TWI811203B - Production method of polysilane compound, composition, cured product and substrate, and selective accelerator for anionic polymerization - Google Patents

Abstract

The present invention provides a method for producing a polysilane compound that can suppress outgassing and microcracks in a film containing a polysilane compound, a composition, a cured product and a substrate containing the polysilane compound, and a method for producing a polysilane compound. Select accelerator for anionic polymerization. The method for producing a polysilane compound of the present invention includes reacting a halosilane compound in the presence of a nitrosilyl compound. The anionic polymerization selective accelerator used in the production of the polysilane compound of the present invention contains a nitroxyl compound having a structure represented by the following general formula (A). (In the formula (A), R ^a1 , R ^a2 , R ^a3 and R ^a4 are each independently a hydrogen atom or an organic group. R ^a1 and R ^a2 may be bonded to each other to form a ring. In addition, R ^a3 and R ^a4 may be mutually bonded. bond to form a ring).

Description

Polysilane compound, composition, method for manufacturing hardened product and substrate, and anionic polymerization selective accelerator

The present invention relates to a method for manufacturing a polysilane compound, a composition, a hardened product and a substrate, as well as an anionic polymerization selective accelerator in the manufacture of the polysilane compound.

Polysilane compounds are used in ceramic precursors, optoelectronic materials (such as photoresists, optoelectronic photographic materials such as organic photoreceptors, optical transmission materials such as optical waveguides, optical recording materials such as optical memories, materials for electroluminescent devices), and various components Interlayer insulating films, sealing materials for light-emitting elements such as LED (Light Emitting Diode) elements or organic EL (Electroluminescence) elements, coating films used to diffuse impurities into semiconductor substrates, And used in gap filling materials for semiconductor manufacturing processes. As a method of producing such a polysilane compound, for example, Patent Document 1 discloses a method of producing polysilane by reacting a halosilane compound with metal magnesium in the presence of a lithium compound and a specific metal halide. In the reaction system of polysilane, the above-mentioned raw materials (lithium compound, metal halide, and halogenated silane compound) are newly added to the active metal magnesium as the solid content remaining after the reaction, and the reaction proceeds to produce polysilane. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent No. 4559642

[Problems to be Solved by the Invention] When a composition containing a polysilane compound is used to form a film, microcracks and outgassing may occur. In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a method for producing a polysilane compound that can suppress outgassing and microcracks in a film containing a polysilane compound, a composition and a cured product containing the polysilane compound. and substrates, as well as anionic polymerization selective accelerators in the manufacture of polysilane compounds. [Technical Means for Solving the Problem] The present inventors discovered that in a method for producing a polysilane compound, by reacting a halosilane compound in the presence of a nitryl compound, the generation of outgassing and the generation of microcracks can be suppressed, thus The present invention was completed. A first aspect of the present invention is a method for producing a polysilane compound, which includes: reacting a halosilane compound in the presence of a nitrosilyl compound. A second aspect of the present invention is a polysilane compound obtained by the manufacturing method of the first aspect. A third aspect of the present invention is a composition including the polysilane compound of the second aspect. A fourth aspect of the present invention is a hardened product of the composition of the third aspect. A fifth aspect of the present invention is a substrate provided with the hardened material of the fourth aspect. A sixth aspect of the present invention is an anionic polymerization selective accelerator for the production of a polysilane compound containing a nitroxyl compound having a structure represented by the following general formula (A). [Chemical 1] (In the formula (A), R ^a1 , R ^a2 , R ^a3 and R ^a4 are each independently a hydrogen atom or an organic group. R ^a1 and R ^a2 may be bonded to each other to form a ring. In addition, R ^a3 and R ^a4 may be mutually bonded. bond to form a ring). A seventh aspect of the present invention is a method for producing a composition containing a polysilane compound, and the polysilane compound is produced by the method of the first aspect. An eighth aspect of the present invention is a method for producing a hardened product of a composition, and the composition is produced by the method of the seventh aspect. A ninth aspect of the present invention is a method of manufacturing a substrate provided with a hardened object, and the hardened object is manufactured by the method of the eighth aspect. [Effects of the Invention] According to the present invention, it is possible to provide a method for producing a polysilane compound that can suppress outgassing and microcracks in a film containing a polysilane compound, a composition, a cured product, and a substrate containing the polysilane compound. , and anionic polymerization selective accelerators in the manufacture of polysilane compounds.

Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments and can be implemented with appropriate modifications within the scope of the purpose of the present invention. In addition, in this specification, "～" means above to below unless otherwise specified. <Method for producing a polysilane compound> The method for producing a polysilane compound according to the first aspect includes reacting a halosilane compound in the presence of a nitrosilyl compound. In the manufacture of polysilane compounds, silyl radical cations and silyl radical anions (Electronic Structure of Radical Anions and Cations of Polysilanes with Structural Defects Seki, Shu; Yoshida, Yoichi; Tagawa, Seiichi; Asai, Keisuke, Macromolecules, 1999, 32 (4), pp1080 - 1086). Silyl radical anions can be used in the production of polysilane compounds through anionic polymerization. On the other hand, water (H ₂ O) or oxygen (O ₂ ) in the air selectively reacts with silyl radical cations. In this case, side reactants such as siloxane bonds (Si-O) and silanol groups (Si-OH) are generated. The present inventors discovered that when a film is formed using a composition containing a polysilane compound containing side reactants such as siloxane bonds, silanol groups, etc., the siloxane bonds, silanol groups, etc. cause microscopic crack. In addition, it is believed that silyl radical cations are more likely to detach substituents such as aryl groups and alkyl groups (especially aryl groups) than silyl radical anions, leading to outgassing. On the other hand, it is presumed that in the method for producing a polysilane compound according to the first aspect, the nitryl compound causes the silyl radical cations to perform charge spin and reduces the silyl radical cations, thereby selectively promoting the formation of silane. Anionic polymerization of radical anions. It is presumed that this can inhibit the formation of side reactants such as siloxane bonds and silanol groups that cause micro-cracks, and also inhibit the generation of outgassing. (Nitrogenyl compound) The nitrogenyl compound is not particularly limited as long as it is a compound that can stably exist in the form of a nitroxide radical. Preferably, it is a compound having a structure represented by the following general formula (A). compound. [Chemicalization 2] (In the formula (A), R ^a1 , R ^a2 , R ^a3 and R ^a4 are each independently a hydrogen atom or an organic group. R ^a1 and R ^a2 may be bonded to each other to form a ring. In addition, R ^a3 and R ^a4 may be mutually bonded. bond to form a ring). In the formula (A), examples of the organic groups represented by R ^a1 to R ^a4 include organic groups having 1 to 10 carbon atoms. It is preferred that R ^a1 , R ^a2 , R ^a3 and R ^a4 are each independently an alkane. group or an alkyl group substituted by a heteroatom. As the alkyl group, methyl, ethyl, n-propyl and isopropyl are preferred. Preferable examples of heteroatoms include halogen atoms, oxygen atoms, sulfur atoms, nitrogen atoms, and the like. Preferable specific examples of the nitrogen compound include di-tert-butyl oxynitride, di-1,1-dimethylpropyl oxynitride, and di-1,2-dimethylpropyl oxynitride. nitrogen oxide, di-2,2-dimethylpropyl nitrogen oxide, and compounds represented by the following formula (A1), (A2), or (A3), more preferably the following formula (A1) , (A2), or a compound represented by (A3). [Chemical 3] In formulas (A1), (A2), and (A3), R ^a5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a cyano group, an alkyl group substituted with a heteroatom, or A monovalent organic group bonded via an ether bond, ester bond, amide bond or urethane bond. R ^a6 represents a divalent or trivalent organic group. n1 and n2 are integers satisfying 1≦n1+n2≦2. n3 and n4 are integers satisfying 1≦n3＋n4≦2. n5 and n6 are integers satisfying 1≦n5＋n6≦2. n7 is 2 or 3. Preferable specific examples of the compound represented by formula (A1) include the following compounds. In the following formula, R ^a7 each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic group which may have a substituent, or an alicyclic group which may have a substituent. [Chemical 4] Preferable specific examples of the compound represented by formula (A2) include the following compounds. [Chemistry 5] Preferable specific examples of the compound represented by formula (A3) include the following compounds. [Chemical 6] Further preferred nitrogen compounds include: 2,2,6,6-tetramethylpiperidine 1-alkoxy radical (TEMPO), 4-hydroxy-2,2,6,6-tetramethyl Piperidine 1-alkoxy radical, 4-amino-2,2,6,6-tetramethylpiperidine 1-alkoxy radical, 4-carboxy-2,2,6,6-tetramethyl Methylpiperidine 1-alkoxy radical, 4-cyano-2,2,6,6-tetramethylpiperidine 1-alkoxy radical, 4-methacrylic acid-2,2,6, 6-Tetramethylpiperidine 1-alkoxy radical, 4-acrylic acid-2,2,6,6-tetramethylpiperidine 1-alkoxy radical, 4-side oxy-2,2, 6,6-Tetramethylpiperidine 1-alkoxy radical, 3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-alkoxy radical, 4-acetamide-2, 2,6,6-Tetramethylpiperidine 1-alkoxy radical, 4-(2-chloroacetamide)-2,2,6,6-tetramethylpiperidine 1-alkoxy radical , 4-hydroxy-2,2,6,6-tetramethylpiperidine benzoate 1-alkoxy ester free radical, 4-isothiocyanato-2,2,6,6-tetramethylpiperidine 1 -Alkoxyl radical, 4-(2-iodoacetamide)-2,2,6,6-tetramethylpiperidine 1-alkoxyl radical, and 4-methoxy-2,2, 6,6-tetramethylpiperidine 1-alkoxy radical. A nitrogenyl compound can be used individually or in combination of 2 or more types. Relative to the halosilane compound, the usage amount of the above-mentioned nitryl compound is preferably in the range of 0.0001 to 10 molar times, more preferably in the range of 0.0005 to 5 molar times, and further preferably in the range of 0.0008 to 1 molar times. , especially preferably in the range of 0.001 to 0.1 mol times. (Halosilane compound) As the above-mentioned halosilane compound, a compound represented by the following formula (1) is preferred. X _n SiR _{4 - n} (1) (In the formula, n is an integer from 2 to 4, n Xs are independently halogen atoms, (4-n) R are independently hydrogen atoms, organic groups or silane groups ). Examples of the halogen atom represented by Examples of the organic group represented by R include alkyl groups [alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms) such as methyl, ethyl, propyl, isopropyl, butyl, and tert-butyl. 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 cycloalkyl groups with 5 to 6 carbon atoms) Alkyl), alkenyl [vinyl, propenyl, butenyl and other alkenyl groups with 2 to 10 carbon atoms (preferably alkenyl groups with 2 to 6 carbon atoms, especially alkenyl groups with 2 to 4 carbon atoms) etc.)], cycloalkenyl [1-cyclopentenyl, 1-cyclohexenyl and other cycloalkenyl groups with 5 to 10 carbon atoms (preferably cycloalkenyl groups with 5 to 8 carbon atoms, especially carbon Cycloalkenyl groups with 5 to 7 carbon atoms, etc.)], aryl groups (aryl groups with 6 to 10 carbon atoms such as phenyl and naphthyl groups), aralkyl groups [C _6-10 aryl groups such as benzyl and phenethyl groups -C _1-6 alkyl (C _6-10 aryl-C _1-4 alkyl, etc.)], amino group, N-substituted amino group (via the above alkyl group, cycloalkyl group, aryl group, aralkyl group, N-mono- or disubstituted amino groups substituted by acyl groups, etc.), etc. The alkyl group, cycloalkyl group, aryl group or aryl group constituting the aralkyl group may have one or a plurality of substituents. Examples of such substituents include the alkyl groups exemplified above (especially alkyl groups having 1 to 6 carbon atoms, etc.). Examples of the organic group having such a substituent include C _1-6 alkyl groups such as tolyl (methylphenyl), xylyl (dimethylphenyl), ethylphenyl, and methylnaphthyl. -C _6-10 aryl group (preferably mono-, di- or tri-C _1-4 alkyl-C _6-10 aryl group, especially mono- or di-C _1-4 alkyl phenyl group, etc.). Examples of the silyl group include substituted silyl groups substituted by the above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, aralkyl group, alkoxy group, and the like. When n is 2 (dihalosilane compound), R is preferably a hydrocarbon group such as an alkyl group or an aryl group. At least one R may be an aryl group. Previously, when the silyl radical cation had an organic group (especially an aryl group) such as an alkyl group or aryl group that was directly bonded to the silicon atom, detachment of the above-mentioned organic group easily occurred, leading to outgassing. On the other hand, it is presumed that in the method for producing a polysilane compound of the first aspect, even when the silyl radical cation has an organic group directly bonded to a silicon atom (R is an organic group (especially an aryl group) In this case), the above-mentioned nitroxyl compound also causes the silyl radical cations to carry out charge spin and the silyl radical cations are reduced, thereby making it difficult for the organic radicals to detach and inhibit the generation of outgassing. Representative dihalosilane compounds include, for example, di-C _1-10 alkyl dihalosilane such as dialkyl dihalosilane (dimethyldichlorosilane), preferably di-C _1-6 alkyl dihalosilane. , 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) Dihalosilane, preferably mono-C _1-6 alkyl mono-C _6-10 aryl dihalosilane, more preferably mono-C _1-4 alkyl mono-C _6-8 aryl dihalosilane, etc.), dihalosilane Aryldihalosilane (diphenyldichlorosilane and other di-C _6-12 aryldihalosilane, preferably di-C _6-10 aryldihalosilane, further preferably di-C _6-8 aryldihalosilane Halosilane, etc.) etc. As the dihalosilane compound, dialkyldihalosilane or monoalkylmonoaryldihalosilane is preferred. The dihalosilane compounds can be used alone or in combination of two or more. 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, or an aralkyl group, and particularly preferably an alkyl group or an aryl group. More preferably, it is an aryl group. As described above, in the method for producing a polysilane compound according to the first aspect, when the silyl radical cation has an organic group directly bonded to a silicon atom (R is an organic group (especially an aryl group)) (In this case), through the action of the above-mentioned nitrogen compound, the detachment of organic radicals is less likely to occur and the generation of outgassing can be suppressed. Representative trihalosilane compounds include C _1-10 alkyl trihalogens such as alkyltrihalosilane (methyltrichlorosilane, butyltrichlorosilane, tert-butyltrichlorosilane, hexyltrichlorosilane, etc.) Silane, preferably C _1-6 alkyl trihalosilane, further preferably C _1-4 alkyl trihalosilane, etc.), cycloalkyl trihalosilane (cyclohexyl trihalosilane, etc. single C _6-10 ring Alkyl trihalosilane, etc.), aryl trihalosilane (phenyl trichlorosilane, tolyl trichlorosilane, xylyl trichlorosilane, etc. C _6-12 aryl trihalosilane, preferably C _6-10 Aryltrihalosilane, more preferably C _6-8 aryltrihalosilane, etc.). The trihalosilane compound is preferably an alkyl trihalosilane or an aryl trihalosilane. The trihalosilane compounds can be used alone or in combination of two or more. Specific examples of the case where n is 4 (tetrahalosilane compounds) include tetrachlorosilane, dibromodichlorosilane, tetrabromosilane, and the like. A tetrahalosilane compound can be used individually or in combination of 2 or more types. Furthermore, tetrahalosilane compounds may be used in combination with mono-, di- or trihalosilane compounds. In addition, the halosilane compound may be a monohalosilane compound. Representative monohalosilanes include, for example, tri-C _1-10 alkyl monohalosilane such as trialkyl monohalosilane (trimethylchlorosilane), and preferably tri-C _1-6 alkyl monohalosilane. Preferred are tri-C _1-4 alkyl monohalosilane, etc.), dialkyl monoaryl monohalosilane (dimethylphenyl chlorosilane, etc. di-C _1-10 alkyl mono-C _6-12 aryl monohalogen Silane, preferably di-C _1-6 alkyl mono-C _6-10 aryl monohalosilane, more preferably di-C _1-4 alkyl mono-C _6-8 aryl monohalosilane, etc.), monoalkyl Diaryl monohalosilane (methyldiphenylchlorosilane and other mono-C _1-10 alkyl di-C _6-12 aryl monohalosilane, 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 (tri-C _6-12 aryl monohalosilanes such as triphenyl chlorosilane) , preferably tris C _6-10 aryl monohalosilane, further preferably tris C _6-8 aryl monohalosilane, etc.). The monohalosilane compounds can be used alone or in combination of two or more. These halosilane compounds can be used individually or in combination of 2 or more types. The halosilane compound preferably contains at least one selected from dihalosilane compounds and trihalosilane compounds. Furthermore, when the halosilane compound contains a trihalosilane compound and/or a tetrahalosilane compound, a network-like (net-like or branched) polysilane compound can be generated. When a network-like polysilane compound is obtained, representative halosilanes (or combinations thereof) include: (a) alkyl trihalosilane (for example, alkyl trihalosilane alone, methyl trihalosilane and Combinations of C _2-10 alkyl trihalosilane, C _2-10 alkyl trihalosilane, etc.), (b) aryl trihalosilane (for example, aryl trihalosilane alone), (c) aryl trihalosilane Combination with dihalosilane (such as monoalkyl monoaryl dihalosilane, etc.), etc. In the halosilane compound, the ratio (usage ratio) of at least one selected from dihalosilane compounds and trihalosilane compounds may be 50 mol% or more (for example, 60 mol% or more) relative to the total halosilane compound, It is preferably 70 mol% or more (for example, 80 mol% or more), and further preferably 90 mol% or more (for example, 95 mol% or more). Furthermore, in the case of obtaining a network-like polysilane, the ratio (usage ratio) of the trihalosilane compound may be 30 mol% or more (for example, 40 mol% or more) of the total halosilane compounds, and preferably It is 50 mol% or more (for example, 60 mol% or more), more preferably, it is 70 mol% or more (for example, 75 mol% or more), especially 80 mol% or more. Furthermore, when a dihalosilane compound and a trihalosilane compound are combined, the ratio may be dihalosilane compound/trihalosilane compound (molar ratio) = 99/1 to 1/99, preferably It can be 90/10～2/98 (for example, 85/15～2/98), more preferably, it can be 80/20～3/97 (for example, 70/30～4/96), especially it can be 60/40～5 /95 (for example, 50/50～7/93), usually 50/50～5/95 (for example, 45/55～7/93, preferably 40/60～10/90, further preferably 30 /70～88/12). The halosilane compound is preferably as pure as possible. For example, a liquid halosilane compound is preferably dried using a desiccant such as calcium hydride and distilled before use, while a solid halosilane compound is preferably purified by a recrystallization method or the like before use. Furthermore, the concentration (matrix concentration) of the halosilane compound in the raw material mixture (reaction liquid) can be, for example, about 0.05 to 20 mol/l, preferably about 0.1 to 15 mol/l, and still more preferably 0.2 to 0.2 mol/l. About 5 mol/l. The method for producing a polysilane compound according to the first aspect can be applied to the method for producing a polysilane compound including the following (a) to (c) by reacting a halosilane compound. (a) A method of dehalogenating and condensing a halogenated silane compound using magnesium as a reducing agent ("magnesium reduction method", methods described in WO98/29476, Japanese Patent Application Laid-Open No. 2003-277507, etc.) (b ) A method of dehalogenating and condensing a halogenated silane compound in the presence of an alkali metal such as metallic sodium, metallic lithium, metallic potassium (preferably metallic sodium) ("Kipping method", J. Am. Chem. Soc., 110, 124 (1988), Macromolecules, 23, 3423 (1990), etc.) (c) Method for dehalogenating and condensing silane compounds by electrode reduction (J. Chem. Soc., Chem. Commun., 1161 (1990), J. Chem. Soc., Chem. Commun. 897 (1992), etc.) The method for producing the polysilane compound of the first aspect preferably involves reacting the above-mentioned halosilane compound in the presence of a nitryl compound and magnesium. Reduction method, or Kipping method in which the above-mentioned halogenated silane compound is reacted in the presence of an alkali metal such as metallic sodium, metallic lithium, metallic potassium, etc. (preferably metallic sodium), and more preferably a nitryl compound The magnesium reduction method involves reacting the above halosilane compound with the presence of magnesium. Magnesium may be in the form of metallic magnesium (magnesium element), a magnesium alloy, or a mixture thereof (hereinafter also referred to as "magnesium component"). The type of magnesium alloy is not particularly limited, and examples thereof include commonly used magnesium alloys, such as magnesium alloys containing components such as aluminum, zinc, and rare earth elements (scandium, yttrium, etc.). The shape of the magnesium component is not particularly limited as long as it does not impair the reaction of the halosilane compound. Examples thereof include powdery form (powder, granular form, etc.), strip form, cut sheet form, block form, and rod. Shaped bodies, plate-shaped bodies (flat plates, etc.), etc., particularly preferably powders, granular bodies, strip-shaped bodies, cut sheet-shaped bodies, etc. The average particle diameter of magnesium (for example, powdered magnesium) can be, for example, 1 to 10000 μm, preferably 10 to 7000 μm, and more preferably 15 to 5000 μm (for example, 20 to 3000 μm). The magnesium component and the alkali metal may be used alone or in combination of two or more types. The usage amount of the magnesium component or the alkali metal is preferably 1 to 20 equivalents, more preferably 1.1 to 14 equivalents, and even more preferably 1.2 to 10 equivalents, in terms of magnesium conversion or alkali metal conversion, relative to the halogen atom of the halosilane compound. Preferably, it is 1.2 to 5 equivalents. In addition, the usage amount of the magnesium component or the alkali metal is preferably 1 to 20 times, more preferably 1.1 to 14 times, still more preferably 1.2 to 10 times in terms of moles relative to the halosilane compound. times, preferably 1.2 to 5 times. The method for producing a polysilane compound according to the first aspect may also include the above-mentioned halogen in the presence of a nitrogenyl compound, a magnesium component or an alkali metal, and an organic metal complex represented by the following general formula (Z1). Silane compounds react. M ^p L _p/q (Z1) (In the above general formula (Z1), 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). As the metal atoms constituting the p-valent metal cation M ^p , there can be enumerated: selected from iron, silver, aluminum, bismuth, cerium, cobalt, copper, dysprosium, erbium, europium, gallium, gallium, hafnium, 鈥, indium, iridium, lanthanum , gallium, manganese, molybdenum, neodymium, nickel, osmium, palladium, cadmium, chromium, platinum, rhenium, rhodium, ruthenium, samarium, scandium, tin, phosphorus, titanium, gallium, vanadium, chromium, tantalum, ytterbium, gold, mercury , tungsten, yttrium, zinc and zirconium composed of metals in the group. As p, an integer of 1 to 4 is preferable, an integer of 1 to 3 is more preferable, and 2 or 3 is even more preferable. As q, an integer of 1 to 4 is preferred, an integer of 1 to 3 is more preferred, and 1 or 2 is even more preferred. Examples of the q-valent organic ligand L include: β-diketone ligand, olefin, conjugated ketone, nitrile, amine, carboxyl ligand, carbon monoxide, phosphine, phosphinite, and phosphine Organic ligands such as acid diester (phosphonite) and phosphite (phosphite). The q-valent organic ligand L can also be a chelating ligand. As the above-mentioned organometallic complex, an organometallic complex represented by the following general formula (Z2) is preferred. [Chemical 7] (In the above general formula (Z2), M represents a group selected from iron, silver, aluminum, bismuth, cerium, cobalt, copper, dysprosium, erbium, europium, gallium, hafnium, indium, iridium, lanthanum, gallium, and manganese , molybdenum, neodymium, nickel, osmium, palladium, cadmium, platinum, rhenium, rhodium, ruthenium, samarium, scandium, tin, phosphorus, titanium, gallium, vanadium, chromium, tantalum, ytterbium, gold, mercury, tungsten, yttrium Metals in the group consisting of zinc and zirconium, R ^z1 independently represents a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group or an aryloxyalkyl group. , R ^z2 represents a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or the above-mentioned aralkyl group. p represents an integer of 1 or more). Examples of the saturated hydrocarbon group represented by R ^z1 and R ^z2 include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, hexyl, Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, behenyl, 2- Dodecyl hexadecyl, triacontyl, triacontyl, tetradecyl and other straight-chain or branched alkyl groups with 1 to 40 carbon atoms, and these halogen atoms (fluorine atoms , chlorine atom, bromine atom, iodine atom), alkoxy group (to be described below, etc.), silyl group (to be described below, etc.) and other substituents. An alkyl group substituted with one or two or more substituents, such as chlorine Propyl, 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydro Octyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, 3-(heptafluoroisopropoxy)propyl, trimethylsilylmethyl, etc.; cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, bicycloheptyl, cyclooctyl, adamantyl and other monocyclic or bicyclic or above polycyclic cyclic saturated hydrocarbon groups with 3 to 18 carbon atoms, as well as these cyclic saturated hydrocarbon groups through alkyl groups (the above, etc.), aryl (the above, etc.) and other substituents substituted with one or more than two types, such as 4-tert-butylcyclohexyl, 4-phenylcyclohexyl, etc.; or having the above ring Alkyl groups of saturated hydrocarbon groups (the above, etc.), such as cyclohexylmethyl, adamantylethyl, etc. Examples of the unsaturated hydrocarbon group represented by R ^z1 and R ^z2 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, as well as these unsaturated hydrocarbon groups via halogen atoms (the above, etc.) , an alkoxy group (to be described below, etc.), a silyl group (to be described below, etc.), an aryl group (to be described below, etc.), one or two or more substituents are substituted, such as 2-tris Fluoromethylvinyl, 2-trifluoromethylethynyl, 3-methoxy-1-propenyl, 3-methoxy-1-propynyl, 2-trimethylsilylvinyl, 2- Trimethylsilyl ethynyl, 2-phenylethynyl, 2-phenylethynyl, etc.; cyclopropenyl, cyclohexenyl, cyclooctenyl and other cyclic unsaturated hydrocarbon groups with 3 to 18 carbon atoms; having The alkyl group of the above-mentioned cyclic unsaturated hydrocarbon group (the above-mentioned ones, etc.), for example, cyclohexenylethyl group, etc. Examples of the aromatic hydrocarbon group represented by R ^z1 and R ^z2 include phenyl, and one or two of tolyl, butylphenyl, butoxyphenyl, etc. via an alkyl group, alkoxy group, amino group, etc. Substituted phenyl groups formed by more than one substitution, etc. Examples of the aralkyl group represented by R ^z1 and R ^z2 include benzyl, phenethyl, methylphenylethyl, butylphenylethyl, phenylpropyl, methoxyphenylpropyl, etc. Examples of the aralkyl group include pyridylmethyl, pyridylethyl, and the like. Examples of the alkoxy group represented by R ^z1 include alkoxy groups having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, and octyloxy groups. Examples of the aryloxy group include , examples include phenoxy, and substituted phenoxy groups such as tolyloxy and butylphenoxy groups substituted with substituents such as alkyl groups. Examples of the aralkoxy group represented by R ^z1 include benzyloxy group, phenethoxy group, etc., and examples of the aryloxyalkyl group include phenoxypropyl group, phenoxybutyl group, and the like. R ^z1 is preferably a saturated hydrocarbon group, aromatic hydrocarbon group, etc. having 1 to 30 carbon atoms, more preferably an alkyl group, phenyl group, etc. having 1 to 15 carbon atoms, and particularly preferably a methyl group. R ^z2 is preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 18 carbon atoms, an aromatic hydrocarbon group, etc., and further preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a phenylethyl group. The radicals are preferably hydrogen atoms. Preferred examples of p are as shown above. As the metal complex, various metal complexes can be cited based on the combination of the above-mentioned metal M and R ^z1 and R ^z2 . Specific examples include: silver acetyl acetonate (I), tris (acetyl acetonate) aluminum (III), tris (2,2,6,6-tetramethyl-3,5-heptanedione) Aluminum(III), tris(2,2,6,6-tetramethyl-3,5-heptanedione)bismuth(III), tris(acetylacetone)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) Dione)cobalt(III), tris(3-phenyl-2,4-pentanedione)cobalt(III), tris(3-(1-phenylethyl)-2,4-pentanedione)cobalt (III), bis(benzoylacetone)cobalt(II), bis(hexafluoroacetylacetone)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(hexafluoroacetylacetone) Copper(II), bis(trifluoroacetylacetone)copper(II), tris(acetylacetone)dysprosium(III), tris(acetylacetone)erbium(III), tris(2,2,6,6, -Tetramethyl-3,5-heptanedione)erbium(III), tris(acetylacetone)europium(III), bis(acetylacetone)iron(II), tris(acetylacetone)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- Tetramethyl-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- Phenyl-3,5-heptanedione) iron (III), tetrakis (acetyl acetone) hafnium (IV), tris (acetyl acetone) gallium (III), tris (acetyl acetone) gallium (III), tris (acetyl acetone) indium (III), tris (acetyl acetone) iridium (III), tris (acetyl acetone) lanthanum (III), tris (acetyl acetone) iridium (III) (III), Bis(acetyl acetone)manganese(II), Tris(acetyl acetone)manganese(III), Bis(hexafluoroacetyl acetone)manganese(II), Bis(acetyl acetone) dioxymolybdenum (IV), tris(acetyl acetone) neodymium(III), tris(2,2,6,6-tetramethyl-3,5-heptanedione) neodymium(III), bis(acetyl acetone) nickel( II), bis(2,2,6,6-tetramethyl-3,5-heptanedione)nickel(II), bis(hexafluoroacetylacetone)nickel(II), bis(1,3-di Phenyl-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(acetylacetone)palladium(II), bis(hexafluoroacetylacetone) 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)cadmium (III), tris(acetyl acetone) chelate(III), tris(hexafluoroacetyl acetone) chelate(III), bis(acetyl acetone) platinum(II), tris(acetyl acetone) rhodium(III), Tris(acetyl acetone)ruthenium(III), tris(acetyl acetone)scandium(III), tris(hexafluoroacetyl acetone)scandium(III), tris(2,2,6,6-tetramethyl-3 , 5-heptanedione) scandium (III), tris (acetyl acetone) samarium (III), tris (2,2,6,6-tetramethyl-3,5-heptanedione) samarium (III), Bis(acetyl acetone)tin(II), tris(acetyl acetone)tin(III), tris(2,2,6,6-tetramethyl-3,5-heptanedione)trian(III), tris(acetyl acetone)tin(III) (2,2,6,6-tetramethyl-3,5-heptanedione)quinol(III), tris(acetylacetone)vanadium(III), tris(acetylacetone)yttrium(III), tris( Hexafluoroacetyl acetone) yttrium (III), tris (2,2,6,6-tetramethyl-3,5-heptanedione) yttrium (III), bis (acetyl acetone) zinc (II), bis(acetyl acetone) (Hexafluoroacetyl acetone) zinc (II), bis (2,2,6,6-tetramethyl-3,5-heptanedione) zinc (II), tetrakis (acetyl acetone) zirconium (IV), Tetrakis (2,2,6,6-tetramethyl-3,5-heptanedione) zirconium (IV), tetrakis (trifluoroacetyl acetone) zirconium (IV), etc. These organic metal complexes can be used individually or in combination of 2 or more types. As the organometallic complex, a metal complex synthesized in advance can be used, or one produced in a system can be used. Relative to the halosilane compound, the usage amount of the above-mentioned organometallic complex is preferably in the range of 0.001 to 10 mol times, more preferably in the range of 0.001 to 1 mol times, and particularly preferably in the range of 0.001 to 0.1 mol times. . (Metal Halide) The method for producing a polysilane compound according to the first aspect may also react the above-mentioned halosilane compound in the presence of a nitrosilyl compound, magnesium or an alkali metal, and a further metal halide. Examples of metal halides include: polyvalent metal halides, such as transition metals (e.g., samarium and other periodic table group 3A elements, periodic table group 4A elements such as titanium, periodic table group 5A elements such as vanadium, iron, nickel, cobalt, palladium Halides of metals such as elements from group 8 of the periodic table, elements from group 1B of the periodic table such as copper, elements from group 2B of the periodic table such as zinc, etc.), metals from group 3B of the periodic table (aluminum, etc.), metals from group 4B of the periodic table (tin, etc.) ( chloride, bromide or iodide, etc.). The valence of the above-mentioned metals constituting the metal halide is not particularly limited, but is preferably 2 to 4 valences, especially 2 or 3 valences. These metal halides can be used alone or in combination of two or more. The metal halide is preferably a chloride or bromide of at least one metal selected from the group consisting of iron, aluminum, zinc, copper, tin, nickel, cobalt, vanadium, titanium, palladium, samarium, and the like. 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 (iron bromide such as FeBr ₂ and FeBr ₃ , etc.), iodide (SmI _2, etc.), etc. Among these metal halides, chlorides (such as ferric chlorides such as iron (II) chloride and iron (III) chloride, zinc chloride, etc.) and bromides are preferred. Ferric chloride and/or zinc chloride are usually used, especially zinc chloride and the like. The usage amount of the metal halide is preferably in the range of 0.001 to 10 mol times, more preferably in the range of 0.001 to 1 mol times, and particularly preferably in the range of 0.001 to 0.1 mol times relative to the halosilane compound. In addition, the concentration of the metal halide in the solvent (reaction liquid) is usually about 0.001 to 6 mol/L, preferably about 0.005 to 4 mol/L, and further preferably about 0.01 to 3 mol/L. (Aprotic solvent) In the method for producing a polysilane compound according to the first aspect, the reaction of the halosilane compound in the presence of the nitrosilyl compound is preferably carried out in a solvent (reaction solvent), and more preferably in an aprotic solvent in a solvent. Aprotic solvents as solvents (reaction solvents) include, for example, ethers (1,4-dioxane, tetrahydrofuran, tetrahydropyran, diethyl ether, diisopropyl ether, 1,2-dimethoxyethyl Alkanes, bis(2-methoxyethyl) ether and other cyclic or chain C _4-6 ethers), carbonates (propylene carbonate, etc.), nitriles (acetonitrile, benzonitrile, etc.), amide Hydrocarbons (dimethylformamide, dimethylacetamide, etc.), styrenes (dimethylsyanide, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), aliphatic hydrocarbons (e.g. Hexane, cyclohexane, octane, cyclooctane and other chain or cyclic hydrocarbons), etc. These aprotic solvents can be used alone or in combination of two or more to form 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-dioxane etc. (especially tetrahydrofuran, 1,2-dimethoxyethane)]. A polar solvent may be used individually or in combination of 2 or more types, and a polar solvent and a nonpolar solvent may be combined. The method for producing a polysilane compound according to the first aspect may further include contacting the liquid after the reaction (reaction liquid) with an aqueous solution containing at least one selected from the group consisting of a base and an acid. Purification, thereby obtaining the above-mentioned polysilane compound. By contacting the above-mentioned polysilane compound with an alkali or acid for purification treatment, inclusions such as halogen atoms (for example, halide ions (chloride ions, etc.), Si-Cl remaining in the polysilane compound) can be removed, and inclusions such as Promoting the low molecular weight of the polysilane compound can improve the solvent solubility of the polysilane compound. In addition, the acid may also function as a quencher for the reaction of the halosilane compound. Furthermore, by bringing the above-mentioned polysilane compound into contact with a metal halide described below and performing a purification treatment, the remaining metal atoms (for example, Mg, Zn, etc.) in the polysilane compound can be removed. The treatment temperature is preferably -50°C to about the boiling point of the solvent, and more preferably room temperature to 100°C. In addition, as the base used, various compounds can be used as long as they are alkaline. For example, sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia, tetramethylammonium hydroxide, sodium carbonate, carbonic acid can be used. Inorganic bases such as sodium hydride, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, calcium hydride; 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; alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide; triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 4 -Dimethylaminopyridine, diazabicycloundecene (DBU) and other organic bases. Various acids can be used, and inorganic acids such as hydrogen chloride can be used. Here, various solvents can be used for the alkali or acid treatment. For example, one or more solvents selected from the following solvents can be used: hydrocarbon solvents such as benzene, toluene, and xylene, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Diol solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane and other ether solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, etc. Ketone solvents such as ketone, cyclopentanone, and cyclohexanone, and alcohol solvents such as ethanol, isopropanol, butanol, etc. In addition, an acetate compound containing a cyclic skeleton can also be preferably used as a solvent used in the above-mentioned treatment under alkaline conditions. The acetate compound containing a cyclic skeleton is not particularly limited as long as it is an acetate solvent having a cyclic skeleton that does not impair the effects of the present invention. Preferably, it is acetic acid represented by the following formula (S1). Cycloalkyl esters. [Chemical 8] (In the formula (S1), R ^s1 is each independently an alkyl group, p is an integer from 1 to 6, and q is an integer from 0 to (p+1)). Examples of the alkyl group represented by R ^s1 include alkyl groups having 1 to 3 carbon atoms, and examples include methyl, ethyl, n-propyl, and isopropyl. Specific examples of the cycloalkyl acetate represented by formula (S1) include cyclopropyl acetate, cyclobutyl acetate, cyclopentyl acetate, cyclohexyl acetate, cycloheptyl acetate, and cyclooctyl acetate. Among these, cyclohexyl acetate is preferred from the viewpoint of ease of acquisition. The reaction of the above halosilane compound can also be quenched by acid treatment. Various acids can be used, and inorganic acids such as hydrogen chloride can be used. According to the manufacturing method of the polysilane compound of the first aspect, the polysilane compound can be obtained with a yield of 50% or more, preferably a yield of 70% or more. <Polysilane compound> According to the method for producing a polysiloxane compound according to the first aspect, as described above, the formation of side reactants such as siloxane bonds and silanol groups can be suppressed, thereby reducing the silicon content in the polysiloxane compound. The amount of oxyalkane bonds (Si-O) present. According to the manufacturing method of the polysilane compound of the first aspect, the ratio of the following (2X) to the sum of the peak areas of the following (1X) and (2X), that is, the ratio represented by the following formula (3X) can be Set to 0.4 or less. The peak areas of the above (1X) and (2X) are the polysilane compounds with maximum detection in the bond energy range of 99 eV and above and 104 eV and below as measured by X-ray photoelectron spectroscopy. The spectrum of the peak height is obtained by separating the peaks. The ratio is preferably 0.35 or less, more preferably 0.3 or less, further preferably 0.2 or less, particularly preferably 0.1 or less, and most preferably 0.05 or less. (1X)・・・The area of the peak with the maximum peak height in the range of bond energy above 99.0 eV and below 99.5 eV (2X)・・・The maximum peak height in the range of bond energy above 100 eV and below 104 eV The area of the peak of the peak height (3X)・・・(2X)/[(1X)+(2X)] Measure the intensity of the peak (Intensity). Regarding the above (1X) and (2X), perform it within each bond energy range. The area of the peak obtained by separating the peaks can be used to determine the content ratio of Si-O and Si-C based on (2X), the area of the peak with the maximum peak height in the range of bond energy 100 eV or more and 104 eV or less. In addition, the content ratio of Si-Si can be known from the area of the peak with the maximum peak height in the range of bond energy 99.0 eV or more and 99.5 eV or less (1X). It is considered that when the polysilane compound contains not only Si-C but also Si-O, two peaks with the maximum peak height overlap after peak separation in the range of 100 eV or more and 104 eV or less, but the second state Such a polysilane compound is preferably in the range of 100 eV or more and 104 eV or less. After the peak separation, only one peak with the maximum peak height appears. Since it is ideal that only one peak appears, it does not substantially contain Si-O bond. Furthermore, in the case where the previous polysilane compound contains not only Si-C but also Si-O, two peaks with the maximum peak height overlap and appear after the peak separation in the range of 100 eV or more and 104 eV or less, so The area ratio becomes larger, so the ratio expressed by the above formula exceeds 0.4. The polysilane compound of the second aspect is a polysilane compound produced by the production method of the first aspect described above. Examples of the polysilane compound of the second aspect produced by the production method of the first aspect include polysilane compounds having 3 to 40 Si atoms, and preferably polysilane compounds having 5 to 30 Si atoms. The polysilane compound is preferably at least one selected from the group consisting of polysilane compounds represented by the following general formulas (T-1) and (T-2). (R ^t10 R ^t11 R ^t12 Si) _t1 (R ^t13 R ^t14 Si) _t2 (R ^t15 Si) _t3 (Si) _t4 (T-1) (In the above general formula, R ^t10 , R ^t11 , R ^t12 , R ^t13 , R ^t14 and R ^t15 are independently hydrogen atoms, hydroxyl groups or organic groups. t1, t2, t3 and t4 are independently molar fractions, which are t1+t2+t3+t4=1, 0≦t1≦1, 0≦t2≦1 , 0≦t3≦1 and 0≦t4≦1). [Chemical 9] (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) Examples of the organic groups represented by R ^t10 to R ^t17 include The same specific examples and preferred examples as described above as the organic group represented by R. As the organic group represented by R ^t10 to R ^t17 , for example, any organic group can be introduced by the method described in paragraph 0031 of Japanese Patent Application Laid-Open No. 2003-261681. The mass average molecular weight (Mw) of the polysilane compound is not particularly limited as long as it does not hinder the object of the present invention, but is preferably 500 to 10,000, more preferably 1,000 to 7,000, and even more preferably 2,000 to 5,000. In this specification, the mass average molecular weight (Mw) is a value measured in polystyrene conversion by gel permeation chromatography (GPC). <Composition> The composition of the third aspect is a composition containing the polysilane compound of the second aspect produced by the production method of the first aspect. Furthermore, from the viewpoint of suppressing the generation of outgassing and microcracks, the composition of the third aspect preferably further contains the above-mentioned nitrogenyl compound. The composition of the third aspect further contains the above-mentioned nitrate compound. There is no particular limitation as long as the effect of the present invention is not impaired. The method of making the above-mentioned nitrate compound used in the production method of the first aspect can be used. This can be achieved by leaving the nitryl compound remaining in the composition of the third aspect, or by adding the above-mentioned nitryl compound to the composition containing the polysilane compound of the second aspect. The above-mentioned nitrogenyl compound may be used alone or in combination of two or more types. The content of the nitroxyl compound in the composition of the third aspect is preferably 0.005 mass% or more, more preferably 0.009 mass% or more, relative to the total mass of components other than the solvent in the composition of the third aspect. Furthermore, the content of the nitroxyl compound in the composition of the third aspect is preferably 2 mass% or less, more preferably 1 mass%, relative to the total mass of components other than the solvent in the composition of the third aspect. the following. Furthermore, the composition of the third aspect may or may not be a thermosetting composition. In addition, the composition of the third aspect may be a radiation-sensitive composition, or may not be a radiation-sensitive composition. It may be a positive-type radiation-sensitive composition that dissolves the developer by exposure, or it may be a radiation-sensitive composition. Negative radiation-sensitive compositions that are insolubilized by exposure to developing solutions. Examples of the light source of the above-mentioned radiation include active energy rays such as ultraviolet rays and excimer laser light; light sources that emit ultraviolet rays such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and carbon arc lamps. (Solvent) The composition of the third aspect preferably contains a solvent. Examples of the solvent include the above-mentioned cyclic skeleton-containing acetate compounds such as cycloalkyl acetate represented by the above formula (S1); alcohols such as methanol, ethanol, propanol, and n-butanol; ethylene glycol, dihydrogen Polyols such as ethylene glycol, propylene glycol, and dipropylene glycol; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl n-amyl ketone, methyl isopentyl ketone, and 2-heptanone; γ-butanone Lactones and other organic solvents containing lactone rings; compounds with ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the above-mentioned polyvalent Derivatives of alcohols or polyols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether and other monoalkyl ethers of the above-mentioned compounds with ester bonds or compounds with ether bonds such as monophenyl ether; such as Methane-like cyclic ethers, 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, cresolyl methyl ether, diphenyl ether, dibenzyl ether, phenylethyl ether, butyl phenyl ether, ethyl benzene, dibenzoyl ether, etc. Aromatic organic solvents such as ethylbenzene, amylbenzene, cumene, toluene, xylene, cumene, and mesitylene; N,N,N',N'-tetramethylurea, N, N,2-trimethylpropionamide, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylacetamide, N,N-diethyl Nitrogen-containing organic solvents such as methylformamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-ethylpyrrolidone, etc. Among them, preferred are cycloalkyl acetate represented by the above formula (S1), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), N,N,N',N'-tetramethyl urea (TMU), and butanol, more preferably cyclopropyl acetate, cyclobutyl acetate, cyclopentyl acetate, cyclohexyl acetate, cycloheptyl acetate or cyclooctyl acetate, further preferably cyclohexyl acetate ester. These solvents can also be used in combination of 2 or more types. Regarding the composition of the third aspect, in terms of suppressing microcracking, the moisture content of the composition of the third aspect is preferably 1.0 mass% or less, more preferably 0.5 mass% or less, and still more preferably 0.3 mass%. % or less, preferably less than 0.3% by mass. In addition, the water content in the solvent can be measured by the Karnofsky method. The moisture of the composition of the third aspect comes from the solvent in most cases. 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. The amount of solvent used is not particularly limited as long as it does not hinder the purpose of the present 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 mass %, more preferably 10 to 40 mass %. (Other components) The composition of the third aspect may also contain polysilane other than the polysilane compound of the second aspect. For example, in terms of improving chemical resistance, polysilane compounds with a relatively high Mw (hereinafter also referred to as "high molecular weight polysilane") can be used. The Mw of the high molecular weight polysilane is, for example, more than 5,000 and 100,000 or less. , preferably about 6,000 to 60,000. In order to improve processability, the composition of the third aspect may also contain a silicon-containing resin other than the polysilane compound. Examples of silicon-containing resins other than polysiloxane compounds include polysiloxane resins or polysiloxane-polysiloxane resins having a polysiloxane structure (I-1) and a polysiloxane structure (I-2). The Mw of the silicon-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. Furthermore, the above-mentioned polysilane-polysiloxane resin can be produced, for example, by treating the polysilane compound of the second aspect in a solvent under the above-mentioned alkaline conditions, and then mixing it with a substance selected from the following: At least one of the group consisting of at least one silicon selected from the group consisting of silicon compounds represented by the following general formulas (A-1-1) to (A-1-4) undergoes a hydrolysis condensation reaction: compounds and hydrolysates, condensates and hydrolysis condensates of the above-mentioned silicon compounds. R ¹ R ² R ³ SiX ¹ (A-1-1) R ⁴ R ⁵ SiX ² ₂ (A-1-2) R ⁶ SiX ³ ₃ (A-1-3) SiX ⁴ ₄ (A-1-4 ) (In the above general formula, X ¹ to X ⁴ are each independently a hydrolyzable group, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an organic group. The hydrogen atoms in can also be replaced by halogen atoms). Examples of the hydrolyzable group represented by X ¹ to X ⁴ include an alkoxy group, a halogen atom or an isocyanato group (NCO), and an alkoxy group is preferred. Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms. Specific examples include: methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, and third group. Butoxy, pentoxy, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom is preferred. Examples of the organic groups represented by R ¹ to R ⁶ include organic groups having 1 to 30 carbon atoms. Examples include alkyl groups [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 (cyclohexyl, etc. with 5 carbon atoms) ~8 cycloalkyl groups, especially cycloalkyl groups with 5 to 6 carbon atoms), alkenyl groups [vinyl, propenyl, butenyl and other alkenyl groups with 2 to 10 carbon atoms (preferably cycloalkyl groups with 5 to 6 carbon atoms) Alkenyl groups with 2 to 6 carbon atoms, especially alkenyl groups with 2 to 4 carbon atoms, etc.)], cycloalkenyl groups [1-cyclopentenyl, 1-cyclohexenyl, etc. cycloalkenyl groups with 5 to 10 carbon atoms ( Preferred are cycloalkenyl groups with 5 to 8 carbon atoms, especially cycloalkenyl groups with 5 to 7 carbon atoms, etc.)], aryl groups (aryl groups with 6 to 10 carbon atoms, such as phenyl and naphthyl groups, etc.), Aralkyl [benzyl, phenethyl, etc. C _6-10 aryl-C _1-6 alkyl (C _6-10 aryl-C _1-4 alkyl, etc.)], amino group, N-substituted amino group (N-mono- or disubstituted amino groups substituted by the above-mentioned alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, acyl groups, etc.), etc. The alkyl group, cycloalkyl group, aryl group or aryl group constituting the aralkyl group may have one or a plurality of substituents. Examples of such substituents include the alkyl groups exemplified above (especially alkyl groups having 1 to 6 carbon atoms, etc.), the alkoxy groups exemplified above, and the like. Examples of organic groups having such substituents include C _1-6 alkyl-C _6-10 aryl groups such as tolyl, xylyl, ethylphenyl, and methylnaphthyl groups (preferably mono, Two or three C _1-4 alkyl-C _6-10 aryl, especially mono or two C _1-4 alkylphenyl, etc.); methoxyphenyl, ethoxyphenyl, methoxynaphthyl etc. C _1-10 alkoxy C _6-10 aryl group (preferably C _1-6 alkoxy C _6-10 aryl group, especially C _1-4 alkoxy phenyl group, etc.), etc. Furthermore, the silicon compound represented by the general formula (A-1-3) may be a silicon compound represented by the following formula (A-3). HOOC-UZY-Si(OR ^a ) ₃ (A-3) (In the above general formula (A-3), U represents that the two ring carbon atoms are removed from the aromatic ring group or the alicyclic group. A divalent group generated from a hydrogen atom, or an alkylene group that may have a branched chain and/or a double bond, Z represents -NHCO- or -CONH-, Y represents a single bond, an alkylene group, an aryl group or -R ^Y1 -NH-R ^Y2 - (in the formula, R ^Y1 and R ^Y2 each independently represent an alkylene group), R ^a each independently represents a hydrocarbon group. Among them, U and/or Y may have a group selected from (meth)acrylic acid group, At least one of the group consisting of vinyl and epoxy groups serves as a substituent). Examples of the aromatic ring in U include an aromatic ring having 6 to 10 carbon atoms (for example, benzene ring, naphthalene ring, tolyl group, xylyl group, etc.) which may have a substituent having 1 to 2 carbon atoms. Examples of the alicyclic ring in U include alicyclic rings having 5 to 10 carbon atoms (for example, monocyclic cycloalkyl groups, monocyclic cycloalkenyl groups, bicyclic alkyl groups, cage alkyl groups, etc., specifically , such as cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, dicyclopentadiene ring, nor𦯉ane ring, nor𦯉ene ring, Cubane ring, basalane ring, etc.). Examples of the alkylene group in U mentioned above that may have a branched chain and/or a double bond include an alkylene group having 1 to 4 carbon atoms. Examples include: methylene, ethylene, propylene, and vinylidene. , (2-octenyl)ethylidene, (2,4,6-trimethyl-2-nonenyl)ethylidene and other alkylene groups, alkylene groups with double bonds or carbon numbers from 1 to 9 branched alkylene group. Examples of the alkylene group in Y include an alkylene group having 1 to 6 carbon atoms. Examples thereof include methylene, ethylene, propylene, butylene, and the like. The aryl group in Y above is preferably one having 6 to 10 carbon atoms. Examples of such aryl groups include phenylene groups (ortho, meta or para, etc.), naphthylene groups (1,4-, 1,5-, 2,6-, etc.). Specific examples of -R ^Y1 -NH-R ^Y2 - among 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 -, etc. Examples of the polysiloxane resin include at least one selected from the group consisting of silicon compounds represented by the above general formulas (A-1-1) to (A-1-4). Hydrolysates, condensates and hydrolysis condensates of at least one silicon compound in the group. Resins other than the polysilane compound of the first aspect (hereinafter referred to as other Si resins) may be used alone or in combination of a plurality of types. When the above-mentioned other Si resin is included, the blending ratio (mass ratio) of the polysilane compound of the first aspect and the other Si resin in the composition of the third aspect may be appropriately changed depending on the use, for example 1:99～99:1, preferably 10:90～90:10. The composition of the third aspect may also include an organic compound having two or more hydroxyl groups or carboxyl groups in one molecule as a dissolution accelerator for an alkaline aqueous solution or solution. Examples of such organic compounds include the compounds shown below. [Chemical 10] [Chemical 11] [Chemical 12] 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 phenyl 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. Enantiomers or diastereomers may exist in the above structural formulas, and each structural formula represents all of these stereoisomers representatively. These stereoisomers can be used individually or in the form of mixtures. The above-mentioned organic compounds can be used individually by 1 type or in combination of 2 or more types. The usage amount is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass relative to the total amount of solid components excluding the solvent of the composition of the third aspect. By adding such an organic compound, when the film of the resin composition is removed during processing in the manufacturing process or when the resin composition is given photolithographic properties, the disintegration of the film formed by using the above composition Speed up and peeling becomes easy. In order to improve stability, the composition of the third aspect may also contain a monovalent or divalent or higher organic acid with a carbon number of 1 to 30. Examples of acids to be added at this time include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, nonanoic acid, capric acid, oleic acid, stearic acid, linoleic acid, linoleic 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, methylpropanol Diacid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid , itaconic acid, maleic acid, fumaric acid, citraconic acid, citric acid, etc. Among these, oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid, etc. are particularly preferred. In addition, in order to maintain stability, two or more types of acids may be mixed and used. It is preferable to prepare the above-mentioned organic compound in such a way that the pH value of the composition is converted to 0≦pH≦7, more preferably 0.3≦pH≦6.5, and still more preferably 0.5≦pH≦6. acid. Furthermore, the composition of the third aspect may also contain a monovalent or divalent or higher alcohol or ether compound having a cyclic ether as a substituent as a stabilizer. Specific examples of stabilizers that can be used include those described in paragraphs (0180) to (0184) of Japanese Patent Application Laid-Open No. 2009-126940. The composition of the third aspect may also contain water. By adding water, lithographic performance is improved. The content of water in the solvent component of the composition of the third 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. The composition of the third aspect may also include a photoacid generator. Specific examples of photoacid generators that can be used include those described in paragraphs (0160) to (0179) of Japanese Patent Application Laid-Open No. 2009-126940. The composition of the third aspect may also contain a surfactant if necessary. Specific examples of surfactants that can be used include those described in paragraph (0185) of Japanese Patent Application Laid-Open No. 2009-126940. The composition of the third aspect may also include a thermal cross-linking accelerator. Specific examples of usable thermal cross-linking accelerators include those described in Japanese Patent Application Laid-Open No. 2007-302873. Examples of the thermal crosslinking accelerator include phosphate compounds and borate compounds. Examples of such phosphate compounds include ammonium salts such as ammonium phosphate, tetramethylammonium phosphate, and tetrabutylammonium phosphate; and sulfonium salts such as triphenylsulfonium phosphate. Examples of such borate compounds include ammonium salts such as ammonium borate, tetramethylammonium borate, and tetrabutylammonium borate; and sulfonium salts such as triphenylsulfonate borate. In addition, the said thermal crosslinking accelerator can be used individually by 1 type or in combination of 2 or more types. Moreover, the added amount of the thermal crosslinking accelerator is preferably 0.01 to 50 mass%, more preferably 0.1 to 40 mass%, relative to the total solid content of the composition excluding the solvent. The composition of the third aspect may also contain various other hardeners. Examples of the hardening agent include: Brnoster acids; imidazoles; organic amines; organic phosphorus compounds and their complexes; organic amine complexes of Lewis acids; amidines; alkali components generated by light or heat Hardener, etc. (Applications) The composition of the third aspect can be used to form protective films or interlayer films that protect various substrates (including films containing metal oxides and films containing various metals). Examples of the above various substrates include semiconductor substrates, liquid crystal displays, organic light-emitting displays (OLED), electrophoretic displays (electronic paper), touch panels, color filters, backlight devices and other display material substrates (including metal oxide-containing substrates). Films, films containing various metals), solar cell substrates (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 Films of various metals), substrates of photovoltaic components (including films containing metal oxides, films containing various metals). <Cured product and substrate provided with the above-mentioned cured product> The cured product of the fourth aspect is a cured product of the composition of the third aspect. The substrate of the fifth aspect is a substrate having the hardened material of the fourth aspect. The method of forming the hardened material of the fourth aspect is not particularly limited as long as the effect of the present invention is not impaired. Examples include the following methods: using a roll coater, a reverse coater, or a rod coater as necessary. Apply to any substrate using a contact transfer coating device such as a machine or a non-contact coating device such as a rotator (rotary coating device) or curtain coater. The substrate is not particularly limited, and examples thereof include: glass substrate, quartz substrate, transparent or translucent resin substrate (such as polycarbonate, polyethylene terephthalate, polyether styrene, polyimide, polyimide, etc.) Heat-resistant materials such as amide, amide, and imine), metals, silicon substrates, etc. It can also be used as substrates for semiconductor substrates, liquid crystal displays, organic light-emitting displays (OLED), electrophoretic displays (electronic paper), touch panels, color filters, backlight devices and other display materials (including films containing metal oxides, films containing various Metal films), solar cell substrates (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) , Optoelectronic component substrates (including films containing metal oxides, films containing various metals) and other various substrates. The thickness of the substrate is not particularly limited, and can be appropriately selected depending on the usage of the pattern forming body. The coating film after the above coating is preferably dried (pre-baked). The drying method is not particularly limited, and examples include: (1) drying for 60 to 120 seconds using a heating plate at a temperature of 80 to 120°C, preferably 90 to 100°C; (2) leaving it at room temperature for several seconds Methods that can take hours to several days; (3) methods of placing it in a hot air heater or infrared heater for tens of minutes to several hours to remove the solvent, etc. The dried coating film may be exposed by irradiation with active energy rays such as ultraviolet rays or excimer laser light, or may not be exposed. The amount of energy rays to be irradiated is not particularly limited, but may be about 30 to 2000 mJ/cm ² , for example. The exposure step can also be performed in place of or together with the baking step described below. Moreover, in the exposure step, for example, the formed coating film may be selectively exposed. When the selective exposure step is included, a development step may also be included. Furthermore, for example, the formed coating film may be subjected to imprint lithography. In the case of imprint lithography, for example, a method may include the following steps: a step of applying the composition of the third aspect on a substrate to form a coating film; pressing the coating film to form a specific pattern The steps of molding the concave-convex structure; and the steps of exposure. The step of exposing is performed on the coating film containing the composition of the third aspect while pressing the mold against the coating film. After curing by exposure, the mold is peeled off to obtain a cured product of the fourth aspect patterned according to the shape of the mold. In order to improve the physical properties of the film, it is preferable that the coating film after drying, exposure or development is baked (post-baked). The baking 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 baking 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 also be under the atmosphere, and the oxygen concentration can be appropriately controlled. The baking time may be appropriately changed, and is approximately 10 minutes to 120 minutes. The cured product of the fourth aspect is preferably a protective film that protects the above-mentioned various substrates (including films containing metal oxides and films containing various metals). When the hardened material is a film, the thickness is preferably 10 nm to 10000 nm, more preferably 50 to 5000 nm, and further preferably 100 to 3000 nm. <Anionic polymerization selective accelerator in the production of polysilane compounds> The anionic polymerization selective accelerator of the sixth aspect is used in the production of a polysilane compound containing a nitryl compound having a structure represented by the above general formula (A). Selective accelerator for anionic polymerization. The anionic polymerization selective accelerator of the sixth aspect can cause the silyl radical cations generated during the production of polysilane compounds to undergo charge spin and convert them into silyl radical anions, thereby selectively promoting the anion of the silyl radical anions. polymerization. This can inhibit the formation of side reactants such as siloxane bonds and silanol groups that cause micro-cracks, and also inhibit the generation of outgassing. Specific examples and preferred examples of the nitroxyl compound containing the structure represented by the general formula (A) are as described in the method for producing a polysilane compound according to the first aspect. The usage amount of the anionic polymerization selective accelerator of the sixth aspect is preferably in the range of 0.0001 to 10 molar times, more preferably in the range of 0.001 to 5 molar times relative to the halosilane compound used in the production of the polysilane compound. , more preferably in the range of 0.001 to 1 molar times, particularly preferably in the range of 0.001 to 0.1 molar times. [Examples] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. [Example 1] Production of polysilane compound: 25 g of granular (particle diameter 20 to 1000 μm) magnesium and triacetyl acetone as a catalyst were added to a round flask with an internal volume of 1000 ml equipped with a three-way stopcock. ) Iron (III) 2.1 g, 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-alkoxy radical) 0.61 mmol (0.10 g), at 50 Heat and reduce the pressure to 1 mmHg (=133 kPa) at ℃, dry the inside of the reactor (flask), introduce dry argon gas into the reactor, and add tetrahydrofuran (tetrahydrofuran) that has been dried with sodium-benzophenone carbonyl radicals in advance. THF) 500 ml, stir at 25°C for about 60 minutes. 63.5 g (0.3 mol) of methylphenyldichlorosilane previously purified by distillation was added to the reaction mixture using a syringe, and the mixture was stirred at 25° C. for about 24 hours. After the reaction, 1000 ml of 1 N (=1 mol/L) hydrochloric acid was added to the reaction mixture, and then extracted with 500 ml of toluene. Wash the toluene layer 10 times with 200 ml of pure water, dry the toluene layer with anhydrous magnesium sulfate, and then distill the toluene away to obtain 28.4 g of methylphenylsilane polymer (mass average molecular weight 2000) (yield 63 %). [Examples 2 to 4 and Comparative Examples 1 and 2] The polysilane compound was produced as shown in Table 1 below by changing the type of halosilane compound, the type of organometallic complex or metal halide, and the presence or absence of the nitrile compound. The polysilane compounds of Examples 2 to 4 and Comparative Examples 1 and 2 were produced in the same manner as Example 1 except for the type of polysilane compound to be produced. In addition, Example 5 was produced according to the method described in JACS, 110, 124 (1998) and Macromolecules, 23, 3423 (1990), except for adding the nitrogenyl compound. [Table 1] [Preparation Examples 1 to 4 and Comparative Preparation Examples 1 and 2] The composition was prepared so that the solid content concentration of each polysilane compound obtained in the above Examples 1 to 4 and Comparative Examples 1 and 2 was 30% by mass. Each composition of Preparation Examples 1 to 4 and Comparative Preparation Examples 1 and 2 was prepared by dissolving it in a solvent of the type described in Table 2 and filtering it through a fluororesin filter with a pore size of 0.1 μm. [Formation of coating film] The obtained compositions of each preparation example and comparative preparation example were coated on the sample substrate using a spin coater to form a coating film with a thickness capable of forming a coating film with a film thickness of 5.0 μm. After prebaking the coating film at 100°C for 2 minutes, a vertical baking oven (TS8000MB, manufactured by Tokyo Oka Industry Co., Ltd.) was used to bake the coating film at 350°C for 30 minutes to obtain a film thickness of 5.0 μm. The coating. The formed coating was evaluated for the presence or absence of microcracks and the occurrence of outgassing according to the following method. <Evaluation of microcracks> Use an optical microscope (magnification: 100 times) to observe the surface of the formed coating after leaving it for 24 hours, and evaluate the presence or absence of microcracks. The results are shown in Table 2. <Evaluation of outgassing> In addition, the degree of outgassing generation was evaluated based on the temperature rise desorption gas analysis method (TDS). It was confirmed that the outgassing amount of the coatings formed using the compositions of Comparative Preparation Examples 1 and 2 was greater than that of any coating formed using the compositions of Preparation Examples 1 to 5 containing the polysilane compounds of Examples 1 to 5. membrane. [Table 2] The results shown in Table 2 show that the coatings formed using the compositions of Comparative Preparation Examples 1 and 2 containing the polysilane compounds of Comparative Examples 1 and 2 produced without using a nitrogen compound produced microcracks and release. angry. On the other hand, no microcracks were observed in the films formed using the compositions of Preparation Examples 1 to 5 containing the polysilane compounds of Examples 1 to 5 produced using a nitrogen compound, and the generation of outgassing was also suppressed. .

Claims (10)

A method for producing a polysilane compound, which includes reacting a halosilane compound in the presence of a nitrosilane compound, and the halosilane compound is only a compound represented by the following formula (1), X _n SiR _4-n ( 1) (In the formula, n is an integer from 2 to 4, n Xs are independently halogen atoms, (4-n) R are independently hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, and carbon atoms. A cycloalkyl group with 5 to 8 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aralkyl group or a silyl group, the above aralkyl group is a C _6-10 aryl-C _1-6 alkyl group). The production method of claim 1, wherein the nitroxyl compound is a compound having a structure represented by the following general formula (A),

(In the formula (A), R ^a1 , R ^a2 , R ^a3 and R ^a4 are each independently a hydrogen atom or an organic group; R ^a1 and R ^a2 can be bonded to each other to form a ring; and R ^a3 and R ^a4 can be mutually bonded. bond to form a ring). The production method of Claim 1 or 2, wherein the above-mentioned halosilane compound is further reacted in the presence of an alkali metal or magnesium. The production method of Claim 1 or 2, wherein the above-mentioned halosilane compound is further reacted in the presence of an organometallic complex represented by the following general formula (B),

(In the above general formula (B), M represents a member selected from the group consisting of iron, silver, aluminum, bismuth, cerium, cobalt, copper, dysprosium, erbium, europium, gallium, gallium, hafnium, 鈥, indium, iridium, lanthanum, gallium, and manganese , molybdenum, neodymium, nickel, osmium, palladium, cadmium, platinum, rhenium, rhodium, ruthenium, samarium, scandium, tin, phosphorus, titanium, gallium, vanadium, chromium, tantalum, ytterbium, gold, mercury, tungsten, yttrium Metals in the group consisting of zinc and zirconium, R ^b1 independently represents a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group or an aryloxyalkyl group. , R ^b2 represents a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or an aralkyl group; p represents an integer above 1). A method of manufacturing a composition containing a polysilane compound, wherein the polysilane compound is manufactured by a method according to any one of claims 1 to 4. The method of claim 5, wherein the above composition further contains a nitroxyl compound. A method for producing a hardened product of a composition, wherein the composition is produced by the method of claim 5 or 6. A method of manufacturing a substrate having a hardened material, wherein the hardened material is produced as in claim 7 Made by method. An application in which a nitroxyl compound containing a structure represented by the following general formula (A) is used to selectively promote anionic polymerization in the production of a polysilane compound. The production of the above-mentioned polysilane compound includes: in the above-mentioned nitroxyl compound The halosilane compound is reacted in the presence of the compound represented by the following formula (1),

(In the formula (A), R ^a1 , R ^a2 , R ^a3 and R ^a4 are each independently a hydrogen atom or an organic group; R ^a1 and R ^a2 can be bonded to each other to form a ring; and R ^a3 and R ^a4 can be mutually bonded. Bonded to form a ring) X _n SiR _4-n (1) (In the formula, n is an integer from 2 to 4, the n , an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 5 to 8 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aralkyl group or a silyl group. The above aralkyl group is a C _6-10 aryl group. -C _1-6 alkyl). Such as the application of claim 9, wherein the above-mentioned nitryl compound causes silyl radical cations generated during the production of the polysilane compound to perform charge spin.