium simple substance), in the form of magnesium alloy, or in the form of these. Mixtures and the like (hereinafter, also simply referred to as "magnesium components").

鎂合金之種類並無特別限制，可例示慣用之鎂合金、例如包含鋁、鋅、稀土類元素(鈧、釔等)等成分之鎂合金。 The type of magnesium alloy is not particularly limited, and examples thereof include commonly used magnesium alloys, for example, magnesium alloys containing components such as aluminum, zinc, and rare earth elements (scandium, yttrium, etc.).

作為鎂成分之形狀，只要無損鹵矽烷化合物之反應，則並無特別限定，可例示：粉粒狀(粉體、粒狀體等)、帶狀體、切削片狀體、塊狀體、棒狀體、板狀體(平板狀等)等，尤佳為粉體、粒狀體、帶狀體、切削片狀體等。鎂(例如粉粒狀之鎂)之平均粒徑例如可為1~10000μm，較佳為10~7000μm，進而較佳為15~5000μm(例如20~3000μm)。 The shape of the magnesium component is not particularly limited as long as the reaction of the halosilane compound is not impaired, and examples thereof include powder particles (powders, granules, etc.), strips, chips, lumps, and rods. A powder, a granular body, a belt-shaped body, a chip-shaped body, etc. are particularly preferable. The average particle size of magnesium (eg, powdered magnesium) may be, for example, 1-10,000 μm, preferably 10-7,000 μm, and more preferably 15-5,000 μm (eg, 20-3,000 μm).

上述鎂成分可單獨使用，亦可將2種以上組合使用。 The above-mentioned magnesium components may be used alone or in combination of two or more.

鎂成分之使用量相對於鹵矽烷化合物之鹵素原子，以鎂換算計，較佳為1~20當量，更佳為1.1~14當量，進而較佳為1.2~10當量，尤佳為1.2~5當量。 The use amount of the magnesium component is preferably 1 to 20 equivalents, more preferably 1.1 to 14 equivalents, more preferably 1.2 to 10 equivalents, and particularly preferably 1.2 to 5 equivalents, in terms of magnesium conversion, relative to the halogen atoms of the halosilane compound. equivalent.

又，鎂之使用量相對於鹵矽烷化合物，以莫耳數計，就鎂而言，較佳為1~20倍，更佳為1.1~14倍，進而較佳為1.2~10倍，尤佳為1.2~5倍。 In addition, the amount of magnesium to be used is preferably 1 to 20 times, more preferably 1.1 to 14 times, and further preferably 1.2 to 10 times, more preferably 1.2 to 10 times, in terms of molar number relative to the halosilane compound. 1.2 to 5 times.

(鹵矽烷化合物) (halosilane compound)

於第1態樣之聚矽烷化合物之製造方法中，作為鹵矽烷化合物，較佳為下述式(1)所表示之化合物。 In the method for producing a polysilane compound of the first aspect, the halosilane compound is preferably a compound represented by the following formula (1).

X_nSiR_4-n (1) X _n SiR _4-n (1)

(式中，n為2~4之整數，n個X分別獨立地為鹵素原子，(4-n)個R分別獨立地為氫原子、有機基或矽烷基) (in the formula, n is an integer from 2 to 4, n X’s are each independently a halogen atom, (4-n) R’s are each independently a hydrogen atom, an organic group or a silyl group)

作為X所表示之鹵素原子，可列舉：氟原子、氯原子、溴原子或碘原子，較佳為氯原子或溴原子，更佳為氯原子。 As a halogen atom represented by X, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is mentioned, Preferably it is a chlorine atom or a bromine atom, More preferably, it is a chlorine atom.

作為R所表示之有機基，可列舉：烷基[甲基、乙基、丙基、異丙基、丁基及第三丁基等碳原子數1~10之烷基(較佳為碳原子數1~6之烷基，尤其是碳數1~4之烷基等)]、環烷基(環己基等碳原子數5~8之環烷基，尤其是碳原子數5~6之環烷基)、烯基[乙烯基、丙烯基、丁烯基等碳原子數2~10之烯基(較佳為碳原子數2~6之烯基，尤其是碳數2~4之烯基等)]、環烯基[1-環戊烯基、1-環己烯基等碳原子數5~10之環烯基(較佳為碳原子數5~8之環烯基，尤其是碳數5~7之環烯基等)]、芳基(苯基、萘基等碳原子數6~10之芳基)、芳烷基[苄基、苯乙基等C_6-10芳基-C_1-6烷基(C_6-10芳基-C_1-4烷基等)]、胺基、N-取代胺基(經上述烷基、環烷基、芳基、芳烷基、醯基等取代之N-單或二取代胺基等)等。上述烷基、環烷基、芳基或構成芳烷基之芳基等亦可具有1個或複數個取代基。作為此種取代基，可列舉上述例示之烷基(尤其是碳原子數1~6之烷基等)等。作為具有此種取代基之有機基，例如可列舉：甲苯基(甲基苯基)、二甲苯基(2,6-二甲基苯基)、乙基苯基、甲基萘基等C_1-6烷基-C_6-10芳基(較佳為單、二或三C_1-4烷基-C_6-10芳基，尤其是單或二C_1-4烷基苯基等)等。 Examples of the organic group represented by R include alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, and tert-butyl groups) having 1 to 10 carbon atoms (preferably carbon atoms). Alkyl groups with 1 to 6 carbon atoms, especially alkyl groups with 1 to 4 carbon atoms, etc.)], cycloalkyl groups (cycloalkyl groups with 5 to 8 carbon atoms such as cyclohexyl, especially rings with 5 to 6 carbon atoms) Alkyl), alkenyl [vinyl, propenyl, butenyl and other alkenyl groups with 2 to 10 carbon atoms (preferably alkenyl with 2 to 6 carbon atoms, especially alkenyl with 2 to 4 carbon atoms) etc.)], cycloalkenyl [1-cyclopentenyl, 1-cyclohexenyl and other cycloalkenyl with 5 to 10 carbon atoms (preferably cycloalkenyl with 5 to 8 carbon atoms, especially carbon 5-7 cycloalkenyl, etc.)], aryl (phenyl, naphthyl and other C 6-10 aryl), aralkyl [benzyl, phenethyl and other C _6-10 aryl- C _1-6 alkyl (C _6-10 aryl-C _1-4 alkyl, etc.)], amine group, N-substituted amine group (through the above-mentioned alkyl, cycloalkyl, aryl, aralkyl, amide N-mono- or di-substituted amine groups, etc. substituted by bases, etc.) and the like. The above-mentioned alkyl group, cycloalkyl group, aryl group, or aryl group constituting an aralkyl group, etc. may have one or a plurality of substituents. As such a substituent, the above-exemplified alkyl groups (in particular, alkyl groups having 1 to 6 carbon atoms, etc.) and the like can be mentioned. Examples of organic groups having such a substituent include C ₁ such as tolyl (methylphenyl), xylyl (2,6-dimethylphenyl), ethylphenyl, and methylnaphthyl. _-6 alkyl-C _6-10 aryl (preferably mono-, di- or tri-C _1-4 alkyl-C _6-10 aryl, especially mono- or di- C _1-4 alkyl phenyl, etc.), etc. .

矽烷基可列舉經上述烷基、環烷基、烯基、環烯基、芳基、芳烷基及烷氧基等取代之取代矽烷基。 Examples of the silyl group include substituted silyl groups substituted with the above-mentioned alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups, aralkyl groups, and alkoxy groups.

於n為2之情形(二鹵矽烷化合物)時，作為R，較佳為烷基、芳基等烴基。 When n is 2 (dihalosilane compound), as R, hydrocarbon groups, such as an alkyl group and an aryl group, are preferable.

作為代表性之二鹵矽烷化合物，例如可列舉：二烷基二鹵矽烷(二甲基二氯矽烷等二C_1-10烷基二鹵矽烷，較佳為二C_1-6烷基二鹵矽烷，進而較佳為二C_1-4烷基二鹵矽烷等)、單烷基單芳基二鹵矽烷(甲基苯基二氯矽烷等單C_1-10烷基單C_6-12芳基二鹵矽烷，較佳為單C_1-6烷基單C6-10芳基二鹵矽烷，進而較佳為單C_1-4烷基單C_6-8芳基二鹵矽烷等)、二芳基二鹵矽烷(二苯基二氯矽烷等二C_6-12芳基二鹵矽烷，較佳為二C_6-10芳基二鹵矽烷，進而較佳為二C_6-8芳基二鹵矽烷等)等。作為二鹵矽烷化合物，較佳為二烷基二鹵矽烷或單烷基單芳基二鹵矽烷。二鹵矽烷化合物可單獨使用或將兩種以上組合使用。 Typical examples of dihalosilane compounds include dialkyldihalosilanes (di-C _1-10 alkyl dihalosilanes such as dimethyl dichlorosilane, preferably di-C _1-6 alkyl dihalosilanes) Silane, more preferably di-C _1-4 alkyl dihalosilane, etc.), monoalkyl monoaryl dihalosilane (mono-C _1-10 alkyl mono-C _6-12 aryl such as methylphenyl dichlorosilane, etc.) dihalosilanes, preferably mono-C _1-6 alkyl mono-C6-10 aryl dihalosilanes, and more preferably mono-C _1-4 alkyl mono-C _6-8 aryl dihalosilanes, etc.), two Aryl dihalosilanes (diphenyl dichlorosilane and other di-C _6-12 aryl dihalosilanes, preferably di-C _6-10 aryl dihalo silanes, and more preferably di-C _6-8 aryl dihalosilanes) Halosilanes, etc.), etc. As the dihalosilane compound, a dialkyldihalosilane or a monoalkylmonoaryldihalosilane is preferable. The dihalosilane compound may be used alone or in combination of two or more.

於n為3之情形(三鹵矽烷化合物)時，作為R，較佳為烷基、環烷基、可具有取代基之芳基、芳烷基等烴基，尤佳為烷基或芳基。 When n is 3 (trihalosilane compound), R is preferably a hydrocarbon group such as an alkyl group, a cycloalkyl group, an optionally substituted aryl group, an aralkyl group, and more preferably an alkyl group or an aryl group.

作為代表性之三鹵矽烷化合物，可列舉：烷基三鹵矽烷(甲基三氯矽烷、丁基三氯矽烷、第三丁基三氯矽烷、己基三氯矽烷等C_1-10烷基三鹵矽烷，較佳為C_1-6烷基三鹵矽烷，進而較佳為C_1-4烷基三鹵矽烷等)、環烷基三鹵矽烷(環己基三鹵矽烷等單C_6-10環烷基三鹵矽烷等)、芳基三鹵矽烷(苯基三氯矽烷、甲苯基三氯矽烷、二甲苯基三氯矽烷等C_6-12芳基三鹵矽烷，較佳為C_6-10芳基三鹵矽烷，進而較佳為C_6-8芳基三鹵矽烷等)等。三鹵矽烷化合物較佳為烷基三鹵矽烷或芳基三鹵矽烷。 Typical examples of trihalosilane compounds include C _1-10 alkyl trihalosilanes such as alkyl trihalosilanes (methyl trichlorosilane, butyl trichlorosilane, tert-butyl trichlorosilane, and hexyl trichlorosilane). Halosilanes, preferably C _1-6 alkyl trihalosilanes, more preferably C _1-4 alkyl trihalosilanes, etc.), cycloalkyl trihalosilanes (mono-C _6-10 cyclohexyl trihalosilanes, etc.) Cycloalkyl trihalosilane, etc.), aryl trihalosilane (phenyl trichlorosilane, tolyl trichlorosilane, xylyl trichlorosilane, etc. C _6-12 aryl trihalosilane, preferably C _{6- 10} aryl trihalosilane, more preferably C _6-8 aryl trihalosilane, etc.) and the like. The trihalosilane compound is preferably an alkyl trihalosilane or an aryl trihalosilane.

三鹵矽烷化合物可單獨使用或將兩種以上組合使用。 The trihalosilane compound may be used alone or in combination of two or more.

作為n為4之情形(四鹵矽烷化合物)時之具體例，例如可列舉：四氯矽烷、二溴二氯矽烷、四溴矽烷等。四鹵矽烷化合物可單獨或將2種以上組合。 As a specific example when n is 4 (tetrahalosilane compound), a tetrachlorosilane, a dibromodichlorosilane, a tetrabromosilane, etc. are mentioned, for example. The tetrahalosilane compound may be used alone or in combination of two or more.

再者，四鹵矽烷化合物較佳為與單、二或三鹵矽烷化合物組合使用。 Furthermore, the tetrahalosilane compound is preferably used in combination with a mono-, di- or trihalosilane compound.

又，作為鹵矽烷化合物，亦可為單鹵矽烷化合物。作為代表性之單鹵矽烷，例如可列舉：三烷基單鹵矽烷(三甲基氯矽烷等三C_1-10烷基單鹵矽烷，較佳為三C_1-6烷基單鹵矽烷，進而較佳為三C_1-4烷基單鹵矽烷等)、二烷基單芳基單鹵矽烷(二甲基苯基氯矽烷等二C_1-10烷基單C_6-12芳基單鹵矽烷，較佳為二C_1-6烷基單C_6-10芳基單鹵矽烷，進而較佳為二C_1-4烷基單C_6-8芳基單鹵矽烷等)、單烷基二芳基單鹵矽烷(甲基二苯基氯矽烷等單C_1-10烷基二C_6-12芳基單鹵矽烷，較佳為單C_1-6烷基二C_6-10芳基單鹵矽烷，進而較佳為單C_1-4烷基二C_6-8芳基單鹵矽烷等)、三芳基單鹵矽烷(三苯基氯矽烷等三C_6-12芳基單鹵矽烷，較佳為三C_6-10芳基單鹵矽烷，進而較佳為三C_6-8芳基單鹵矽烷等)等。單鹵矽烷化合物可單獨使用或將兩種以上組合使用。 Moreover, as a halosilane compound, a monohalosilane compound may be sufficient. As representative monohalosilanes, for example, trialkyl monohalosilanes (tri-C _1-10 alkyl monohalosilanes such as trimethylchlorosilane, preferably tri-C _1-6 alkyl monohalosilanes, Further preferred are tri-C _1-4 alkyl monohalosilanes, etc.), dialkyl monoaryl monohalosilanes (di-C _1-10 alkyl mono-C _6-12 aryl monosilanes such as dimethylphenyl chlorosilane, etc.) Halosilanes, preferably di-C _1-6 alkyl mono-C _6-10 aryl monohalosilanes, more preferably di-C _1-4 alkyl mono-C _6-8 aryl monohalosilanes, etc.), monoalkanes mono-C _1-10 alkyl di-C _6-12 aryl monohalosilane such as methyldiphenyl chlorosilane, preferably mono-C _1-6 alkyl di-C _6-10 aryl monohalosilanes, more preferably mono-C _1-4 alkyl di-C _6-8 aryl monohalosilanes, etc.), triaryl monohalosilanes (triphenyl chlorosilanes, etc. tri-C _6-12 aryl monohalosilanes, etc.) Silane, preferably tri-C _6-10 aryl monohalosilane, more preferably tri-C _6-8 aryl monohalosilane, etc.) and the like. The monohalosilane compounds may be used alone or in combination of two or more.

該等鹵矽烷化合物可單獨使用或將2種以上組合使用。 These halosilane compounds may be used alone or in combination of two or more.

鹵矽烷化合物較佳為包含選自二鹵矽烷化合物及三鹵矽烷化合物中之至少1種。 The halosilane compound preferably contains at least one selected from the group consisting of dihalosilane compounds and trihalosilane compounds.

再者，於鹵矽烷化合物包含三鹵矽烷化合物及/或四鹵矽烷化合物之情形時，可能生成網狀(網狀或支鏈狀)之聚矽烷化合物。於獲得網狀之聚矽烷化合物之情形時，作為代表性之鹵矽烷(或其組合)，可列舉：(a)烷基三鹵矽烷(例如烷基三鹵矽烷單獨、甲基三鹵矽烷與C_2-10烷基三鹵矽烷之組合、C_2-10烷基三鹵矽烷等)、(b)芳基三鹵矽烷(例如芳基三鹵矽烷單獨)、(c)芳基三鹵矽烷與二鹵矽烷(例如單烷基單芳基二鹵矽烷等)之組合等。 Furthermore, when the halosilane compound includes a trihalosilane compound and/or a tetrahalosilane compound, a network-like (network-like or branched-chain) polysilane compound may be generated. In the case of obtaining a network-like polysilane compound, representative halosilanes (or combinations thereof) include: (a) alkyl trihalosilanes (such as alkyl trihalosilanes alone, methyltrihalosilanes and A combination of _C2-10 alkyl trihalosilanes, _C2-10 alkyl trihalosilanes, etc.), (b) aryl trihalosilanes (eg, aryl trihalosilanes alone), (c) aryl trihalosilanes Combinations with dihalosilanes (such as monoalkyl monoaryl dihalosilanes, etc.), etc.

於鹵矽烷化合物中，選自二鹵矽烷化合物及三鹵矽烷化合物中之至少1種之比率(使用比率)相對於鹵矽烷整體，可為50莫耳%以上(例如60莫耳%以上)，較佳為70莫耳%以上(例如80莫耳%以上)，進而較佳為90莫耳%以上(例如95莫耳%以上)。 Among the halosilane compounds, the ratio (use ratio) of at least one selected from the group consisting of dihalosilane compounds and trihalosilane compounds may be 50 mol % or more (for example, 60 mol % or more) with respect to the whole halosilane, Preferably, it is 70 mol% or more (for example, 80 mol% or more), and more preferably 90 mol% or more (for example, 95 mol% or more).

再者，於獲得網狀之聚矽烷之情形等時，三鹵矽烷化合物之比率(使用比率)可為鹵矽烷化合物整體之30莫耳%以上(例如40莫耳%以上)，較佳為50莫耳%以上(例如60莫耳%以上)，進而較佳為70莫耳%以上(例如75莫耳%以上)，尤其是80莫耳%以上。 Furthermore, in the case of obtaining a network-like polysilane, etc., the ratio of the trihalosilane compound (so that ratio) can be 30 mol % or more (for example, 40 mol % or more) of the whole halosilane compound, preferably 50 mol % or more (for example, 60 mol % or more), and more preferably 70 mol % or more (For example, 75 mol% or more), especially 80 mol% or more.

又，於將二鹵矽烷化合物與三鹵矽烷化合物組合之情形時，該等之比率可為前者/後者(莫耳比)=99/1~1/99，較佳為90/10~2/98(例如85/15~2/98)，進而較佳為80/20~3/97(例如70/30~4/96)，尤其是60/40~5/95(例如50/50~7/93)，通常亦可為50/50~5/95(例如45/55~7/93，較佳為40/60~10/90，進而較佳為30/70~88/12)。 In addition, when the dihalosilane compound and the trihalosilane compound are combined, the ratio can be the former/the latter (molar ratio)=99/1~1/99, preferably 90/10~2/ 98 (eg 85/15~2/98), more preferably 80/20~3/97 (eg 70/30~4/96), especially 60/40~5/95 (eg 50/50~7 /93), usually 50/50~5/95 (for example, 45/55~7/93, preferably 40/60~10/90, and more preferably 30/70~88/12).

鹵矽烷化合物較佳為儘可能為高純度。例如，關於液體之鹵矽烷化合物，較佳為使用氫化鈣等乾燥劑進行乾燥並進行蒸餾而使用，關於固體之鹵矽烷化合物，較佳為藉由再結晶法等進行精製而使用。 The halosilane compound is preferably as pure as possible. For example, the liquid halosilane compound is preferably used by drying with a desiccant such as calcium hydride, followed by distillation, and the solid halosilane compound is preferably used after being purified by a recrystallization method or the like.

再者，原料混合物(反應液)中之鹵矽烷化合物之濃度(基質濃度)例如可為0.05~20mol/l左右，較佳為0.1~15mol/l左右，進而較佳為0.2~5mol/l左右。 Furthermore, the concentration (substrate concentration) of the halosilane compound in the raw material mixture (reaction solution) may be, for example, about 0.05 to 20 mol/l, preferably about 0.1 to 15 mol/l, and more preferably about 0.2 to 5 mol/l. .

(金屬鹵化物) (metal halide)

第1態樣之聚矽烷化合物之製造方法亦可於上述有機金屬錯合物及鎂、進而金屬鹵化物之存在下使上述鹵矽烷化合物反應。 In the production method of the polysilane compound of the first aspect, the above-mentioned halosilane compound may be reacted in the presence of the above-mentioned organometallic complex, magnesium, and further a metal halide.

作為金屬鹵化物，可列舉多價金屬鹵化物，例如過渡金屬(例如釤等週期表3A族元素、鈦等週期表4A族元素、釩等週期表5A族元素、鐵、鎳、鈷、鈀等週期表8族元素、銅等週期表1B族元素、鋅等週期表2B族元素等)、週期表3B族金屬(鋁等)、週期表4B族金屬(錫等)等金屬之鹵化物(氯化物、溴化物或碘化物等)。構成金屬鹵化物之上述金屬之價數並無特別限制，較佳為2~4價，尤其是2或3價。該等金屬鹵化物可單獨使用或將兩種以上組合使用。 Examples of metal halides include polyvalent metal halides, such as transition metals (such as samarium and other periodic table group 3A elements, titanium and other periodic table group 4A elements, vanadium and other periodic table group 5A elements, iron, nickel, cobalt, palladium, etc. Periodic table group 8 elements, copper and other periodic table 1B group elements, zinc and other periodic table 2B group elements, etc.), periodic table group 3B metals (aluminum, etc.), periodic table 4B metals (tin, etc.) and other metal halides (chlorine compound, bromide or iodide, etc.). The valence of the above-mentioned metal constituting the metal halide is not particularly limited, but is preferably 2 to 4 valence, especially 2 or 3 valence. These metal halides can be used alone or Use two or more in combination.

作為金屬鹵化物，較佳為選自鐵、鋁、鋅、銅、錫、鎳、鈷、釩、鈦、鈀、釤等中之至少一種金屬之氯化物或溴化物。 The metal halide is preferably a chloride or bromide of at least one metal selected from iron, aluminum, zinc, copper, tin, nickel, cobalt, vanadium, titanium, palladium, samarium, and the like.

作為此種金屬鹵化物，例如可例示：氯化物(FeCl₂、FeCl₃等氯化鐵；AlCl₃、ZnCl₂、SnCl₂、CoCl₂、VCl₂、TiCl₄、PdCl₂、SmCl₂等)、溴化物(FeBr₂、FeBr₃等溴化鐵等)、碘化物(SmI₂等)等。該等金屬鹵化物之中，較佳為氯化物(例如氯化鐵(II)、氯化鐵(III)等氯化鐵、氯化鋅等)及溴化物。通常使用氯化鐵及/或氯化鋅，尤其是氯化鋅等。 Examples of such metal halides include chlorides (ferric chlorides such as FeCl ₂ and FeCl ₃ ; AlCl ₃ , ZnCl ₂ , SnCl ₂ , CoCl ₂ , VCl ₂ , TiCl ₄ , PdCl ₂ , SmCl ₂ , etc.), Bromide (FeBr ₂ , FeBr ₃ and other iron bromide, etc.), iodide (SmI ₂ etc.) and the like. Among these metal halides, chlorides (for example, iron chlorides such as iron(II) chloride and iron(III) chloride, zinc chloride, etc.) and bromides are preferable. Usually ferric chloride and/or zinc chloride, especially zinc chloride, etc. are used.

作為金屬鹵化物之使用量，相對於鹵矽烷化合物，較佳為0.001~10莫耳倍之範圍，更佳為0.001~1莫耳倍之範圍，尤佳為0.001~0.1莫耳倍之範圍。 The amount of the metal halide used is preferably in the range of 0.001 to 10 mol times, more preferably 0.001 to 1 mol times, and particularly preferably 0.001 to 0.1 mol times, relative to the halosilane compound.

又，反應液中之金屬鹵化物之濃度通常可為0.001~6莫耳/L左右，較佳為0.005~4莫耳/L，進而較佳為0.01~3莫耳/L左右。 In addition, the concentration of the metal halide in the reaction solution is usually about 0.001-6 mol/L, preferably about 0.005-4 mol/L, and more preferably about 0.01-3 mol/L.

(非質子性溶劑) (aprotic solvent)

第1態樣之聚矽烷化合物之製造方法中之鹵矽烷化合物之反應較佳為於溶劑(反應溶劑)中進行，更佳為於非質子性溶劑中進行。 The reaction of the halosilane compound in the method for producing a polysilane compound of the first aspect is preferably performed in a solvent (reaction solvent), and more preferably performed in an aprotic solvent.

作為溶劑(反應溶劑)之非質子性溶劑中例如包含：醚類(1,4-二

烷、四氫呋喃、四氫吡喃、二***、二異丙醚、1,2-二甲氧基乙烷、雙(2-甲氧基乙基)醚等環狀或鏈狀C_4-6醚)、碳酸酯類(碳酸丙二酯等)、腈類(乙腈、苯甲腈等)、醯胺類(二甲基甲醯胺、二甲基乙醯胺等)、亞碸類(二甲基亞碸等)、芳香族烴類(苯、甲苯、二甲苯等)、脂肪族烴類(例如己烷、環己烷、辛烷、環辛烷等鏈狀或環狀烴類)等。 The aprotic solvent used as a solvent (reaction solvent) includes, for example, ethers (1,4-di

Alkane, tetrahydrofuran, tetrahydropyran, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether and other cyclic or chain C _4-6 ethers ), carbonates (propylene carbonate, etc.), nitriles (acetonitrile, benzonitrile, etc.), amides (dimethylformamide, dimethylacetamide, etc.), sulfites (dimethylformamide, etc.) sulfite, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), aliphatic hydrocarbons (eg, chain or cyclic hydrocarbons such as hexane, cyclohexane, octane, cyclooctane, etc.), and the like.

該等非質子性溶劑可單獨使用或將兩種以上組合而作為混合溶劑使用。該等溶劑之中，較佳為至少使用極性溶劑[例如醚類[例如四氫呋喃、1,2-二甲氧基乙烷、雙(2-甲氧基乙基)醚、1,4-二

烷等(尤其是四氫呋喃、1,2-二甲氧基乙烷)]]。極性溶劑可單獨使用或將兩種以上組合使用，亦可將極性溶劑與非極性溶劑組合。 These aprotic solvents may be used alone or in combination of two or more as a mixed solvent. Among these solvents, it is preferable to use at least polar solvents [such as ethers [such as tetrahydrofuran, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,4-dimethoxyethane]

alkane, etc. (especially tetrahydrofuran, 1,2-dimethoxyethane)]]. The polar solvent may be used alone or in combination of two or more, and may be used in combination with a polar solvent and a non-polar solvent.

於第1態樣之聚矽烷化合物之製造方法中，較佳為進而包括藉由使上述反應後之溶液(反應液)與包含選自鹼、及酸所組成之群中之至少1種之水溶液接觸進行精製而獲得上述聚矽烷化合物。 In the manufacturing method of the polysilane compound of the 1st aspect, it is preferable to further comprise by making the solution (reaction liquid) after the said reaction and the aqueous solution containing at least 1 sort(s) chosen from the group which consists of an alkali and an acid. The above-mentioned polysilane compound is obtained by contact and purification.

藉由使上述聚矽烷化合物與鹼或酸接觸而進行精製處理，可將鹵素原子(例如鹵素離子(氯化物離子等)、聚矽烷化合物中所殘存之Si-Cl)等夾雜物去除，又，可促進聚矽烷化合物之低分子量化，而可提高上述聚矽烷化合物之溶劑溶解性。 By contacting the above-mentioned polysilane compound with an alkali or an acid and performing a purification treatment, inclusions such as halogen atoms (for example, halogen ions (chloride ions, etc.), Si-Cl remaining in the polysilane compound) can be removed, and further, The low molecular weight of the polysilane compound can be promoted, and the solvent solubility of the above-mentioned polysilane compound can be improved.

又，酸亦可作為上述鹵矽烷化合物之反應之驟冷劑發揮功能。 In addition, the acid can also function as a quenching agent for the reaction of the above-mentioned halosilane compound.

又，藉由使上述聚矽烷化合物與下述金屬鹵化物接觸而進行精製處理，可將聚矽烷化合物中所殘存之金屬原子(例如Mg、Zn、Cu、Fe等)去除。 In addition, the metal atoms (eg, Mg, Zn, Cu, Fe, etc.) remaining in the polysilane compound can be removed by contacting the above-mentioned polysilane compound with the following metal halide and performing purification treatment.

處理溫度較佳為-50℃~溶劑之沸點左右，進而較佳為室溫~100℃。 The treatment temperature is preferably about -50°C to the boiling point of the solvent, and more preferably room temperature to 100°C.

又，作為所使用之鹼，只要為呈鹼性之化合物，則可使用各種鹼，例如可使用：氫氧化鈉、氫氧化鉀、氫氧化鋇、氨、氫氧化四甲基銨、碳酸鈉、碳酸氫鈉、碳酸鉀、氫化鋰、氫化鈉、氫化鉀、氫化鈣等無機鹼類；甲基鋰、正丁基鋰、氯化甲基鎂、溴化乙基鎂等烷基金屬類；包含Cr、Ga、Fe(Fe(II)、Fe(III))、Cd、Co、Ni、Sn、Pb、Cu(Cu(II)、Cu(I))、Ag、Pd、Pt、Au等金屬(或金屬離子)之金屬鹵化物；甲醇鈉、乙醇鈉、第三丁醇鉀等烷氧化物類；三乙基胺、二異丙基乙基胺、N,N-二甲基苯胺、吡啶、4-二甲胺基吡啶、二氮雜雙環十一烯(DBU)等有機鹼類。反應溫度較佳為-50℃~溶劑之沸點左右，進而較佳為室溫~100℃。 Moreover, as the base to be used, as long as it is an alkaline compound, various bases can be used, for example, sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia, tetramethylammonium hydroxide, sodium carbonate, Inorganic bases such as sodium bicarbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, calcium hydride, etc.; alkyl metals such as methyllithium, n-butyllithium, methylmagnesium chloride, ethylmagnesium bromide; including Cr, Ga, Fe (Fe(II), Fe(III)), Cd, Co, Ni, Sn, Pb, Cu(Cu(II), Cu(I)), Ag, Pd, Pt, Au and other metals ( or metal ions) metal halides; sodium methoxide, ethyl acetate Sodium alkoxide, potassium tert-butoxide and other alkoxides; triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, diazabicyclo Organic bases such as undecene (DBU). The reaction temperature is preferably about -50°C to the boiling point of the solvent, and more preferably room temperature to 100°C.

作為所使用之酸，可使用各種酸，可使用氯化氫等無機酸。 As the acid to be used, various acids can be used, and inorganic acids such as hydrogen chloride can be used.

此處，作為用於上述鹼或酸處理之溶劑，可使用各種溶劑，例如可使用選自苯、甲苯、二甲苯等烴系溶劑；丙二醇單甲醚、丙二醇單***等二醇系溶劑；二***、二異丙醚、二丁醚、四氫呋喃、1,4-二

烷等醚系溶劑；丙酮、甲基乙基酮、甲基異丁基酮、甲基戊基酮、環戊酮、環己酮等酮系溶劑；乙醇、異丙醇、丁醇等醇系溶劑中之1種以上。 Here, as the solvent used for the above-mentioned alkali or acid treatment, various solvents can be used, for example, hydrocarbon-based solvents such as benzene, toluene, and xylene; glycol-based solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; Diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-diethyl ether

Ether series solvents such as alkane; ketone series solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone; alcohol series such as ethanol, isopropanol, butanol One or more of the solvents.

又，含環狀骨架之乙酸酯化合物亦可較佳地用作用於上述鹼或酸處理之溶劑。 In addition, an acetate compound containing a cyclic skeleton can also be preferably used as a solvent for the above-mentioned alkali or acid treatment.

作為含環狀骨架之乙酸酯化合物，只要為無損本發明之效果之具有環狀骨架之乙酸酯系溶劑，則並無特別限制，較佳為下述式(S1)所表示之乙酸環烷基酯。 The acetate compound containing a cyclic skeleton is not particularly limited as long as it is an acetate-based solvent having a cyclic skeleton that does not impair the effect of the present invention, and an acetic acid ring represented by the following formula (S1) is preferred. Alkyl esters.

(式(S1)中，R^s1分別獨立地為烷基，p為1~6之整數，q為0~(p+1)之整數) (In formula (S1), R ^s1 are each independently an alkyl group, p is an integer of 1 to 6, and q is an integer of 0 to (p+1))

作為R^s1所表示之烷基，可列舉碳原子數1~3之烷基，可列舉：甲基、乙基、正丙基、異丙基。 Examples of the alkyl group represented by R ^s1 include alkyl groups having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, a n-propyl group, and an isopropyl group.

作為式(S1)所表示之乙酸環烷基酯之具體例，可列舉：乙酸環丙酯、乙酸環丁酯、乙酸環戊酯、乙酸環己酯、乙酸環庚酯、及乙酸環辛酯。 Specific examples of the cycloalkyl acetate represented by the formula (S1) include cyclopropyl acetate, cyclobutyl acetate, cyclopentyl acetate, cyclohexyl acetate, cycloheptyl acetate, and cyclooctyl acetate .

該等之中，就獲取容易性等觀點而言，較佳為乙酸環己酯。 Among these, cyclohexyl acetate is preferred from the viewpoint of availability and the like.

根據第1態樣之聚矽烷化合物之製造方法，可以產率50%以上獲得聚矽烷化合物，較佳為產率70%以上。 According to the method for producing a polysilane compound of the first aspect, the polysilane compound can be obtained in a yield of 50% or more, preferably in a yield of 70% or more.

<聚矽烷化合物> <Polysilane compound>

根據第1態樣之聚矽烷化合物之製造方法，可製造質量平均分子量(Mw)5000以下之聚矽烷化合物。 According to the method for producing a polysilane compound of the first aspect, a polysilane compound having a mass average molecular weight (Mw) of 5,000 or less can be produced.

於本說明書中，質量平均分子量(Mw)係藉由凝膠滲透層析法(GPC)之聚苯乙烯換算所得之測定值。 In this specification, the mass average molecular weight (Mw) is a measured value in terms of polystyrene by gel permeation chromatography (GPC).

作為上述聚矽烷化合物之Mw，就間隙填充性之觀點而言，較佳為4000以下，更佳為3000以下，進而較佳為2500以下。 As Mw of the said polysilane compound, from a viewpoint of gap filling property, it is preferable that it is 4000 or less, it is more preferable that it is 3000 or less, and it is still more preferable that it is 2500 or less.

作為上述聚矽烷化合物之Mw之下限值，只要無損本發明之效果，則並無特別限制，較佳為300以上，更佳為400以上，進而較佳為500以上，尤佳為600以上，最佳為700以上。 The lower limit of Mw of the above-mentioned polysilane compound is not particularly limited as long as the effect of the present invention is not impaired. The best is above 700.

根據第1態樣之聚矽烷化合物之製造方法，可製造選自由直鏈狀聚矽烷、支鏈狀聚矽烷及環狀聚矽烷所組成之群中之至少1種聚矽烷化合物。尤其是亦可選擇性地製造環狀聚矽烷化合物。 According to the method for producing a polysilane compound of the first aspect, at least one polysilane compound selected from the group consisting of linear polysilane, branched polysilane, and cyclic polysilane can be produced. In particular, a cyclic polysilane compound can also be selectively produced.

就化學結構及化學性質之方面而言，環狀聚矽烷化合物可較佳地成為Mw5000以下之聚矽烷化合物。 In terms of chemical structure and chemical properties, the cyclic polysilane compound can preferably be a polysilane compound below Mw5000.

作為上述聚矽烷化合物，例如可列舉Si原子數3~40之聚矽烷化合物，較佳為Si原子數5~30之聚矽烷化合物。 Examples of the above-mentioned polysilane compound include polysilane compounds having 3 to 40 Si atoms. compound, preferably a polysilane compound having 5 to 30 Si atoms.

上述聚矽烷化合物較佳為選自由下述通式(T-1)及(T-2)所表示之聚矽烷化合物所組成之群中之至少1種。 The above-mentioned polysilane compound is preferably at least one selected from the group consisting of polysilane compounds represented by the following general formulae (T-1) and (T-2).

(R^t10R^t11R^t12Si)_t1(R^t13R^t14Si)_t2(R^t15Si)_t3(Si)_t4 (T-1) (R ^t10 R ^t11 R ^t12 Si) _t1 (R ^t13 R ^t14 Si) _t2 (R ^t15 Si) _t3 (Si) _t4 (T-1)

(上述通式中，R^t10、R^t11、R^t12、R^t13、R^t14及R^t15分別獨立地為氫原子、羥基或有機基；t1、t2、t3及t4分別獨立地為莫耳分率，t1+t2+t3+t4=1，0≦t1≦1，0≦t2≦1，0≦t3≦1及0≦t4≦1) (In the above general formula, R ^t10 , R ^t11 , R ^t12 , R ^t13 , R ^t14 and R ^t15 are each independently a hydrogen atom, a hydroxyl group or an organic group; t1 , t2 , t3 and t4 are independently mole fractions , t1+t2+t3+t4=1, 0≦t1≦1, 0≦t2≦1, 0≦t3≦1 and 0≦t4≦1)

(上述通式(T-2)中，R^t16及R^t17分別獨立地表示氫原子、羥基或有機基；U表示3~20之整數) (In the above general formula (T-2), R ^t16 and R ^t17 each independently represent a hydrogen atom, a hydroxyl group or an organic group; U represents an integer of 3 to 20)

作為R^t10~R^t17所表示之有機基，可列舉與作為R所表示之有機基而於上文中敍述之具體例及較佳例相同者。 As the organic group represented by R ^t10 to R ^t17 , the same specific examples and preferred examples as described above as the organic group represented by R can be exemplified.

作為R^t10~R^t17所表示之有機基，例如亦可藉由日本專利特開2003-261681號公報段落0031所記載之方法導入任意有機基。 As the organic group represented by R ^t10 to R ^t17 , an arbitrary organic group may be introduced, for example, by the method described in paragraph 0031 of Japanese Patent Laid-Open No. 2003-261681.

第2態樣之聚矽烷化合物較佳為聚矽烷化合物中之藉由X射線光電子光譜法所測得之矽氧烷鍵(Si-O)之下述式所表示之比率為0.5以下。 In the polysilane compound of the second aspect, the ratio represented by the following formula of the siloxane bond (Si—O) measured by X-ray photoelectron spectroscopy in the polysilane compound is preferably 0.5 or less.

根據第1態樣之聚矽烷化合物之製造方法，可將下述(2X)相對於下述(1X)及(2X)之波峰之面積之和的比即下述式(3X)所表示之比率設為0.4以下，上述波峰之面積係將上述聚矽烷化合物中藉由X射線光電子光譜法測定之於99eV以上且104eV以下之鍵結能量範圍內具有最大檢測波峰高度之光譜進行波峰分離而求出，上述比率較佳為0.35以下，更佳為0.3以下，進而較佳為0.2以下，尤佳為0.1以下，最佳為0.05以下。 According to the method for producing a polysilane compound of the first aspect, the ratio of the following (2X) to the sum of the areas of the peaks of the following (1X) and (2X) can be the ratio represented by the following formula (3X) Set to 0.4 or less, the area of the above-mentioned peak is obtained by peak-separating the spectrum of the above-mentioned polysilane compound having the maximum detection peak height in the bonding energy range of 99 eV or more and 104 eV or less measured by X-ray photoelectron spectroscopy. , the above ratio is preferably 0.35 or less, more preferably 0.3 or less, still more preferably 0.2 or less, particularly preferably 0.1 or less, and most preferably 0.05 or less.

(1X)‧‧‧於鍵結能量為99.0eV以上且99.5eV以下之範圍內具有最大波峰高度之波峰之面積 (1X)‧‧‧The area of the peak with the largest peak height in the range of bonding energy of 99.0eV or more and 99.5eV or less

(2X)‧‧‧於鍵結能量為100eV以上且104eV以下之範圍內具有最大波峰高度之波峰之面積 (2X)‧‧‧The area of the crest with the largest crest height in the range of bonding energy of 100eV or more and 104eV or less

(3X)‧‧‧(2X)/[(1X)+(2X)] (3X)‧‧‧(2X)/[(1X)+(2X)]

關於對波峰之強度(Intensity)進行測定，並於上述(1X)及(2X)之各鍵結能量範圍內進行波峰分離而求出之波峰之面積，根據(2X)之於鍵結能量為100eV以上且104eV以下之範圍內具有最大波峰高度之波峰之面積得知Si-O及Si-C之含有比率。又，根據(1X)之於鍵結能量為99.0eV以上且99.5eV以下之範圍內具有最大波峰高度之波峰之面積得知Si-Si之含有比率。 Regarding the area of the peak obtained by measuring the intensity of the peak and separating the peaks in the bonding energy ranges of (1X) and (2X) above, the bonding energy based on (2X) is 100eV The content ratio of Si-O and Si-C is obtained by the area of the peak having the maximum peak height in the range of 104 eV or more. In addition, the content ratio of Si-Si was obtained from the area of the peak having the largest peak height in the range of (1X) where the bonding energy is 99.0 eV or more and 99.5 eV or less.

於聚矽烷化合物不僅包含Si-C亦包含Si-O之情形時，於100eV以上且104eV以下之範圍內進行波峰分離後，2個具有最大波峰高度之波峰重疊顯示，但第2態樣之聚矽烷化合物較佳為於100eV以上且104eV以下之範圍內進行波峰分離後，僅出現1個具有最大波峰高度之波峰，認為就理想的是僅出現1個波峰而言，實質上不包含Si-O鍵。 When the polysilane compound contains not only Si-C but also Si-O, after the peak separation is performed in the range of 100eV or more and 104eV or less, the two peaks with the largest peak heights are displayed as overlapping, but the polysilane of the second aspect is The silane compound preferably has only one peak with the largest peak height after peak separation in the range of 100 eV or more and 104 eV or less, and it is considered that only one peak is ideal, and does not substantially contain Si-O. key.

又，於先前之聚矽烷化合物不僅包含Si-C亦包含Si-O之情形時，於 100eV以上且104eV以下之範圍內進行波峰分離後，具有最大波峰高度之2個波峰重疊顯示，故而面積比增大，因此上述式所表示之比率超過0.4。 In addition, when the previous polysilane compound contains not only Si-C but also Si-O, the When the peaks are separated in the range of 100eV or more and 104eV or less, the two peaks with the largest peak height are overlapped and displayed, so that the area ratio increases. Therefore, the ratio represented by the above formula exceeds 0.4.

根據第1態樣之聚矽烷化合物之製造方法，上述有機金屬錯合物不包含鹵素原子，因此可抑制生成矽氧烷鍵、矽烷醇基等副反應物，可減少聚矽烷化合物中之矽氧烷鍵(Si-O)之存在量，從而可提高抑制產生微龜裂等膜之性能。 According to the method for producing a polysilane compound of the first aspect, since the organometallic complex does not contain halogen atoms, the formation of side reactants such as siloxane bonds and silanol groups can be suppressed, and the amount of siloxane in the polysilane compound can be reduced. The presence of alkane bonds (Si-O) can improve the performance of inhibiting the generation of micro-cracks and other films.

根據第1態樣之聚矽烷化合物之製造方法，可減少聚矽烷化合物中之殘存金屬之含量，可將聚矽烷化合物中之金屬之含量設為500ppb以下，較佳為400ppb以下，更佳為100ppb以下，進而較佳為50ppb以下，尤佳為10ppb以下。 According to the method for producing a polysilane compound of the first aspect, the content of the residual metal in the polysilane compound can be reduced, and the content of the metal in the polysilane compound can be set to 500 ppb or less, preferably 400 ppb or less, more preferably 100 ppb Below, it is more preferable that it is 50 ppb or less, and it is especially preferable that it is 10 ppb or less.

藉由設為上述範圍內，可防止作為包含上述聚矽烷化合物之膜等光電子材料之性能降低。 By setting it in the said range, it can prevent that the performance as an optoelectronic material, such as a film containing the said polysilane compound, falls.

<組合物> <composition>

第3態樣之組合物係包含第2態樣之聚矽烷化合物之組合物。 The composition of the third aspect is a composition comprising the polysilane compound of the second aspect.

又，第3態樣之組合物可為熱硬化性組合物，亦可不為熱硬化性組合物。 In addition, the composition of the third aspect may or may not be a thermosetting composition.

又，第3態樣之組合物可為感輻射性組合物，亦可不為感輻射性組合物，可為可藉由曝光而對顯影液可溶之正型之感輻射性組合物，亦可為藉由曝光而對顯影液不可溶之負型之感輻射性組合物。 In addition, the composition of the third aspect may be a radiation-sensitive composition, or may not be a radiation-sensitive composition, may be a positive-type radiation-sensitive composition that is soluble in a developer by exposure, or may be It is a negative radioactive composition which is insoluble in developing solution by exposure.

作為上述放射線之光源，可列舉：紫外線、準分子雷射光等活性能量線、高壓水銀燈、超高壓水銀燈、氙氣燈、碳弧燈等發出紫外線之光源等。 Examples of the above-mentioned radiation source include active energy rays such as ultraviolet rays and excimer laser light, and light sources that emit ultraviolet rays such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and carbon arc lamps.

(溶劑) (solvent)

第3態樣之組合物較佳為含有溶劑。作為溶劑，可列舉：上述含環狀骨架之乙酸酯化合物、甲醇、乙醇、丙醇、正丁醇等醇類；乙二醇、二乙二醇、丙二醇、二丙二醇等多元醇類；丙酮、甲基乙基酮、環己酮、甲基正戊基酮、甲基異戊基酮、2-庚酮等酮類；γ-丁內酯等含內酯環之有機溶劑；乙二醇單乙酸酯、二乙二醇單乙酸酯、丙二醇單乙酸酯、或二丙二醇單乙酸酯等具有酯鍵之化合物、上述多元醇類或上述具有酯鍵之化合物之單甲醚、單***、單丙醚、單丁醚等單烷基醚或單苯基醚等具有醚鍵之化合物等多元醇類之衍生物；如二

烷之類的環式醚類或乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮酸甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯等酯類；苯甲醚、乙基苄醚、甲苯基甲醚、二苯醚、二苄醚、苯***、丁基苯醚、乙基苯、二乙基苯、戊基苯、異丙基苯、甲苯、二甲苯、異丙基甲苯、均三甲苯等芳香族系有機溶劑；N,N,N',N'-四甲基脲、N,N,2-三甲基丙醯胺、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N,N-二乙基乙醯胺、N,N-二乙基甲醯胺、1,3-二甲基-2-咪唑啶酮、N-甲基吡咯啶酮、N-乙基吡咯啶酮等含氮有機溶劑。其中，較佳為上述含環狀骨架之乙酸酯化合物、丙二醇單甲醚乙酸酯(PGMEA)、丙二醇單甲醚(PGME)、N,N,N',N'-四甲基脲(TMU)、及丁醇。 The composition of the third aspect preferably contains a solvent. Examples of the solvent include the above-mentioned cyclic skeleton-containing acetate compounds, alcohols such as methanol, ethanol, propanol, and n-butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; and acetone , methyl ethyl ketone, cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone, 2-heptanone and other ketones; γ-butyrolactone and other organic solvents containing lactone rings; ethylene glycol Compounds with ester bonds such as monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, monomethyl ethers of the above polyols or the above compounds with ester bonds, Derivatives of polyols such as monoalkyl ethers such as monoethyl ether, monopropyl ether and monobutyl ether, or compounds with ether bonds such as monophenyl ether;

Cyclic ethers such as alkanes or methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxy Esters such as ethyl propionate; anisole, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, ethyl benzene, diethyl benzene, amyl benzene , cumene, toluene, xylene, cumene, mesitylene and other aromatic organic solvents; N,N,N',N'-tetramethylurea, N,N,2-trimethyl Propionamide, N,N-Dimethylacetamide, N,N-Dimethylformamide, N,N-Diethylacetamide, N,N-Diethylformamide, 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-ethylpyrrolidone and other nitrogen-containing organic solvents. Among them, preferred are the above-mentioned cyclic skeleton-containing acetate compounds, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), N,N,N',N'-tetramethylurea ( TMU), and butanol.

該等溶劑亦可將2種以上組合使用。 These solvents may be used in combination of two or more.

第3態樣之組合物中，就抑制微龜裂之方面或容易形成介電常數較低之二氧化矽系覆膜之方面而言，第3態樣之組合物之水分量較佳為0.5質量%以下，更佳為0.3質量%以下，尤佳為未達0.3質量%。 In the composition of the third aspect, the moisture content of the composition of the third aspect is preferably 0.5 in terms of suppressing micro-cracking or easily forming a silicon dioxide-based film with a low dielectric constant It is less than or equal to 0.3 mass %, more preferably less than or equal to 0.3 mass %.

第3態樣之組合物之水分多數情況下來自溶劑。因此，較佳為以第3態樣之組合物之水分量成為上述量之方式將溶劑脫水。 In many cases, the water content of the composition of the third aspect is derived from the solvent. Therefore, it is preferable to dehydrate the solvent so that the water content of the composition of the third aspect becomes the above-mentioned amount.

溶劑之使用量於無損本發明之目的之範圍內並無特別限定。就製膜性之方面而言，溶劑係以第3態樣之組合物之固形物成分濃度成為較佳為1~50質量%、更佳為10~40質量%之方式使用。 The usage-amount of a solvent is not specifically limited in the range which does not impair the objective of this invention. In terms of film-forming properties, the solvent is used so that the solid content concentration of the composition of the third aspect is preferably 1 to 50% by mass, more preferably 10 to 40% by mass.

(其他成分) (other ingredients)

第3態樣之組合物亦可包含第1態樣之聚矽烷化合物以外之聚矽烷。例如，就提高耐化學品性等方面而言，可列舉Mw較高之聚矽烷化合物(以下，亦簡稱為「高分子量聚矽烷」)，作為高分子量聚矽烷之Mw，例如超過5000且為100000以下，較佳為6000~60000左右。 The composition of the third aspect may contain polysilanes other than the polysilane compound of the first aspect. For example, in terms of improving chemical resistance, polysilane compounds with high Mw (hereinafter, also simply referred to as "high molecular weight polysilane") can be cited. The Mw of high molecular weight polysilane is, for example, more than 5,000 and 100,000 Hereinafter, it is preferably about 6,000 to 60,000.

就提高加工性之方面而言，第3態樣之組合物亦可包含聚矽烷化合物以外之含矽樹脂。作為聚矽烷化合物以外之含矽樹脂，可列舉聚矽氧烷樹脂或具有聚矽烷結構(I-1)及聚矽氧烷結構(I-2)之聚矽烷-聚矽氧烷樹脂。作為聚矽烷化合物以外之含矽樹脂之Mw，較佳為500~20000，更佳為1000~10000，進而較佳為2000~8000。 In terms of improving processability, the composition of the third aspect may contain a silicon-containing resin other than the polysilane compound. As the silicon-containing resin other than the polysilane compound, a polysiloxane resin or a polysilane-polysiloxane resin having a polysilane structure (I-1) and a polysiloxane structure (I-2) can be mentioned. The Mw of the silicone-containing resin other than the polysilane compound is preferably 500 to 20,000, more preferably 1,000 to 10,000, and still more preferably 2,000 to 8,000.

再者，上述聚矽烷-聚矽氧烷樹脂例如可藉由下述方式而製造，即，將第1態樣之聚矽烷化合物於溶劑中且於上述鹼性條件下進行處理後，使之與選自由矽化合物以及上述矽化合物之水解物、縮合物及水解縮合物所組成之群中之至少1種進行水解縮合反應，上述矽化合物係選自由下述通式(A-1-1)~(A-1-4)所表示之矽化合物所組成之群中之至少1種。 In addition, the above-mentioned polysilane-polysiloxane resin can be produced, for example, by treating the polysilane compound of the first aspect in a solvent under the above-mentioned alkaline conditions, and then mixing it with the polysilane compound. Selected from silicon compounds and hydrolyzates, condensates and hydrolysis condensates of the above-mentioned silicon compounds At least one of the group consisting of undergoes a hydrolysis condensation reaction, and the above-mentioned silicon compound is at least one selected from the group consisting of silicon compounds represented by the following general formulas (A-1-1) to (A-1-4) 1 type.

R¹R²R³SiX¹ (A-1-1) R ¹ R ² R ³ SiX ¹ (A-1-1)

R⁴R⁵SiX² ₂ (A-1-2) R ⁴ R ⁵ SiX ² ₂ (A-1-2)

R⁶SiX³ ₃ (A-1-3) R ⁶ SiX ³ ₃ (A-1-3)

SiX⁴ ₄ (A-1-4) SiX ⁴ ₄ (A-1-4)

(上述通式中，X¹~X⁴分別獨立地為水解性基，R¹、R²、R³、R⁴、R⁵及R⁶分別獨立地為氫原子或有機基，該有機基中之氫原子亦可被鹵素原子取代) (In the above general formula, X ¹ to X ⁴ are independently hydrolyzable groups, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently hydrogen atoms or organic groups, and in the organic group The hydrogen atom can also be replaced by a halogen atom)

作為X¹~X⁴所表示之水解性基，可列舉：烷氧基、鹵素原子或異氰酸酯基(NCO)等，較佳為烷氧基。 Examples of the hydrolyzable group represented by X ¹ to X ⁴ include an alkoxy group, a halogen atom, an isocyanate group (NCO), and the like, and an alkoxy group is preferred.

作為上述烷氧基，可列舉碳原子數1~6之烷氧基，具體而言，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第三丁氧基、戊氧基等。 Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms, and specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, th Tributoxy, pentoxy, etc.

作為上述鹵素原子，可列舉：氟原子、氯原子、溴原子或碘原子，較佳為氯原子。 As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, Preferably it is a chlorine atom.

作為R¹~R⁶所表示之有機基，可列舉碳數1~30之有機基，可列舉：烷基[甲基、乙基、正丙基、異丙基、正丁基及第三丁基等碳原子數1~10之烷基(較佳為碳原子數1~6之烷基，尤其是碳數1~4之烷基等)]、環烷基(環己基等碳原子數5~8之環烷基，尤其是碳原子數5~6之環烷基)、烯基[乙烯基、丙烯基、丁烯基等碳原子數2~10之烯基(較佳為碳原子數2~6之烯基，尤其是碳數2~4之烯基等)]、環烯基[1-環戊烯基、1-環己烯基等碳原子數5~10之環烯基(較佳為碳原子數5~8之環烯基，尤其是碳數5 ~7之環烯基等)]、芳基(苯基、萘基等碳原子數6~10之芳基)、芳烷基[苄基、苯乙基等C_6-10芳基-C_1-6烷基(C_6-10芳基-C_1-4烷基等)]、胺基、N-取代胺基(經上述烷基、環烷基、芳基、芳烷基、醯基等取代而成之N-單或二取代胺基等)等。上述烷基、環烷基、芳基或構成芳烷基之芳基等亦可具有1個或複數個取代基。作為此種取代基，可列舉：上述例示之烷基(尤其是碳原子數1~6之烷基等)、上述例示之烷氧基等。作為具有此種取代基之有機基，例如可列舉：甲苯基、二甲苯基、乙基苯基、甲基萘基等C_1-6烷基-C_6-10芳基(較佳為單、二或三C_1-4烷基-C_6-10芳基，尤其是單或二C_1-4烷基苯基等)；甲氧基苯基、乙氧基苯基、甲氧基萘基等C_1-10烷氧基C_6-10芳基(較佳為C_1-6烷氧基C_6-10芳基，尤其是C_1-4烷氧基苯基等)等。 Examples of the organic group represented by R ¹ to R ⁶ include organic groups having 1 to 30 carbon atoms, and examples thereof include alkyl [methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl]. Alkyl groups with 1 to 10 carbon atoms (preferably alkyl groups with 1 to 6 carbon atoms, especially alkyl groups with 1 to 4 carbon atoms, etc.)], cycloalkyl groups (such as cyclohexyl with 5 carbon atoms) Cycloalkyl groups of ~8, especially cycloalkyl groups of 5 to 6 carbon atoms), alkenyl [vinyl, propenyl, butenyl and other alkenyl groups of 2 to 10 carbon atoms (preferably carbon atoms) 2-6 alkenyl, especially alkenyl with 2-4 carbon atoms, etc.)], cycloalkenyl [1-cyclopentenyl, 1-cyclohexenyl and other cycloalkenyl with 5-10 carbon atoms ( Preferably it is a cycloalkenyl group with 5 to 8 carbon atoms, especially a cycloalkenyl group with 5 to 7 carbon atoms, etc.)], an aryl group (an aryl group with a carbon number of 6 to 10 such as phenyl, naphthyl, etc.), aryl Alkyl [benzyl, phenethyl, etc. C _6-10 aryl-C _1-6 alkyl (C _6-10 aryl-C _1-4 alkyl, etc.)], amino, N-substituted amino ( N-mono- or di-substituted amine groups, etc., substituted by the above-mentioned alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, acyl groups, etc.) and the like. The above-mentioned alkyl group, cycloalkyl group, aryl group, or aryl group constituting an aralkyl group, etc. may have one or a plurality of substituents. Examples of such a substituent include the above-exemplified alkyl groups (especially, the alkyl groups having 1 to 6 carbon atoms, etc.), the above-exemplified alkoxy groups, and the like. Examples of organic groups having such a substituent include C _1-6 alkyl-C _6-10 aryl groups (preferably mono-, Di- or tri-C _1-4 alkyl-C _6-10 aryl, especially mono- or di- C _1-4 alkyl phenyl, etc.); methoxyphenyl, ethoxyphenyl, methoxynaphthyl C _1-10 alkoxy C _6-10 aryl groups (preferably C _1-6 alkoxy C _6-10 aryl groups, especially C _1-4 alkoxy phenyl groups, etc.) and the like.

又，上述通式(A-1-3)所表示之矽化合物亦可為下述式(A-3)所表示之矽化合物。 Moreover, the silicon compound represented by the said general formula (A-1-3) may be the silicon compound represented by the following formula (A-3).

HOOC-U-Z-Y-Si(OR^a)₃ (A-3) HOOC-UZY-Si(OR ^a ) ₃ (A-3)

(上述通式(A-3)中，U表示藉由自芳香族環基或脂環基中將2個環碳原子之各1個氫原子去除而生成之2價基或可具有支鏈及/或雙鍵之伸烷基，Z表示-NHCO-或-CONH-，Y表示單鍵、伸烷基、伸芳基或-R^Y1-NH-R^Y2-(式中，R^Y1及R^Y2分別獨立地表示伸烷基)，R^a分別獨立地表示烴基；其中，U及/或Y亦可具有選自由(甲基)丙烯酸基、乙烯基及環氧基所組成之群中之至少1種基作為取代基) (In the above general formula (A-3), U represents a divalent group generated by removing one hydrogen atom of each of two ring carbon atoms from an aromatic ring group or an alicyclic group, or may have a branched chain and / or double bond alkylene, Z represents -NHCO- or -CONH-, Y represents single bond, alkylene, aryl or -R ^Y1 -NH-R ^Y2 - (in the formula, R ^Y1 and R ^Y2 each independently represents an alkylene group), and R ^a each independently represents a hydrocarbon group; wherein, U and/or Y may also have at least 1 selected from the group consisting of (meth)acrylic group, vinyl group and epoxy group seed group as a substituent)

作為上述U中之芳香族環，可列舉可具有碳數1~2之取代基之碳數6~10之芳香環(例如苯環、萘環、甲苯基、二甲苯基等)。 As the aromatic ring in the above-mentioned U, an aromatic ring having 6 to 10 carbon atoms (for example, a benzene ring, a naphthalene ring, a tolyl group, a xylyl group, etc.) which may have a substituent of 1 to 2 carbon atoms can be mentioned.

作為上述U中之脂環，可列舉碳數5~10之脂環(例如可列舉：單環環烷基、單環環烯基、2環式烷基、籠型烷基等，具體而言，例如為環戊烷環、環己烷環、環庚烷環、環辛烷環、環壬烷環、環癸烷環、二環戊二烯環、降

烷環、降

烯環、金剛烷環、籃烷環等)。 Examples of the alicyclic ring in the above U include alicyclic rings having 5 to 10 carbon atoms (for example, a monocyclic cycloalkyl group, a monocyclic cycloalkenyl group, a bicyclic alkyl group, a cage alkyl group, etc., specifically , such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, dicyclopentadiene, norm

alkane, norm

alkene ring, adamantane ring, basketane ring, etc.).

作為上述U中之可具有支鏈及/或雙鍵之伸烷基，可列舉碳數1~4之伸烷基，例如可列舉：亞甲基、伸乙基、伸丙基、伸乙烯基、(2-辛烯基)伸乙基、(2,4,6-三甲基-2-壬烯基)伸乙基等伸烷基、具有雙鍵之伸烷基或具有碳數1~9之支鏈之伸烷基。 As the alkylene group which may have a branched chain and/or a double bond in the above-mentioned U, an alkylene group having 1 to 4 carbon atoms can be mentioned, for example, a methylene group, an ethylidene group, a propylidene group and a vinylidene group can be mentioned. , (2-octenyl) ethylidene, (2,4,6-trimethyl-2-nonenyl) ethylidene and other alkylene groups, alkylene groups with double bonds or carbon number 1~ 9 branched chain extension.

作為上述Y中之伸烷基，可列舉碳數1~6之伸烷基，例如可列舉：亞甲基、伸乙基、伸丙基、伸丁基等。作為上述Y中之伸芳基，較佳為碳數6~10者。作為此種伸芳基，例如可列舉：伸苯基(鄰、間或對等)、伸萘基(1,4-、1,5-、2,6-等)等。作為上述Y中之-R^Y1-NH-R^Y2-，具體而言，例如可列舉：-CH₂-NH-CH₂-、-(CH₂)₂-NH-(CH₂)₂-、-(CH₂)₃-NH-(CH₂)₃-、-CH₂-NH-(CH₂)₂-、-(CH₂)₂-NH-CH₂-、-(CH₂)₂-NH-(CH₂)₃-、-(CH₂)₃-NH-(CH₂)₂-、-CH₂-NH-(CH₂)₃-、-(CH₂)₃-NH-CH₂-等。 As an alkylene group in the said Y, the C1-C6 alkylene group is mentioned, For example, a methylene group, an ethylene group, a propylidene group, a butylene group, etc. are mentioned. As the aryl group in the above-mentioned Y, those having 6 to 10 carbon atoms are preferable. As such an aryl-extended group, for example, a phenylene-extended group (ortho, meta, or para-extended group), a naphthylene-extended group (1,4-, 1,5-, 2,6-, etc.), etc. are mentioned. Specific examples of -R ^Y1 -NH-R ^Y2 - in the above Y include -CH ₂ -NH-CH ₂ -, -(CH ₂ ) ₂ -NH-(CH ₂ ) ₂ -, - (CH ₂ ) ₃ -NH-(CH ₂ ) ₃ -, -CH ₂ -NH-(CH ₂ ) ₂ -, -(CH ₂ ) ₂ -NH-CH ₂ -, -(CH ₂ ) ₂ -NH- (CH ₂ ) ₃ -, -(CH ₂ ) ₃ -NH-(CH ₂ ) ₂ -, -CH ₂ -NH-(CH ₂ ) ₃ -, -(CH ₂ ) ₃ -NH-CH ₂ - and the like.

作為聚矽氧烷樹脂，可列舉選自由矽化合物之水解物、縮合物及水解縮合物所組成之群中之至少1種，上述矽化合物係選自由上述通式(A-1-1)~(A-1-4)所表示之矽化合物所組成之群中之至少1種。 Examples of the polysiloxane resin include at least one selected from the group consisting of hydrolyzates, condensates, and hydrolysis condensates of silicon compounds, wherein the silicon compounds are selected from the above-mentioned general formula (A-1-1)~ At least one of the group consisting of the silicon compounds represented by (A-1-4).

上述第1態樣之聚矽烷化合物以外之樹脂(以下，稱為其他Si樹脂)可單獨使用，亦可將複數種組合使用。 Resins other than the polysilane compound of the above-mentioned first aspect (hereinafter, referred to as other Si resins) may be used alone or in combination of two or more.

於包含上述其他Si樹脂之情形時，第3態樣之組合物中之第1態樣之聚矽烷化合物與其他Si樹脂之調配比(質量比)根據用途適當變更即可，例如為1：99~99：1，較佳為10：90~90：10。 When the other Si resins are included, the blending ratio (mass ratio) of the polysilane compound of the first aspect and the other Si resins in the composition of the third aspect can be appropriately changed according to the application, for example, 1:99 ~99:1, preferably 10:90~90:10.

第3態樣之組合物亦可包含1分子中具有2個以上之羥基或羧基之有機化合物作為於鹼性之水溶液或溶液中之溶解促進劑。作為此種有機化合物，可列舉下述所示之化合物。 The composition of the third aspect may also contain an organic compound having two or more hydroxyl or carboxyl groups in one molecule as a dissolution accelerator in an alkaline aqueous solution or solution. as such an organic compound The compounds include the compounds shown below.

[化6]

[hua 6]

再者，上述結構式中之E為氫原子、甲基或羥基甲基，R¹⁵為亞甲基、羰基或伸苯基，n為3以上且未達100之整數。na表示1~3之自然數，nb表示1以上之自然數，nc表示2~4之自然數，nd表示2以上之自然數。 Furthermore, E in the above structural formula is a hydrogen atom, a methyl group or a hydroxymethyl group, R ¹⁵ is a methylene group, a carbonyl group or a phenylene group, and n is an integer of 3 or more and less than 100. na represents a natural number from 1 to 3, nb represents a natural number above 1, nc represents a natural number from 2 to 4, and nd represents a natural number above 2.

上述結構式中可存在鏡像異構物(enantiomer)或非鏡像異構物(diastereomer)，但各結構式代表性地表示該等立體異構物之全部。該等立體異構物可單獨使用，亦可作為混合物而使用。 In the above structural formulas, enantiomers or diastereomers may exist, but each structural formula typically represents all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

上述有機化合物可單獨使用1種或將2種以上組合使用。該使用量相對於第3態樣之組合物之除去溶劑之固形物成分總量，較佳為0.001~50質量%，更佳為0.01~30質量%。 The above-mentioned organic compounds may be used alone or in combination of two or more. The usage-amount is preferably 0.001 to 50 mass %, more preferably 0.01 to 30 mass % with respect to the total amount of the solid content of the composition of the third aspect excluding the solvent.

藉由添加此種有機化合物，使用上述組合物形成之膜之崩解加速而容易剝離。 By adding such an organic compound, the disintegration of the film formed using the above-mentioned composition is accelerated and peeling is facilitated.

為了提高穩定性，第3態樣之組合物中亦可包含碳數為1~30之1價或2價以上之有機酸。作為此時添加之酸，可列舉：甲酸、乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、油酸、硬脂酸、亞麻油酸、次亞麻油酸、苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、水楊酸、三氟乙酸、單氯乙酸、二氯乙酸、三氯乙酸、草酸、丙二酸、甲基丙二酸、乙基丙二酸、丙基丙二酸、丁基丙二酸、二甲基丙二酸、二乙基丙二酸、琥珀酸、甲基琥珀酸、戊二酸、己二酸、伊康酸、順丁烯二酸、反丁烯二酸、檸康酸、檸檬酸等。該等之中，尤佳為草酸、順丁烯二酸、甲酸、乙酸、丙酸、檸檬酸等。又，為了保持穩定性，亦可將2種以上之酸混合使用。可將上述有機酸以換算成組合物之pH值而成為較佳為0≦pH≦7、更佳為0.3≦pH≦6.5、進而較佳為0.5≦pH≦6之方式進行調配。 In order to improve stability, the composition of the third aspect may contain a monovalent or divalent organic acid having 1 to 30 carbon atoms. Examples of the acid to be added at this time include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, oleic acid, stearic acid, linoleic acid, and hydrinoic acid. Sesoleic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methyl propylene Diacid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid , Iconic acid, maleic acid, fumaric acid, citraconic acid, citric acid, etc. Among these, oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid and the like are particularly preferred. Moreover, in order to maintain stability, you may mix and use 2 or more types of acids. The above-mentioned organic acid can be formulated so as to be preferably 0≦pH≦7, more preferably 0.3≦pH≦6.5, and still more preferably 0.5≦pH≦6 in terms of pH of the composition.

又，第3態樣之組合物亦可包含具有環狀醚作為取代基之1價或2價以上之醇或醚化合物作為穩定劑。作為可使用之穩定劑，具體而言，可列舉日本專利特開2009-126940號公報(0180)~(0184)段落所記載之穩定劑。 In addition, the composition of the third aspect may contain, as a stabilizer, a monovalent or divalent alcohol or ether compound having a cyclic ether as a substituent. Specific examples of stabilizers that can be used include stabilizers described in paragraphs (0180) to (0184) of Japanese Patent Laid-Open No. 2009-126940.

第3態樣之組合物亦可包含水。藉由添加水，而微影性能提高。第3 態樣之組合物之溶劑成分中之水之含有率較佳為超過0質量%且未達50質量%，更佳為0.3~30質量%，進而較佳為0.5~20質量%。 The composition of the third aspect may also contain water. By adding water, the lithography performance is improved. 3rd The content rate of water in the solvent component of the composition of this aspect is preferably more than 0% by mass and less than 50% by mass, more preferably 0.3 to 30% by mass, and still more preferably 0.5 to 20% by mass.

第3態樣之組合物亦可包含光酸產生劑。作為可使用之光酸產生劑，具體而言，可列舉日本專利特開2009-126940號公報(0160)~(0179)段落所記載之光酸產生劑。 The composition of the third aspect may also contain a photoacid generator. As a photoacid generator which can be used, the photoacid generator described in the paragraphs (0160)-(0179) of Unexamined-Japanese-Patent No. 2009-126940 is mentioned specifically,.

第3態樣之組合物亦可視需要包含界面活性劑。作為可使用之界面活性劑，具體而言，可列舉日本專利特開2009-126940號公報(0185)段落所記載之界面活性劑。 The composition of the third aspect may optionally contain a surfactant. As the surfactant that can be used, specifically, the surfactant described in the paragraph (0185) of Japanese Patent Laid-Open No. 2009-126940 can be mentioned.

第3態樣之組合物亦可包含熱交聯促進劑。作為可使用之熱交聯促進劑，具體而言，可列舉日本專利特開2007-302873號公報所記載之熱交聯促進劑。作為熱交聯促進劑，例如可列舉磷酸鹽化合物或硼酸鹽化合物。作為此種磷酸鹽化合物，例如可列舉：磷酸銨、磷酸四甲基銨、磷酸四丁基銨等銨鹽、磷酸三苯基鋶等鋶鹽。又，作為此種硼酸鹽化合物，例如可列舉：硼酸銨、硼酸四甲基銨、硼酸四丁基銨等銨鹽、硼酸三苯基鋶等鋶鹽。 The composition of the third aspect may also contain a thermal crosslinking accelerator. As a thermal crosslinking accelerator which can be used, the thermal crosslinking accelerator described in Unexamined-Japanese-Patent No. 2007-302873 is mentioned specifically,. As a thermal crosslinking accelerator, a phosphate compound or a borate compound is mentioned, for example. As such a phosphate compound, ammonium salts, such as ammonium phosphate, tetramethylammonium phosphate, and tetrabutylammonium phosphate, and pericynium salts, such as triphenyl pericynium phosphate, are mentioned, for example. Moreover, as such a borate compound, ammonium salts, such as ammonium borate, tetramethylammonium borate, and tetrabutylammonium borate, and periconium salts, such as triphenyl periconium borate, are mentioned, for example.

再者，上述熱交聯促進劑可單獨使用1種或將2種以上組合使用。又，熱交聯促進劑之添加量相對於上述組合物之除去溶劑後之固形物成分總量，較佳為0.01~50質量%，更佳為0.1~40質量%。 In addition, the said thermal crosslinking accelerator can be used individually by 1 type or in combination of 2 or more types. Moreover, the addition amount of the thermal crosslinking accelerator is preferably 0.01 to 50 mass %, more preferably 0.1 to 40 mass % with respect to the total solid content of the composition after removing the solvent.

第3態樣之組合物亦可包含其他各種硬化劑。 The composition of the third aspect may contain other various curing agents.

作為硬化劑，例如可列舉：布忍斯特酸；咪唑類；有機胺類；有機磷化合物及其複合體；路易斯酸之有機胺錯合物；脒類；藉由光或熱而產生鹼成分之硬化劑等。 Examples of the curing agent include: Brunsted acid; imidazoles; organic amines; organic phosphorus compounds and complexes thereof; organic amine complexes of Lewis acids; amidines; Hardener, etc.

(用途) (use)

第3態樣之組合物包含殘存金屬較少且矽氧烷化受到抑制(控制)之聚矽烷化合物，因此可適當用於半導體、顯示器或太陽電池等製造製程用之材料。例如，可用於形成保護各種基板(包括含金屬氧化物之膜、含各種金屬之膜)之保護膜或層間膜之用途。 The composition of the third aspect contains a polysilane compound with less residual metal and suppressed (controlled) siloxane, so it can be suitably used as a material for manufacturing processes such as semiconductors, displays, or solar cells. For example, it can be used to form protective films or interlayer films for protecting various substrates (including metal oxide-containing films and various metal-containing films).

作為上述各種基板，可列舉：半導體基板、液晶顯示器、有機發光顯示器(OLED)、電泳顯示器(電子紙)、觸控面板、彩色濾光片、背光裝置等顯示器材料之基板(包括含金屬氧化物之膜、含各種金屬之膜)、太陽電池之基板(包括含金屬氧化物之膜、含各種金屬之膜)、光感測器等光電轉換元件之基板(包括含金屬氧化物之膜、含各種金屬之膜)、光電元件之基板(包括含金屬氧化物之膜、含各種金屬之膜)。 Examples of the above-mentioned various substrates include semiconductor substrates, liquid crystal displays, organic light-emitting displays (OLEDs), electrophoretic displays (electronic paper), touch panels, color filters, and substrates for display materials such as backlight devices (including metal oxide-containing substrates). films, films containing various metals), substrates of solar cells (including films containing metal oxides, films containing various metals), substrates of photoelectric conversion elements such as photo sensors (including films containing metal oxides, films containing various metals) Films of various metals), substrates of optoelectronic components (including films containing metal oxides, films containing various metals).

又，於第3態樣之組合物中之基材成分(樹脂成分)實質上僅由第1態樣之聚矽烷化合物構成之情形時，由於間隙填充特性尤其優異，故而包含於半導體基板之表面形成微細之槽，於該槽之內部填充第3態樣之組合物，使形成於槽之兩側之元件之間電性分離的溝槽、隔離結構，可用於形成絕緣膜、鈍化膜、平坦化膜、保護膜等之用途。 In addition, when the base material component (resin component) in the composition of the third aspect consists substantially only of the polysilane compound of the first aspect, it is included in the surface of the semiconductor substrate because of its excellent gap-filling properties. Forming a fine groove, filling the inside of the groove with the composition of the third aspect, and forming a groove and an isolation structure for electrical separation between elements formed on both sides of the groove, can be used to form an insulating film, a passivation film, a flat Chemical film, protective film, etc.

<膜及具備上述膜之基板> <Film and substrate provided with the above film>

第4態樣之膜係包含第2態樣之聚矽烷化合物之膜。 The film of the fourth aspect is a film of the polysilane compound of the second aspect.

第5態樣之基板係具備包含第2態樣之聚矽烷化合物之膜之基板。 The substrate of the fifth aspect is a substrate including the film of the polysilane compound of the second aspect.

第4態樣之膜較佳為如上所述般包含溝槽、隔離結構之絕緣膜、鈍化膜、平坦化膜或保護膜。 The film of the fourth aspect preferably includes a trench, an insulating film of an isolation structure, a passivation film, a planarization film, or a protective film as described above.

作為形成第4態樣之膜之方法，只要無損本發明之效果，則並無特別限制，可列舉視需要於任意基板上使用輥式塗佈機、反向塗佈機、棒式塗佈機等接觸轉印型塗佈裝置或旋轉器(旋轉式塗佈裝置)、淋幕式平面塗佈機等非接觸型塗佈裝置進行塗佈之方法。 The method of forming the film of the fourth aspect is not particularly limited as long as the effect of the present invention is not impaired, and as necessary, a roll coater, a reverse coater, and a bar coater may be used on any substrate. Equal contact transfer type coating device or spinner (rotary coating device), curtain type flat coating A method of coating with a non-contact coating device such as a machine.

作為基板，並無特別限制，例如可列舉：半導體基板、液晶顯示器、有機發光顯示器(OLED)、電泳顯示器(電子紙)、觸控面板、彩色濾光片、背光裝置等顯示器材料之基板(包括含金屬氧化物之膜、含各種金屬之膜)、太陽電池之基板(包括含金屬氧化物之膜、含各種金屬之膜)、光感測器等光電轉換元件之基板(包括含金屬氧化物之膜、含各種金屬之膜)、光電元件之基板(包括含金屬氧化物之膜、含各種金屬之膜)，以及玻璃基板、石英基板、透明或半透明之樹脂基板(例如聚碳酸酯、聚對苯二甲酸乙二酯、聚醚碸、聚醯亞胺、聚醯胺醯亞胺等耐熱性之材料等)、金屬、矽基板等。 The substrate is not particularly limited, and examples include semiconductor substrates, liquid crystal displays, organic light-emitting displays (OLEDs), electrophoretic displays (electronic paper), touch panels, color filters, and substrates for display materials such as backlight devices (including Films containing metal oxides, films containing various metals), substrates for solar cells (including films containing metal oxides, films containing various metals), substrates for photoelectric conversion elements such as photo sensors (including metal oxides) films, films containing various metals), substrates of photovoltaic elements (including films containing metal oxides, films containing various metals), as well as glass substrates, quartz substrates, transparent or translucent resin substrates (such as polycarbonate, Heat-resistant materials such as polyethylene terephthalate, polyether, polyimide, polyimide, etc.), metal, silicon substrate, etc.

基板之厚度並無特別限定，可根據圖案形成體之使用態樣適當選擇。 The thickness of the substrate is not particularly limited, and can be appropriately selected according to the usage of the patterned body.

上述塗佈後之塗膜較佳為進行乾燥(預烘烤)。乾燥方法並無特別限定，例如可列舉：(1)利用加熱板於80~120℃、較佳為90~100℃之溫度下使之乾燥60~120秒之方法，(2)於室溫下放置數小時~數天之方法，(3)放入至熱風加熱器或紅外線加熱器中數十分鐘~數小時而將溶劑去除之方法等。 The coating film after the above-mentioned coating is preferably dried (pre-baked). The drying method is not particularly limited, for example, (1) a method of drying at a temperature of 80 to 120° C., preferably 90 to 100° C. for 60 to 120 seconds using a hot plate, (2) at room temperature The method of leaving it for several hours to several days, (3) the method of putting it into a hot air heater or an infrared heater for tens of minutes to several hours to remove the solvent, etc.

對於上述乾燥後之塗膜，照射紫外線、準分子雷射光等活性能量線而進行曝光與否均可。所照射之能量線量並無特別限制，例如可列舉30~2000mJ/cm²左右。曝光之步驟亦可代替下述焙燒之步驟或與焙燒之步驟一併進行。又，於曝光之步驟中，例如可選擇性地對所形成之塗佈膜進行曝光，於包含選擇性之曝光步驟之情形時，亦可包含顯影之步驟。又，例如亦可對所形成之塗佈膜進行壓印微影。於進行壓印微影之情形時，例如可列舉包括如下步驟之方法：將第3態樣之組合物塗佈於基板上而形成塗佈膜之步驟；將形成有特定圖案之凹凸結構之模具按壓於塗佈膜之步驟；及曝光之步驟。 The above-mentioned dried coating film may or may not be exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light. The amount of energy rays to be irradiated is not particularly limited, but for example, it is about 30 to 2000 mJ/cm ² . The step of exposing can also be performed in place of or together with the step of firing described below. Moreover, in the step of exposing, for example, the formed coating film can be selectively exposed to light, and when a selective exposure step is included, the step of developing can also be included. Moreover, for example, imprint lithography may be performed on the formed coating film. In the case of imprint lithography, for example, a method including the following steps: a step of applying the composition of the third aspect on a substrate to form a coating film; forming a mold with a specific pattern of concave-convex structure The step of pressing on the coating film; and the step of exposing.

曝光之步驟係於將模具按壓於塗佈膜之狀態下針對包含第3態樣之組合物之塗佈膜而進行。於藉由曝光之硬化後，將上述模具剝離，藉此可獲得對應於模具之形狀而經圖案化之第4態樣之膜。 The step of exposing is performed with respect to the coating film containing the composition of the 3rd aspect in the state which pressed a mold to the coating film. After hardening by exposure, the said mold is peeled, and the film of the 4th aspect patterned according to the shape of a mold can be obtained.

就提高膜物性之方面而言，上述乾燥後、曝光後或顯影後之塗膜較佳為進行焙燒(後烘烤)。焙燒溫度亦取決於底層基板或使用用途，例如為200~1000℃之範圍，較佳為200℃~500℃，更佳為200~250℃。焙燒環境並無特別限定，可為氮氣環境或氬氣環境等惰性氣體環境下、真空下或減壓下。可為大氣下，亦可適當控制氧濃度。焙燒時間適當變更即可，例如為10分鐘~120分鐘左右。 From the viewpoint of improving the physical properties of the film, the coating film after drying, after exposure, or after development is preferably baked (post-baking). The firing temperature also depends on the underlying substrate or usage, for example, it is in the range of 200 to 1000°C, preferably 200 to 500°C, and more preferably 200 to 250°C. The calcination atmosphere is not particularly limited, and may be an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, a vacuum, or a reduced pressure. It can be in the atmosphere, and the oxygen concentration can also be appropriately controlled. The calcination time may be appropriately changed, and is, for example, about 10 minutes to 120 minutes.

作為第4及第5態樣中之膜之膜厚，較佳為10~3000nm，更佳為50~1500nm，進而較佳為100~1000nm。 The film thickness of the film in the fourth and fifth aspects is preferably 10 to 3000 nm, more preferably 50 to 1500 nm, and still more preferably 100 to 1000 nm.

[實施例] [Example]

以下，基於實施例對本發明更詳細地進行說明，但本發明並不受該等實施例限定。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[實施例1] [Example 1]

向安裝有三通活栓之內容積1000ml之圓型燒瓶中添加粒狀(粒徑20~1000μm)之鎂25g及作為觸媒之三(乙醯丙酮)鐵(III)2.1g，於50℃下加熱減壓至1mmHg(=133kPa)，使反應器(燒瓶)內部乾燥後，將乾燥氬氣導入至反應器內，添加預先利用二苯甲酮鈉羰自由基(sodium benzophenone ketyl)進行乾燥之四氫呋喃(THF)500ml，於25℃下攪拌約60分鐘。利用注射器向該反應混合物中添加預先藉由蒸餾進行精製之甲基苯基二氯矽烷63.5g(0.3mol)，並於25℃下攪拌約24小時。反應結束後，向反應混合物中投入1N(=1莫耳/L)之鹽酸1000ml，進而利用甲苯500ml進行萃取。利用純水200ml將甲苯相洗淨10次，並利用無水硫酸鎂使甲苯相乾燥後，將甲苯蒸餾去除，藉此獲得直鏈狀之甲基苯基矽烷聚合物(質量平均分子量2000)28.4g(產率63%)。 Add 25g of granular (20~1000μm particle size) magnesium and 2.1g of tri(acetylacetone)iron(III) as a catalyst to a round flask with an inner volume of 1000ml equipped with a three-way stopcock, and heat at 50°C The pressure was reduced to 1 mmHg (=133 kPa), the inside of the reactor (flask) was dried, and then dry argon gas was introduced into the reactor, and sodium carbonyl radical (sodium benzophenone) was added in advance. benzophenone ketyl) and 500 ml of tetrahydrofuran (THF) for drying, and stirred at 25° C. for about 60 minutes. To this reaction mixture was added 63.5 g (0.3 mol) of methylphenyldichlorosilane previously purified by distillation using a syringe, and the mixture was stirred at 25°C for about 24 hours. After completion of the reaction, 1000 ml of 1N (=1 mol/L) hydrochloric acid was added to the reaction mixture, followed by extraction with 500 ml of toluene. The toluene phase was washed 10 times with 200 ml of pure water, and after drying the toluene phase with anhydrous magnesium sulfate, the toluene was distilled off to obtain 28.4 g of a linear methylphenylsilane polymer (mass average molecular weight: 2000). (63% yield).

[實施例2] [Example 2]

向安裝有三通活栓之內容積1000ml之圓型燒瓶中添加粒狀(粒徑20~1000μm)之鎂25g及作為觸媒之三(乙醯丙酮)鐵(III)2.1g，於50℃下加熱減壓至1mmHg，使反應器內部乾燥後，將乾燥氬氣導入至反應器內，添加預先利用二苯甲酮鈉羰自由基進行乾燥之THF500ml，於25℃下攪拌約60分鐘。利用注射器向該反應混合物中添加預先藉由蒸餾進行精製之甲基苯基二氯矽烷63.5g(0.3mol)，並於25℃下攪拌約24小時。 Add 25g of granular (20~1000μm particle size) magnesium and 2.1g of tri(acetylacetone)iron(III) as a catalyst to a round flask with an inner volume of 1000ml equipped with a three-way stopcock, and heat at 50°C The pressure was reduced to 1 mmHg, the inside of the reactor was dried, dry argon was introduced into the reactor, 500 ml of THF previously dried with benzophenone sodium carbonyl radical was added, and the mixture was stirred at 25° C. for about 60 minutes. To this reaction mixture was added 63.5 g (0.3 mol) of methylphenyldichlorosilane previously purified by distillation using a syringe, and the mixture was stirred at 25°C for about 24 hours.

將所獲得之直鏈狀之甲基苯基矽烷聚合物溶解於甲苯150g與四氫呋喃150g之混合溶液中，進而混合以10質量%之比率包含氯化銅(II)(CuCl₂)之氯化銅水溶液200g並攪拌60分鐘後，將包含直鏈狀之甲基苯基矽烷聚合物之有機相與包含氯化銅之水相進行分離。接下來，利用純水200ml將包含直鏈狀之甲基苯基矽烷聚合物之有機相洗淨3次後，將溶劑成分蒸餾去除，獲得直鏈狀之甲基苯基矽烷聚合物(質量平均分子量2000)32.4g(產率72.6%)。 The obtained linear methylphenylsilane polymer was dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and further mixed with copper chloride containing copper(II) chloride (CuCl ₂ ) at a ratio of 10% by mass After 200 g of the aqueous solution was stirred for 60 minutes, the organic phase containing the linear methylphenylsilane polymer was separated from the aqueous phase containing copper chloride. Next, the organic phase containing the linear methylphenylsilane polymer was washed three times with 200 ml of pure water, and then the solvent component was distilled off to obtain a linear methylphenylsilane polymer (average mass Molecular weight 2000) 32.4 g (yield 72.6%).

[實施例3] [Example 3]

向安裝有三通活栓之內容積1000ml之圓型燒瓶中添加粒狀(粒徑20 ~1000μm)之鎂25g及作為觸媒之三(乙醯丙酮)鐵(III)2.1g，於50℃下加熱減壓至1mmHg，使反應器內部乾燥後，將乾燥氬氣導入至反應器內，添加預先利用二苯甲酮鈉羰自由基進行乾燥之四氫呋喃500ml，於室溫(25℃)下攪拌約30分鐘。向該反應混合物中添加預先藉由蒸餾進行精製之苯基三氯矽烷105.8g(0.50mol)，並於20℃下攪拌約18小時。反應結束後，添加甲苯300ml，然後藉由減壓過濾將藉由反應而生成之氯化鎂、剩餘之鎂去除。利用純水200ml將濾液洗淨10次，並利用無水硫酸鎂使甲苯相乾燥後，將甲苯及四氫呋喃蒸餾去除，藉此獲得支鏈狀之聚苯基矽烷50g。 To a round flask with an inner volume of 1000ml equipped with a three-way stopcock, add granular (particle size 20 ~1000μm) magnesium 25g and three (acetone acetone) iron (III) as a catalyst 2.1g, heated and decompressed to 1mmHg at 50°C, after drying the inside of the reactor, dry argon was introduced into the reactor , 500 ml of tetrahydrofuran previously dried with sodium benzophenone carbonyl radical was added, and the mixture was stirred at room temperature (25° C.) for about 30 minutes. To this reaction mixture was added 105.8 g (0.50 mol) of phenyltrichlorosilane previously purified by distillation, and the mixture was stirred at 20° C. for about 18 hours. After completion of the reaction, 300 ml of toluene was added, and the magnesium chloride and remaining magnesium produced by the reaction were removed by filtration under reduced pressure. The filtrate was washed 10 times with 200 ml of pure water, and the toluene phase was dried with anhydrous magnesium sulfate, and then toluene and tetrahydrofuran were distilled off to obtain 50 g of branched polyphenylsilane.

反應結束後，向反應混合物中投入1N(=1莫耳/L)之鹽酸1000ml，進而利用甲苯500ml進行萃取。利用純水200ml將甲苯相洗淨10次，並利用無水硫酸鎂使甲苯相乾燥後，將甲苯蒸餾去除，藉此獲得支鏈狀之聚苯基矽烷(質量平均分子量2000)38.2g(產率72%)。 After completion of the reaction, 1000 ml of 1N (=1 mol/L) hydrochloric acid was added to the reaction mixture, followed by extraction with 500 ml of toluene. The toluene phase was washed 10 times with 200 ml of pure water, and after drying the toluene phase with anhydrous magnesium sulfate, the toluene was distilled off to obtain 38.2 g of branched polyphenylsilane (mass average molecular weight: 2000) (yield 72%).

[實施例4] [Example 4]

向安裝有三通活栓之內容積1000ml之圓型燒瓶中添加粒狀(粒徑20~1000μm)之鎂25g及作為觸媒之三(乙醯丙酮)鐵(III)2.1g，於50℃下加熱減壓至1mmHg，使反應器(燒瓶)內部乾燥後，將乾燥氬氣導入至反應器內，添加預先利用二苯甲酮鈉羰自由基進行乾燥之四氫呋喃500ml，於室溫下攪拌約30分鐘。向該反應混合物中添加預先藉由蒸餾進行精製之苯基三氯矽烷105.8g(0.50mol)，並於20℃下攪拌約18小時。反應結束後，添加甲苯300ml，然後藉由減壓過濾將藉由反應而生成之氯化鎂、剩餘之鎂去除。利用純水200ml將濾液洗淨10次，並利用無水硫酸鎂使甲苯相乾燥後，將甲苯及四氫呋喃蒸餾去除，藉此獲得支鏈狀之聚苯基矽烷50g。 Add 25g of granular (20~1000μm particle size) magnesium and 2.1g of tri(acetylacetone)iron(III) as a catalyst to a round flask with an inner volume of 1000ml equipped with a three-way stopcock, and heat at 50°C The pressure was reduced to 1 mmHg, the inside of the reactor (flask) was dried, dry argon was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium benzophenone carbonyl radical was added, and the mixture was stirred at room temperature for about 30 minutes. . To this reaction mixture was added 105.8 g (0.50 mol) of phenyltrichlorosilane previously purified by distillation, and the mixture was stirred at 20° C. for about 18 hours. After the completion of the reaction, 300 ml of toluene was added, and the magnesium chloride and residual magnesium produced by the reaction were removed by filtration under reduced pressure. The filtrate was washed 10 times with 200 ml of pure water, and after drying the toluene phase with anhydrous magnesium sulfate, toluene and tetrahydrofuran were distilled off to obtain 50 g of branched polyphenylsilane.

將所獲得之支鏈狀之聚苯基矽烷溶解於甲苯150g與四氫呋喃150g之混合溶液中，進而混合以10質量%之比率包含氯化銅(II)(CuCl₂)之氯化銅水溶液200g並攪拌60分鐘後，將包含支鏈狀之聚苯基矽烷之有機相與包含氯化銅之水相進行分離。接下來，利用純水200ml將包含支鏈狀之聚苯基矽烷之有機相洗淨3次後，將溶劑成分蒸餾去除，獲得支鏈狀之聚苯基矽烷(質量平均分子量2000)41.9g(產率79%)。 The obtained branched polyphenylsilane was dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and then 200 g of an aqueous copper chloride solution containing copper(II) chloride (CuCl ₂ ) was mixed in a ratio of 10% by mass. After stirring for 60 minutes, the organic phase containing branched polyphenylsilane was separated from the aqueous phase containing copper chloride. Next, the organic phase containing the branched polyphenylsilane was washed three times with 200 ml of pure water, and then the solvent component was distilled off to obtain 41.9 g of branched polyphenylsilane (mass average molecular weight: 2000) ( yield 79%).

[實施例5] [Example 5]

向安裝有三通活栓之內容積1000ml之圓型燒瓶中添加粒狀(粒徑20~1000μm)之鎂25g及作為觸媒之三(乙醯丙酮)鐵(III)2.1g，於50℃下加熱減壓至1mmHg，使反應器內部乾燥後，將乾燥氬氣導入至反應器內，添加預先利用二苯甲酮鈉羰自由基進行乾燥之THF 500ml，於25℃下攪拌約60分鐘。利用注射器向該反應混合物中添加預先藉由蒸餾進行精製之苯基三氯矽烷63.5g(0.3mol)及二甲基二氯矽烷34.5g(0.3mol)，並於25℃下攪拌約24小時。反應結束後，向反應混合物中投入1N(=1莫耳/L)之鹽酸1000ml，進而利用甲苯500ml進行萃取。利用純水200ml將甲苯相洗淨10次，並利用無水硫酸鎂使甲苯相乾燥後，將甲苯蒸餾去除，藉此獲得支鏈狀之苯基矽烷-甲基矽烷共聚物(前者/後者(莫耳比)=1/1)(質量平均分子量3000)。 Add 25g of granular (20~1000μm particle size) magnesium and 2.1g of tri(acetylacetone)iron(III) as a catalyst to a round flask with an inner volume of 1000ml equipped with a three-way stopcock, and heat at 50°C The pressure was reduced to 1 mmHg, the inside of the reactor was dried, dry argon was introduced into the reactor, 500 ml of THF previously dried with benzophenone sodium carbonyl radical was added, and the mixture was stirred at 25°C for about 60 minutes. To this reaction mixture, 63.5 g (0.3 mol) of phenyltrichlorosilane previously purified by distillation and 34.5 g (0.3 mol) of dimethyldichlorosilane were added to the reaction mixture, and the mixture was stirred at 25° C. for about 24 hours. After completion of the reaction, 1000 ml of 1N (=1 mol/L) hydrochloric acid was added to the reaction mixture, followed by extraction with 500 ml of toluene. The toluene phase was washed 10 times with 200 ml of pure water, and after drying the toluene phase with anhydrous magnesium sulfate, the toluene was distilled off to obtain a branched phenylsilane-methylsilane copolymer (the former/the latter (Mo Ear ratio) = 1/1) (mass average molecular weight 3000).

將所獲得之支鏈狀之苯基矽烷-二甲基矽烷共聚物溶解於甲苯150g與四氫呋喃150g之混合溶液中，進而混合以10質量%之比率包含氯化銅(II)(CuCl₂)之氯化銅水溶液200g並攪拌60分鐘後，將包含支鏈狀之苯基矽烷-二甲基矽烷共聚物之有機相與包含氯化銅之水相進行分離。接下來，利用純水200ml將包含支鏈狀之苯基矽烷-二甲基矽烷共聚物之有機相洗淨3次後，將溶劑成分蒸餾去除，獲得苯基矽烷-甲基矽烷共聚物(質量平均分子量2000)36.6g(產率74%)。 The obtained branched phenylsilane-dimethylsilane copolymer was dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and then mixed with copper(II) chloride (CuCl ₂ ) at a ratio of 10% by mass. After stirring 200 g of the copper chloride aqueous solution for 60 minutes, the organic phase containing the branched phenylsilane-dimethylsilane copolymer and the aqueous phase containing the cupric chloride were separated. Next, the organic phase containing the branched phenylsilane-dimethylsilane copolymer was washed three times with 200 ml of pure water, and then the solvent component was distilled off to obtain a phenylsilane-methylsilane copolymer (mass Average molecular weight 2000) 36.6 g (74% yield).

[實施例6] [Example 6]

向安裝有三通活栓之內容積1000ml之圓型燒瓶中添加粒狀(粒徑20~1000μm)之鎂25g及作為觸媒之三(乙醯丙酮)鐵(III)2.1g，於50℃下加熱減壓至1mmHg，使反應器內部乾燥後，將乾燥氬氣導入至反應器內，添加預先利用二苯甲酮鈉羰自由基進行乾燥之四氫呋喃500ml，於室溫下攪拌約30分鐘。向該反應混合物中添加預先藉由蒸餾進行精製之甲基苯基二氯矽烷63.5g(0.3mol)，並於20℃下攪拌約6小時。反應結束後，添加甲苯300ml，然後藉由減壓過濾將藉由反應而生成之氯化鎂、剩餘之鎂去除。利用純水200ml將濾液洗淨10次，並利用無水硫酸鎂使甲苯相乾燥後，將甲苯及四氫呋喃蒸餾去除，藉此獲得環狀之甲基苯基矽烷50g。 Add 25g of granular (20~1000μm particle size) magnesium and 2.1g of tri(acetylacetone)iron(III) as a catalyst to a round flask with an inner volume of 1000ml equipped with a three-way stopcock, and heat at 50°C After reducing the pressure to 1 mmHg and drying the inside of the reactor, dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with benzophenone sodium carbonyl radical was added, and the mixture was stirred at room temperature for about 30 minutes. To this reaction mixture was added 63.5 g (0.3 mol) of methylphenyldichlorosilane previously purified by distillation, and the mixture was stirred at 20°C for about 6 hours. After the completion of the reaction, 300 ml of toluene was added, and the magnesium chloride and residual magnesium produced by the reaction were removed by filtration under reduced pressure. The filtrate was washed 10 times with 200 ml of pure water, and the toluene phase was dried with anhydrous magnesium sulfate, and then toluene and tetrahydrofuran were distilled off to obtain 50 g of cyclic methylphenylsilane.

反應結束後，向反應混合物中投入1N(=1莫耳/L)之鹽酸1000ml，進而利用甲苯500ml進行萃取。利用純水200ml將甲苯相洗淨10次，並利用無水硫酸鎂使甲苯相乾燥後，將甲苯蒸餾去除，藉此獲得環狀之甲基苯基矽烷聚合物(質量平均分子量700)31g(產率86%)。 After completion of the reaction, 1000 ml of 1N (=1 mol/L) hydrochloric acid was added to the reaction mixture, followed by extraction with 500 ml of toluene. The toluene phase was washed 10 times with 200 ml of pure water, and after drying the toluene phase with anhydrous magnesium sulfate, the toluene was distilled off to obtain 31 g of a cyclic methylphenylsilane polymer (mass average molecular weight: 700). rate 86%).

[比較例1] [Comparative Example 1]

向安裝有三通活栓之內容積1000ml之圓型燒瓶中添加粒狀(粒徑20~1000μm)之鎂25.0g、無水氯化鋅(ZnCl₂)16.2g，於50℃下加熱減壓至1mmHg，使反應器內部乾燥後，將乾燥氬氣導入至反應器內，添加預先利用二苯甲酮鈉羰自由基進行乾燥之THF500ml，於25℃下攪拌約60分鐘。利用注射器向該反應混合物中添加預先藉由蒸餾進行精製之甲基苯基二氯矽烷63.5g(0.3mol)，並於25℃下攪拌約24小時。反應結束後，向反應混合物中投入1N(=1莫耳/L)之鹽酸1000ml，進而利用甲苯500ml進行萃取。利用純水200ml將甲苯相洗淨10次，並利用無水硫酸鎂使甲苯相乾燥後，將甲苯蒸餾去除，藉此獲得甲基苯基矽烷聚合物(質量平均分子量6000)21.6g(產率60%)。 To a round flask with an inner volume of 1000ml installed with a three-way stopcock, add 25.0g of granular (particle size: 20~1000μm) magnesium and 16.2g of anhydrous zinc chloride (ZnCl ₂ ), and heat and reduce the pressure to 1mmHg at 50°C. After drying the inside of the reactor, dry argon gas was introduced into the reactor, 500 ml of THF previously dried by sodium benzophenone carbonyl radical was added, and the mixture was stirred at 25° C. for about 60 minutes. To this reaction mixture was added 63.5 g (0.3 mol) of methylphenyldichlorosilane previously purified by distillation using a syringe, and the mixture was stirred at 25°C for about 24 hours. After completion of the reaction, 1000 ml of 1N (=1 mol/L) hydrochloric acid was added to the reaction mixture, followed by extraction with 500 ml of toluene. The toluene phase was washed 10 times with 200 ml of pure water, and after drying the toluene phase with anhydrous magnesium sulfate, the toluene was distilled off to obtain 21.6 g of a methylphenylsilane polymer (mass average molecular weight: 6000) (yield: 60 %).

[比較例2] [Comparative Example 2]

向安裝有三通活栓之內容積1000ml之圓型燒瓶中添加粒狀(粒徑20~1000μm)之鎂25.0g、無水氯化鋅(ZnCl₂)16.2g，於50℃下加熱減壓至1mmHg，使反應器內部乾燥後，將乾燥氬氣導入至反應器內，添加預先利用二苯甲酮鈉羰自由基進行乾燥之四氫呋喃(THF)500ml，於25℃下攪拌約60分鐘。利用注射器向該反應混合物中添加預先藉由蒸餾進行精製之甲基苯基二氯矽烷63.5g(0.3mol)，並於25℃下攪拌約24小時。 To a round flask with an inner volume of 1000ml installed with a three-way stopcock, add 25.0g of granular (particle size: 20~1000μm) magnesium and 16.2g of anhydrous zinc chloride (ZnCl ₂ ), and heat and reduce the pressure to 1mmHg at 50°C. After drying the inside of the reactor, dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran (THF) previously dried with sodium benzophenone carbonyl radical was added, and the mixture was stirred at 25° C. for about 60 minutes. To this reaction mixture was added 63.5 g (0.3 mol) of methylphenyldichlorosilane previously purified by distillation using a syringe, and the mixture was stirred at 25°C for about 24 hours.

將所獲得之直鏈狀之苯基矽烷-二甲基矽烷共聚物溶解於甲苯150g與四氫呋喃150g之混合溶液中，進而混合以10質量%之比率包含氯化銅(II)(CuCl₂)之氯化銅水溶液200g並攪拌60分鐘後，將包含直鏈狀之苯基矽烷-二甲基矽烷共聚物之有機相與包含氯化銅之水相進行分離。接下來，利用純水200ml將包含直鏈狀之苯基矽烷-二甲基矽烷共聚物之有機相洗淨3次後，將溶劑成分蒸餾去除，獲得直鏈狀之苯基矽烷-二甲基矽烷共聚物(質量平均分子量3000)21.6g(產率60%)。 The obtained linear phenylsilane-dimethylsilane copolymer was dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and then mixed with copper(II) chloride (CuCl ₂ ) at a ratio of 10% by mass. After stirring 200 g of the cupric chloride aqueous solution for 60 minutes, the organic phase containing the linear phenylsilane-dimethylsilane copolymer and the aqueous phase containing cupric chloride were separated. Next, the organic phase containing the linear phenylsilane-dimethylsilane copolymer was washed three times with 200 ml of pure water, and then the solvent component was distilled off to obtain linear phenylsilane-dimethylsilane. Silane copolymer (mass average molecular weight 3000) 21.6 g (yield 60%).

[比較例3] [Comparative Example 3]

向安裝有三通活栓之內容積1000ml之圓型燒瓶中添加粒狀(粒徑20~1000μm)之鎂25.0g、無水氯化鋰21.4g、氯化鐵4.1g，於50℃下加熱減壓至1mmHg，使反應混合物乾燥後，將乾燥氬氣導入至反應器內，添加預先利用二苯甲酮鈉羰自由基進行乾燥之四氫呋喃500ml，於室溫下攪拌約30分鐘。向該反應混合物中添加預先藉由蒸餾進行精製之甲基苯基二氯矽烷105.8g(0.50mol)，並於20℃下攪拌約18小時。反應結束後，添加甲苯300ml，然後藉由減壓過濾將藉由反應而生成之氯化鎂、剩餘之鎂去除。利用純水200ml將濾液洗淨10次，並利用無水硫酸鎂使甲苯相乾燥後，將甲苯、四氫呋喃蒸餾去除，藉此獲得直鏈狀之甲基苯基矽烷聚合物50g。 Add 25.0g of granular (20~1000μm particle size) magnesium, 21.4g of anhydrous lithium chloride, and 4.1g of ferric chloride to a round flask with an inner volume of 1000ml installed with a three-way stopcock, and heated and decompressed at 50°C to After drying the reaction mixture at 1 mmHg, dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium benzophenone carbonyl radical was added, and the mixture was stirred at room temperature. Mix for about 30 minutes. To this reaction mixture, 105.8 g (0.50 mol) of methylphenyldichlorosilane previously purified by distillation was added, and the mixture was stirred at 20°C for about 18 hours. After the completion of the reaction, 300 ml of toluene was added, and the magnesium chloride and residual magnesium produced by the reaction were removed by filtration under reduced pressure. The filtrate was washed 10 times with 200 ml of pure water, and the toluene phase was dried with anhydrous magnesium sulfate, and then toluene and tetrahydrofuran were distilled off to obtain 50 g of a linear methylphenylsilane polymer.

將所獲得之直鏈狀之甲基苯基矽烷聚合物溶解於甲苯150g與四氫呋喃150g之混合溶液中，進而混合以10質量%之比率包含氯化銅(II)(CuCl₂)之氯化銅水溶液200g並攪拌60分鐘後，將包含直鏈狀之甲基苯基矽烷聚合物之有機相與包含氯化銅之水相進行分離。接下來，利用純水200ml將包含直鏈狀之甲基苯基矽烷聚合物之有機相洗淨3次後，將溶劑成分蒸餾去除，獲得直鏈狀之甲基苯基矽烷聚合物(質量平均分子量2000)36g(產率60%)。 The obtained linear methylphenylsilane polymer was dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and further mixed with copper chloride containing copper(II) chloride (CuCl ₂ ) at a ratio of 10% by mass After 200 g of the aqueous solution was stirred for 60 minutes, the organic phase containing the linear methylphenylsilane polymer was separated from the aqueous phase containing copper chloride. Next, the organic phase containing the linear methylphenylsilane polymer was washed three times with 200 ml of pure water, and then the solvent component was distilled off to obtain a linear methylphenylsilane polymer (average mass Molecular weight 2000) 36 g (yield 60%).

[比較例4] [Comparative Example 4]

向安裝有三通活栓之內容積1000ml之圓型燒瓶中添加粒狀(粒徑20~1000μm)之鎂25.0g、無水氯化鋅(ZnCl₂)16.2g，於50℃下加熱減壓至1mmHg，使反應混合物乾燥後，將乾燥氬氣導入至反應器內，添加預先利用二苯甲酮鈉羰自由基進行乾燥之四氫呋喃500ml，於室溫下攪拌約30分鐘。向該反應混合物中添加預先藉由蒸餾進行精製之苯基三氯矽烷105.8g(0.50mol)，並於20℃下攪拌約18小時。反應結束後，添加甲苯300ml，然後藉由減壓過濾將藉由反應而生成之氯化鎂、剩餘之鎂去除。利用純水200ml將濾液洗淨10次，並利用無水硫酸鎂對甲苯相進行乾燥後，將甲苯及四氫呋喃蒸餾去除，藉此獲得支鏈狀之聚苯基矽烷50g。 To a round flask with an inner volume of 1000ml installed with a three-way stopcock, add 25.0g of granular (particle size: 20~1000μm) magnesium and 16.2g of anhydrous zinc chloride (ZnCl ₂ ), and heat and reduce the pressure to 1mmHg at 50°C. After drying the reaction mixture, dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium benzophenone carbonyl radical was added, and the mixture was stirred at room temperature for about 30 minutes. To this reaction mixture was added 105.8 g (0.50 mol) of phenyltrichlorosilane previously purified by distillation, and the mixture was stirred at 20° C. for about 18 hours. After the completion of the reaction, 300 ml of toluene was added, and the magnesium chloride and residual magnesium produced by the reaction were removed by filtration under reduced pressure. The filtrate was washed 10 times with 200 ml of pure water, and the toluene phase was dried with anhydrous magnesium sulfate, and then toluene and tetrahydrofuran were distilled off to obtain 50 g of branched polyphenylsilane.

反應結束後，向反應混合物中投入1N(=1莫耳/L)之鹽酸1000ml，進而利用甲苯500ml進行萃取。利用純水200ml將甲苯相洗淨10次，並利用無水硫酸鎂對甲苯相進行乾燥後，將甲苯蒸餾去除，藉此獲得支鏈狀之聚苯基矽烷聚合物(質量平均分子量2000)38.2g(產率60%)。 After completion of the reaction, 1000 ml of 1N (=1 mol/L) hydrochloric acid was added to the reaction mixture, followed by extraction with 500 ml of toluene. The toluene phase was washed 10 times with 200 ml of pure water, and after drying the toluene phase with anhydrous magnesium sulfate, the toluene was distilled off to obtain 38.2 g of a branched polyphenylsilane polymer (mass average molecular weight: 2000). (60% yield).

[比較例5] [Comparative Example 5]

向安裝有三通活栓之內容積1000ml之圓型燒瓶中添加粒狀(粒徑20~1000μm)之鎂25.0g、無水氯化鋅(ZnCl₂)16.2g，於50℃下加熱減壓至1mmHg，使反應混合物乾燥後，將乾燥氬氣導入至反應器內，添加預先利用二苯甲酮鈉羰自由基進行乾燥之四氫呋喃500ml，於室溫下攪拌約30分鐘。向該反應混合物中添加預先藉由蒸餾進行精製之苯基三氯矽烷105.8g(0.50mol)，並於20℃下攪拌約18小時。反應結束後添加甲苯300ml，然後藉由減壓過濾將藉由反應而生成之氯化鎂、剩餘之鎂去除。利用純水200ml將濾液洗淨10次，並利用無水硫酸鎂使甲苯層乾燥後，將甲苯及四氫呋喃蒸餾去除，藉此獲得支鏈狀之聚苯基矽烷50g。 To a round flask with an inner volume of 1000ml installed with a three-way stopcock, add 25.0g of granular (particle size: 20~1000μm) magnesium and 16.2g of anhydrous zinc chloride (ZnCl ₂ ), and heat and reduce the pressure to 1mmHg at 50°C. After drying the reaction mixture, dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium benzophenone carbonyl radical was added, and the mixture was stirred at room temperature for about 30 minutes. To this reaction mixture was added 105.8 g (0.50 mol) of phenyltrichlorosilane previously purified by distillation, and the mixture was stirred at 20° C. for about 18 hours. After completion of the reaction, 300 ml of toluene was added, and then magnesium chloride and residual magnesium produced by the reaction were removed by filtration under reduced pressure. The filtrate was washed 10 times with 200 ml of pure water, and after drying the toluene layer with anhydrous magnesium sulfate, toluene and tetrahydrofuran were distilled off to obtain 50 g of branched polyphenylsilane.

將所獲得之支鏈狀之聚苯基矽烷溶解於甲苯150g與四氫呋喃150g之混合溶液中，進而混合以10質量%之比率包含氯化銅(II)(CuCl₂)之氯化銅水溶液200g並攪拌60分鐘後，將包含支鏈狀之聚苯基矽烷之有機相與包含氯化銅之水相進行分離。接下來，利用純水200ml將包含支鏈狀之聚苯基矽烷之有機相洗淨3次後，將溶劑成分蒸餾去除，獲得支鏈狀之聚苯基矽烷聚合物(質量平均分子量2000)31.8g(產率60%)。 The obtained branched polyphenylsilane was dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and then 200 g of an aqueous copper chloride solution containing copper(II) chloride (CuCl ₂ ) was mixed in a ratio of 10% by mass. After stirring for 60 minutes, the organic phase containing branched polyphenylsilane was separated from the aqueous phase containing copper chloride. Next, the organic phase containing the branched polyphenylsilane was washed three times with 200 ml of pure water, and then the solvent component was distilled off to obtain a branched polyphenylsilane polymer (mass average molecular weight 2000) 31.8 g (60% yield).

將實施例1~6及比較例1~5彙總於下述表1。 Examples 1 to 6 and Comparative Examples 1 to 5 are summarized in Table 1 below.

關於實施例1~6及比較例1~5中所獲得之聚矽烷化合物，依據下述方法對Zn、Cu、Fe各者之含量、間隙填充特性及矽氧烷鍵(Si-O)比率進行評價。 Regarding the polysilane compounds obtained in Examples 1 to 6 and Comparative Examples 1 to 5, the content of each of Zn, Cu, and Fe, the gap filling properties, and the ratio of siloxane bonds (Si—O) were measured according to the following methods. Evaluation.

<Zn、Cu、Fe各者之含量評價> <Evaluation of content of each of Zn, Cu, and Fe>

實施例1~6及比較例1~5中所獲得之聚矽烷化合物中之Zn、Cu、Fe各者之含量係使用ICP-MS(Inductively coupled plasma mass spectroscopy，感應耦合電漿-質譜分析法)進行測定。將結果示於表2。 The contents of Zn, Cu, and Fe in the polysilane compounds obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were measured by ICP-MS (Inductively coupled plasma mass spectroscopy, inductively coupled plasma-mass spectrometry). to measure. The results are shown in Table 2.

(評價基準) (Evaluation Criteria)

○：關於Zn、Cu、Fe各者，含量為500ppb以下 ○: For each of Zn, Cu, and Fe, the content is 500 ppb or less

×：關於Zn、Cu、Fe各者，含量超過500ppb ×: For each of Zn, Cu, and Fe, the content exceeds 500 ppb

<間隙填充特性評價> <Evaluation of Gap Filling Properties>

將實施例1~6及比較例1~5中所獲得之聚矽烷化合物以聚矽烷化合物之濃度成為5質量%之方式溶解於乙酸環己酯中，使用所獲得之各聚矽烷化合物溶液(包含聚矽烷化合物之組合物)並依據以下之評價方法對間隙填充特性進行評價。 The polysilane compounds obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were dissolved in cyclohexyl acetate so that the concentration of the polysilane compound was 5% by mass, and each of the obtained polysilicones was used. The alkane compound solution (the composition containing the polysilane compound) was evaluated for gap filling properties according to the following evaluation methods.

(評價基準) (Evaluation Criteria)

將各聚矽烷化合物溶液以後烘烤後之膜厚成為約100nm(距溝槽圖案之底面之高度約185nm)之方式塗佈於形成有線寬40nm、間隙寬度15nm並且高度(間隙之深度)為85nm之重複之溝槽圖案之矽晶圓，於100℃下預烘烤100秒後，於350℃下進行30分鐘焙燒(後烘烤)，獲得聚矽烷化合物膜。將剖面部分於0.4%之氫氟酸水溶液中浸漬1分鐘後，利用SEM(Scanning Electron Microscope，掃描式電子顯微鏡)對剖面形狀進行觀測。依據下述基準進行評價。 Each polysilane compound solution was coated with a film thickness of about 100 nm (about 185 nm in height from the bottom surface of the trench pattern) after post-baking to form a line width of 40 nm, a gap width of 15 nm, and a height (depth of the gap) of 85 nm. The silicon wafer with the repeated groove pattern was pre-baked at 100° C. for 100 seconds, and then baked at 350° C. for 30 minutes (post-baking) to obtain a polysilane compound film. After immersing the cross-sectional part in a 0.4% hydrofluoric acid aqueous solution for 1 minute, the cross-sectional shape was observed by SEM (Scanning Electron Microscope, scanning electron microscope). Evaluation was performed according to the following criteria.

○：聚矽烷化合物膜均質地嵌入至溝槽圖案部。 ○: The polysilane compound film is uniformly embedded in the groove pattern portion.

×：於溝槽圖案部觀測到聚矽烷化合物膜之嵌入不良。 ×: Poor insertion of the polysilane compound film was observed in the groove pattern portion.

<矽氧烷鍵(Si-O)及Si-C鍵之比率評價> <Evaluation of the ratio of siloxane bond (Si-O) and Si-C bond>

針對實施例1~6及比較例1~5中所獲得之聚矽烷化合物進行XPS(X-ray photoelectron spectroscopy，X射線光電子光譜)分析，將於99eV以上且104eV以下之鍵結能量範圍內具有最大檢測波峰高度之光譜進行波峰分離，算出於鍵結能量為100eV以上且104eV以下之範圍內具有最大波峰高度之波峰之面積(2X)(源自矽氧烷鍵(Si-O)及Si-C鍵之波峰面積)及鍵結能量為99.0eV以上且99.5eV以下之範圍之波峰面積(1X)(源自Si-Si之波峰面積)，算出下述式(3X)所表示之比率，並按照以下之基準進行評價。 XPS (X-ray photoelectron spectroscopy, X-ray photoelectron spectroscopy) analysis of the polysilane compounds obtained in Examples 1 to 6 and Comparative Examples 1 to 5 shows that the maximum bonding energy is in the range of bonding energy above 99 eV and below 104 eV Detect the spectrum of the peak height, perform peak separation, and calculate the area (2X) of the peak with the largest peak height in the range of bonding energy above 100eV and below 104eV (derived from siloxane bonds (Si-O) and Si-C Bond peak area) and bonding energy in the range of 99.0eV or more and 99.5eV or less (1X) (the peak area derived from Si-Si), calculate the ratio represented by the following formula (3X), and according to The following criteria were used for evaluation.

(3X)‧‧‧(2X)/[(1X)+(2X)] (3X)‧‧‧(2X)/[(1X)+(2X)]

(評價基準) (Evaluation Criteria)

◎：15%以下 ◎: 15% or less

○：超過15%且為40%以下 ○: More than 15% and 40% or less

×：超過40% ×: More than 40%

將結果示於表2。 The results are shown in Table 2.

再者，表2中，所謂不存在「Si-O波峰」，意指歸屬於100eV以上且104eV以下之範圍內之波峰為1個。所謂存在「Si-O波峰」，意指歸屬於100eV以上且102eV以下之範圍內之波峰為2個。 In addition, in Table 2, "Si-O peak" does not exist means that there is one peak belonging to the range of 100 eV or more and 104 eV or less. The existence of "Si-O peaks" means that there are two peaks belonging to the range of 100 eV or more and 102 eV or less.

根據表2所示之結果明確，聚矽烷化合物之製造未使用有機金屬錯合物而使用氯化鋅之比較例1、2、4及5於聚矽烷化合物中殘存有Zn。 From the results shown in Table 2, it is clear that the production of the polysilane compound did not use the organometallic complex but the comparative examples 1, 2, 4 and 5 using zinc chloride had Zn remaining in the polysilane compound.

又，聚矽烷化合物之製造未使用有機金屬錯合物而藉由氯化銅進行精製處理之比較例2、3及5於聚矽烷化合物中殘存有Cu，又，聚矽烷化合物中之矽氧烷鍵(Si-O)及Si-C鍵之比率超過40%。 In addition, in Comparative Examples 2, 3, and 5, in which the polysilane compound was produced without using an organometallic complex and was purified by copper chloride, Cu remained in the polysilane compound, and the siloxane in the polysilane compound The ratio of bonds (Si-O) and Si-C bonds exceeds 40%.

又，聚矽烷化合物之製造未使用有機金屬錯合物而使用氯化鐵之比較例2及3於聚矽烷化合物中殘存有Fe。 In addition, Fe remained in the polysilane compound in Comparative Examples 2 and 3 in which the organometallic complex was not used but the ferric chloride was used in the production of the polysilane compound.

另一方面，使用有機金屬錯合物製造聚矽烷化合物之實施例1~6均為聚矽烷化合物之Mw為5000以下，聚矽烷化合物中之Zn、Cu及Fe之殘存量較低，矽氧烷鍵(Si-O)及Si-C鍵之含有比率亦為15%以下。又，實施例1~6之間隙填充特性均優異。 On the other hand, in Examples 1 to 6 of using organometallic complexes to produce polysilane compounds, the Mw of the polysilane compounds is below 5000, the residual amounts of Zn, Cu and Fe in the polysilane compounds are relatively low, and the siloxane compounds The content ratio of bond (Si-O) and Si-C bond is also 15% or less. In addition, the gap filling properties of Examples 1 to 6 were all excellent.

Claims

一種質量平均分子量2500以下之聚矽烷化合物之製造方法，其包括於下述通式(A1)所表示之有機金屬錯合物及鎂之存在下使鹵矽烷化合物反應，M^pL_p/q (A1)(上述通式(A)中，M^p表示p價之金屬陽離子，L表示q價之有機配位基，p及q分別獨立地表示1以上之整數)。 A method for producing a polysilane compound having a mass average molecular weight of 2500 or less, comprising reacting a halosilane compound in the presence of an organometallic complex represented by the following general formula (A1) and magnesium, M ^p L _p/q ( A1) (In the above general formula (A), M ^p represents a p-valent metal cation, L represents a q-valent organic ligand, and p and q each independently represent an integer of 1 or more).

如請求項1之製造方法，其為具有獲改善之間隙填充特性之聚矽烷化合物之製造方法。 The manufacturing method of claim 1, which is a manufacturing method of a polysilane compound having improved gap-filling properties.

如請求項2之製造方法，其中上述間隙填充特性為，相較於質量平均分子量6000之直鏈狀之甲基苯基矽烷聚合物、或質量平均分子量3000之直鏈狀之苯基矽烷-二甲基矽烷共聚物，已獲得改善之間隙填充特性。 The production method according to claim 2, wherein the gap-filling property is compared to a linear methylphenylsilane polymer with a mass average molecular weight of 6000 or a linear phenylsilane-dicarbonate with a mass average molecular weight of 3000 Methylsilane copolymers, which have achieved improved gap filling properties.

如請求項2之製造方法，其中上述間隙填充特性為，塗佈於線寬40nm、間隙寬度15nm並且高度為85nm之重複之溝槽圖案後之聚矽烷化合物膜均質地嵌入至上述溝槽圖案部者。 The manufacturing method of claim 2, wherein the above-mentioned gap-filling characteristic is that the polysilane compound film after coating the repeating groove pattern with a line width of 40 nm, a gap width of 15 nm and a height of 85 nm is uniformly embedded in the groove pattern portion By.

一種質量平均分子量5000以下之聚矽烷化合物之製造方法，其包括於下述通式(A1)所表示之有機金屬錯合物及鎂之存在下使鹵矽烷化合物反應，及使上述反應後所得之聚矽烷化合物與金屬鹵化物或鹼接觸而精製，M^pL_p/q (A1)(上述通式(A)中，M^p表示p價之金屬陽離子，L表示q價之有機配位基，p及q分別獨立地表示1以上之整數)。 A method for producing a polysilane compound having a mass average molecular weight of 5,000 or less, which comprises reacting a halosilane compound in the presence of an organometallic complex represented by the following general formula (A1) and magnesium, and reacting the resulting The polysilane compound is purified by contacting a metal halide or an alkali, M ^p L _p/q (A1) (in the above general formula (A), M ^p represents a p-valent metal cation, L represents a q-valent organic ligand, p and q each independently represent an integer of 1 or more).

如請求項5之製造方法，其中上述金屬鹵化物或鹼為包含選自由Cr、Ga、Fe(Fe(II)或Fe(III))、Cd、Co、Ni、Sn、Pb、Cu(Cu(II)或Cu(I))、Ag、Pd、Pt及Au所組成之群中之至少一金屬或金屬離子之金屬鹵化物。 The production method according to claim 5, wherein the metal halide or the base is selected from the group consisting of Cr, Ga, Fe (Fe(II) or Fe(III)), Cd, Co, Ni, Sn, Pb, Cu(Cu( II) or a metal halide of at least one metal or metal ion from the group consisting of Cu(I)), Ag, Pd, Pt and Au.

一種質量平均分子量5000以下之聚矽烷化合物之製造方法，其包括於下述通式(A1)所表示之有機金屬錯合物及鎂之存在下使鹵矽烷化合物反應，且所製造之上述聚矽烷化合物係以產率50%以上包含環狀聚矽烷，M^pL_p/q (A1)(上述通式(A)中，M^p表示p價之金屬陽離子，L表示q價之有機配位基，p及q分別獨立地表示1以上之整數)。 A method for producing a polysilane compound having a mass average molecular weight of 5000 or less, comprising reacting a halosilane compound in the presence of an organometallic complex represented by the following general formula (A1) and magnesium, and producing the above-mentioned polysilane The compound contains a cyclic polysilane with a yield of 50% or more, M ^p L _p/q (A1) (in the above general formula (A), M ^p represents a p-valent metal cation, and L represents a q-valent organic ligand. , p and q each independently represent an integer of 1 or more).

如請求項1、5或7之製造方法，其中上述有機金屬錯合物為下述通式(A2)所表示之有機金屬錯合物，[化1]

(上述通式(A2)中，M表示選自由鐵、銀、鋁、鉍、鈰、鈷、銅、鏑、鉺、銪、鎵、釓、鉿、鈥、銦、銥、鑭、鎦、錳、鉬、釹、鎳、鋨、鈀、鉕、鐠、鉑、錸、銠、釕、釤、鈧、錫、鋱、鈦、銩、釩、鉻、鉭、鐿、金、水銀、鎢、釔、鋅及鋯所組成之群中之金屬，R^a1分別獨立地表示飽和烴基、不飽和烴基、芳香族烴基、芳烷基、烷氧基、芳氧基、芳烷氧基或芳氧基烷基，R^a2表示氫原子、飽和烴基、不飽和烴基、芳香族烴基或芳烷基；p表示1以上之整數)。 The production method of claim 1, 5 or 7, wherein the organometallic complex is an organometallic complex represented by the following general formula (A2), [Chem. 1]

(In the above-mentioned general formula (A2), M represents selected from iron, silver, aluminum, bismuth, cerium, cobalt, copper, dysprosium, erbium, europium, gallium, gadolinium, hafnium, ∥, indium, iridium, lanthanum, tungsten, manganese , Molybdenum, Neodymium, Nickel, Osmium, Palladium, Ni, Fe, Pt, Rhenium, Rhodium, Ruthenium, Samarium, Scandium, Tin, Tb, Titanium, V, Vanadium, Chromium, Tantalum, Ytterbium, Gold, Mercury, Tungsten, Yttrium , a metal in the group consisting of zinc and zirconium, R ^a1 independently represents a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkoxy group or an aryloxyalkane group group, R ^a2 represents a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or an aralkyl group; p represents an integer of 1 or more).

如請求項8之製造方法，其中於上述通式(A2)中，R^a1表示甲基，R^a2表示氫原子。 The production method according to claim 8, wherein in the general formula (A2), R ^a1 represents a methyl group, and R ^a2 represents a hydrogen atom.

如請求項1或5之製造方法，其中所製造之上述聚矽烷化合物為選自由直鏈狀聚矽烷、支鏈狀聚矽烷及環狀聚矽烷所組成之群中之至少1種聚矽烷。 The production method according to claim 1 or 5, wherein the polysilane compound to be produced is at least one polysilane selected from the group consisting of linear polysilane, branched polysilane, and cyclic polysilane.

如請求項10之製造方法，其中上述聚矽烷化合物包含環狀聚矽烷。 The production method according to claim 10, wherein the above-mentioned polysilane compound comprises a cyclic polysilane.

如請求項1、5或7之製造方法，其中下述(2X)相對於下述(1X)及(2X) 之波峰之面積之和的比即下述式(3X)所表示之比率為0.4以下，上述波峰之面積係將上述聚矽烷化合物中藉由X射線光電子光譜法測定之於99eV以上且104eV以下之鍵結能量範圍內具有最大檢測波峰高度之光譜進行波峰分離而求出，(1X)‧‧‧於鍵結能量為99.0eV以上且99.5eV以下之範圍內具有最大波峰高度之波峰之面積(2X)‧‧‧於鍵結能量為100eV以上且104eV以下之範圍內具有最大波峰高度之波峰之面積(3X)‧‧‧(2X)/[(1X)+(2X)]。 The manufacturing method of claim 1, 5 or 7, wherein the following (2X) is relative to the following (1X) and (2X) The ratio of the sum of the areas of the peaks, that is, the ratio represented by the following formula (3X), is 0.4 or less, and the area of the peaks is determined by X-ray photoelectron spectroscopy in the polysilane compound above 99 eV or more and 104 eV or less. The spectrum with the maximum detected peak height within the bonding energy range is obtained by performing peak separation, (1X)‧‧‧The area of the peak with the maximum peak height within the bonding energy range of 99.0eV or more and 99.5eV or less (2X) )‧‧‧The area of the peak with the largest peak height in the range of bonding energy of 100eV or more and 104eV or less (3X)‧‧‧(2X)/[(1X)+(2X)].

如請求項1、5或7之製造方法，其中上述聚矽烷化合物中之金屬之含量為500ppb以下。 The production method according to claim 1, 5 or 7, wherein the content of the metal in the polysilane compound is 500 ppb or less.

如請求項1或7之製造方法，其進而包括藉由使上述反應後之溶液與包含選自由金屬鹵化物及鹼所組成之群中之至少1種之水溶液接觸進行精製而獲得上述聚矽烷化合物。 The production method according to claim 1 or 7, further comprising obtaining the above-mentioned polysilane compound by contacting the solution after the above-mentioned reaction with an aqueous solution containing at least one selected from the group consisting of a metal halide and a base and purifying .

如請求項1、5或7之製造方法，其中上述鹵矽烷化合物為下述式(1)所表示之化合物，X_nSiR_4-n (1)(式中，n為2~4之整數，n個X分別獨立地為鹵素原子，(4-n)個R分別獨立地為氫原子、有機基或矽烷基)。 The production method according to claim 1, 5 or 7, wherein the halosilane compound is a compound represented by the following formula (1), X _n SiR _4-n (1) (in the formula, n is an integer of 2 to 4, The n X's are each independently a halogen atom, and the (4-n) R's are each independently a hydrogen atom, an organic group or a silyl group).

一種質量平均分子量2500以下之聚矽烷化合物，其中下述(2X)相對於下述(1X)及(2X)之波峰之面積之和的比即下述式(3X)所表示之比率為0.4以下，上述波峰之面積係將聚矽烷化合物中藉由X射線光電子光譜法測定之於99eV以上且104eV以下之鍵結能量範圍內具有最大檢測波峰高度之光譜進行波峰分離而求出，並且上述聚矽烷化合物中之金屬之含量為500ppb以下，(1X)‧‧‧於鍵結能量為99.0eV以上且99.5eV以下之範圍內具有最大波峰高度之波峰之面積(2X)‧‧‧於鍵結能量為100eV以上且104eV以下之範圍內具有最大波峰高度之波峰之面積(3X)‧‧‧(2X)/[(1X)+(2X)]。 A polysilane compound having a mass average molecular weight of 2500 or less, wherein the ratio of the following (2X) to the sum of the areas of the peaks of the following (1X) and (2X), that is, the ratio represented by the following formula (3X) is 0.4 or less , the area of the above-mentioned wave peak is obtained by subjecting the spectrum of the polysilane compound with the maximum detection peak height in the bonding energy range of 99 eV to 104 eV measured by X-ray photoelectron spectroscopy to peak separation, and the above-mentioned polysilane The content of metal in the compound is less than 500ppb, (1X)‧‧‧The area of the peak with the largest peak height in the range of bonding energy of 99.0eV or more and 99.5eV or less (2X)‧‧‧The bonding energy is Area (3X)‧‧‧(2X)/[(1X)+(2X)] of the peak with the largest peak height within the range of 100eV or more and 104eV or less.

如請求項16之聚矽烷化合物，其為具有獲改善之間隙填充特性。 The polysilane compound of claim 16 having improved gap filling properties.

如請求項17之聚矽烷化合物，其中上述間隙填充特性為，相較於質量平均分子量6000之直鏈狀之甲基苯基矽烷聚合物、或質量平均分子量3000之直鏈狀之苯基矽烷-二甲基矽烷共聚物，已獲得改善之間隙填充特性。 The polysilane compound according to claim 17, wherein the above-mentioned gap-filling property is compared to a linear methylphenylsilane polymer with a mass average molecular weight of 6000 or a linear phenylsilane polymer with a mass average molecular weight of 3000- Dimethylsilane copolymers have achieved improved gap filling properties.

如請求項16至18中任一項之聚矽烷化合物，其中上述聚矽烷化合物中相對於聚矽烷化合物總量包含50質量%以上之環狀聚矽烷。 The polysilane compound according to any one of claims 16 to 18, wherein the polysilane compound contains 50% by mass or more of cyclic polysilane with respect to the total amount of the polysilane compound.

一種質量平均分子量5000以下之環狀聚矽烷化合物，其中下述(2X) 相對於下述(1X)及(2X)之波峰之面積之和的比即下述式(3X)所表示之比率為0.4以下，上述波峰之面積係將聚矽烷化合物中藉由X射線光電子光譜法測定之於99eV以上且104eV以下之鍵結能量範圍內具有最大檢測波峰高度之光譜進行波峰分離而求出，並且上述聚矽烷化合物中之金屬之含量為500ppb以下，(1X)‧‧‧於鍵結能量為99.0eV以上且99.5eV以下之範圍內具有最大波峰高度之波峰之面積(2X)‧‧‧於鍵結能量為100eV以上且104eV以下之範圍內具有最大波峰高度之波峰之面積(3X)‧‧‧(2X)/[(1X)+(2X)]。 A cyclic polysilane compound with a mass average molecular weight below 5000, wherein the following (2X) The ratio to the sum of the areas of the peaks of the following (1X) and (2X), that is, the ratio represented by the following formula (3X) is 0.4 or less. The spectrum with the maximum detection peak height in the bond energy range above 99eV and below 104eV measured by the method is obtained by peak separation, and the content of the metal in the above-mentioned polysilane compound is below 500ppb, (1X)‧‧‧ in The area of the peak with the largest peak height within the range of bonding energy of 99.0eV or more and 99.5eV or less (2X)‧‧‧The area of the peak with the largest peak height within the range of bonding energy of 100eV or more and 104eV or less ( 3X)‧‧‧(2X)/[(1X)+(2X)].

一種聚矽烷組合物，其包含如請求項16至19中任一項之聚矽烷化合物。 A polysilane composition comprising the polysilane compound of any one of claims 16 to 19.

一種聚矽烷膜，其包含如請求項16至19中任一項之聚矽烷化合物。 A polysilane film comprising the polysilane compound of any one of claims 16 to 19.

一種附聚矽烷膜之基板，其具備包含如請求項16至19中任一項之聚矽烷化合物之膜。 A substrate for agglomerating a silane film having a film comprising the polysilane compound of any one of claims 16 to 19.