JP2018109112A - Method for producing polysilane compound, composition, cured product and substrate, and anionic polymerization selective accelerator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a method for producing a polysilane compound which is capable of suppressing the occurrence of outgassing and microcracking in a film containing the polysilane compound; and an anionic polymerization selective accelerator that is used in the production of the polysilane compound, and a composition, a cured product and a substrate, each of which contains the polysilane compound.SOLUTION: A method for producing a polysilane compound comprises a step for the reaction of a halosilane compound in the presence of a nitroxy compound. An anionic polymerization selective accelerator is used in the production of a polysilane compound, and contains a nitroxy compound having a structure represented by general formula (A). (In formula (A), each of R, R, R, and Rindependently represent a hydrogen atom or an organic group; Rand Rmay combine with each other to form a ring; and Rand Rmay combine with each other to form a ring.)SELECTED DRAWING: None

Description

  The present invention relates to a polysilane compound, a composition, a cured product, a method for producing a substrate, and an anionic polymerization selective accelerator in the production of a polysilane compound.

  Polysilane compounds include ceramic precursors, photoelectron materials (for example, photoelectrophotographic materials such as photoresists and organic photoreceptors, optical transmission materials such as optical waveguides, optical recording materials such as optical memories, and electroluminescent element materials), various elements. Are used in applications such as interlayer insulating films, sealing materials for light emitting elements such as LED elements and organic EL elements, coating films for diffusing impurities into semiconductor substrates, and gap fill materials for semiconductor processes.

  As a method for producing such a polysilane compound, for example, in Patent Document 1, in a reaction system in which a metal magnesium is reacted with a halosilane compound in the presence of a lithium compound and a specific metal halide to form polysilane, the polysilane compound remains after the reaction. A method for producing polysilane is disclosed in which polysilane is produced by adding and reacting the above raw materials (lithium compound, metal halide, and halosilane compound) to active metal magnesium which is a solid component.

Japanese Patent No. 4559642

When a film is formed using a composition containing a polysilane compound, microcracks and outgas may occur.
The present invention has been made in view of the above-described problems of the prior art, and includes a method for producing a polysilane compound capable of suppressing outgas generation and microcrack generation in a film containing a polysilane compound, a composition containing the polysilane compound, a cured product, and a substrate. An object is to provide an anionic polymerization selective accelerator in the production of a polysilane compound.

  The present inventors have found that in the method for producing a polysilane compound, the outgas generation and the generation of microcracks can be suppressed by reacting the halosilane compound in the presence of a nitroxy compound, and the present invention has been completed.

The first aspect of the present invention is:
A method for producing a polysilane compound comprising reacting a halosilane compound in the presence of a nitroxy compound.

（式（Ａ）中、Ｒ^ａ１、Ｒ^ａ２、Ｒ^ａ３、及びＲ^ａ４は、それぞれ独立に、水素原子、又は有機基である。Ｒ^ａ１とＲ^ａ２とは、互いに結合して環を形成してもよい。また、Ｒ^ａ３とＲ^ａ４とは、互いに結合して環を形成してもよい。） The second aspect of the present invention is a polysilane compound obtained by the production method of the first aspect.
The third aspect of the present invention is a composition comprising the polysilane compound of the second aspect.
The fourth aspect of the present invention is a cured product of the composition of the third aspect.
5th aspect of this invention is a board | substrate provided with the hardened | cured material of 4th aspect.
The sixth aspect of the present invention is an anionic polymerization selective accelerator in the production of a polysilane compound containing a nitroxy compound containing 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 are bonded to each other to form a ring. R ^a3 and R ^a4 may be bonded to each other to form a ring.)

A seventh aspect of the present invention is a method for producing a composition containing a polysilane compound, wherein the polysilane compound is produced by the method of the first aspect.
The eighth aspect of the present invention is a method for producing a cured product of the composition, wherein the composition is produced by the method of the seventh aspect.
A ninth aspect of the present invention is a method for manufacturing a substrate including a cured product, wherein the cured product is manufactured by the method of the eighth aspect.

  According to the present invention, a method for producing a polysilane compound capable of suppressing outgas generation and microcrack generation in a film containing a polysilane compound, a composition containing the polysilane compound, a cured product and a substrate, and anionic polymerization in the production of the polysilane compound A selective accelerator can be provided.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. .
Moreover, in this specification, "-" represents the following from the above unless there is particular notice.

<Production method of polysilane compound>
The method for producing a polysilane compound according to the first aspect includes reacting a halosilane compound in the presence of a nitroxy compound.

In the production of polysilane compounds, in general, silyl radical cations and silyl radical anions can be generated (Electronic Structure of Radial Anions and Cations of Polysilicones with Structural Defects Seki, Shiw; 1999, 32 (4), pp 1080-1086).
While the silyl radical anion can be used for the production of a polysilane compound by anionic polymerization, water (H ₂ O) or oxygen (O ₂ ) in the air selectively reacts with the silyl radical cation to form a siloxane bond (Si—O), By-products such as silanol groups (Si—OH) may be generated. When the film is formed using such a composition containing a polysilane compound containing a side reaction product such as a siloxane bond and a silanol group, the present inventors have found that the siloxane bond and the silanol group cause microcracks. Found.
In addition, silyl radical cations are more likely to cause elimination of substituents (particularly aryl groups) such as aryl groups and alkyl groups than silyl radical anions, which may cause outgassing.
In contrast, in the method for producing a polysilane compound according to the first aspect, the nitroxy compound spin-charges the silyl radical cation to reduce the silyl radical cation, thereby selectively promoting anionic polymerization by the silyl radical anion. Is estimated to be possible. Thereby, it is presumed that generation of by-products such as siloxane bonds and silanol groups causing micro cracks can be suppressed, and generation of outgas can also be suppressed.

（式（Ａ）中、Ｒ^ａ１、Ｒ^ａ２、Ｒ^ａ３、及びＲ^ａ４は、各々独立に、水素原子、又は有機基である。Ｒ^ａ１とＲ^ａ２とは、互いに結合して環を形成してもよい。また、Ｒ^ａ３とＲ^ａ４とは、互いに結合して環を形成してもよい。）
式（Ａ）において、Ｒ^ａ１〜Ｒ^ａ４で表される有機基としては、炭素原子数１〜１０の有機基が挙げられ、Ｒ^ａ１、Ｒ^ａ２、Ｒ^ａ３、及びＲ^ａ４は、それぞれ独立に、アルキル基又はヘテロ原子で置換されたアルキル基であることが好ましい。アルキル基としては、メチル基、エチル基、ｎ−プロピル基、及びイソプロピル基が好ましい。ヘテロ原子の好適な例としては、ハロゲン原子、酸素原子、硫黄原子、及び窒素原子等が挙げられる。 (Nitroxy compounds)
Although it will not specifically limit if it is a compound which can exist stably as a nitroxide radical as said nitroxy compound, It is preferable that it is a compound containing the structure represented by the following general formula (A).

(In 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 are bonded to each other to form a ring. R ^a3 and R ^a4 may be bonded to each other to form a ring.)
In the formula (A), examples of the organic group represented by R ^{a1 to} R ^a4 include an organic group having 1 to 10 carbon atoms, and R ^a1 , R ^a2 , R ^a3 , and R ^a4 are each independently , An alkyl group or an alkyl group substituted with a hetero atom is preferable. As the alkyl group, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable. Preferable examples of the hetero atom include a halogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom.

  Suitable specific examples of the nitroxy compound include, for example, di-tert-butyl nitroxide, di-1,1-dimethylpropyl nitroxide, di-1,2-dimethylpropyl nitroxide, di-2,2-dimethylpropyl nitroxide, and A compound represented by the following formula (A1), (A2), or (A3) is preferred, and a compound represented by the following formula (A1), (A2), or (A3) is more preferred.

In formulas (A1), (A2), and (A3), R ^a5 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, a carboxy group, a cyano group, or an alkyl substituted with a heteroatom. Or a monovalent organic group bonded through an ether bond, an ester bond, an amide bond, or a 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 the formula (A1) include the following compounds. In the following formulae, each R ^a7 may independently have an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic group which may have a substituent, or a substituent. Represents a good alicyclic group.

Preferable specific examples of the compound represented by the formula (A2) include the following compounds.

Preferable specific examples of the compound represented by the formula (A3) include the following compounds.

More preferable nitroxy compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO), 4-hydroxy-2,2,6,6-atetramethylpiperidine 1-oxyl free radical, 4 -Amino-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-cyano-2,2,6 , 6-Tetramethylpiperidine 1-oxyl free radical, 4-methacrylic acid-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acrylic acid-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, 3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4- (2 -Chloroacetamido) -2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxylbenzoate free radical, 4-isothiocyanato-2 , 2,6,6-tetramethylpiperidine 1-oxyl free radical, 4- (2-iodoacetamido) -2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-methoxy-2,2 , 6,6-tetramethylpiperidine 1-oxyl free radical .
A nitroxy compound may be used independently and may be used in combination of 2 or more type.

  The amount of the nitroxy compound used is preferably in the range of 0.0001 to 10 mol times, more preferably in the range of 0.0005 to 5 mol times, still more preferably 0.0008 to 1 mol times based on the halosilane compound. The range is particularly preferably 0.001 to 0.1 mole times.

(Halosilane compound)
The halosilane compound is preferably a compound represented by the following formula (1).

X _n SiR _4-n (1)

(Wherein n is an integer of 2 to 4, n Xs are each independently a halogen atom, and (4-n) Rs are each independently a hydrogen atom, an organic group or a silyl group. Group.)

  Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a chlorine atom or a bromine atom is preferred, and a chlorine atom is more preferred.

Examples of the organic group represented by R include alkyl groups [alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl groups (preferably alkyl groups having 1 to 6 carbon atoms). , Especially an alkyl group having 1 to 4 carbon atoms)], a cycloalkyl group (a cycloalkyl group having 5 to 8 carbon atoms such as a cyclohexyl group, particularly a cycloalkyl group having 5 to 6 carbon atoms), an alkenyl group [ethenyl. Group, propenyl group, butenyl group and the like alkenyl group having 2 to 10 carbon atoms (preferably alkenyl group having 2 to 6 carbon atoms, particularly alkenyl group having 2 to 4 carbon atoms)], cycloalkenyl group [1- A cycloalkenyl group having 5 to 10 carbon atoms such as a cyclopentenyl group and a 1-cyclohexenyl group (preferably a cycloalkenyl group having 5 to 8 carbon atoms, Such cycloalkenyl group having 5 to 7 carbon atoms)], the aryl group (phenyl, aryl group having 6 to 10 carbon atoms such as naphthyl group), aralkyl group [a benzyl, _{C 6-10} aryl, such as phenethyl group - C _1-6 alkyl group (such as C _6-10 aryl-C _1-4 alkyl group)], amino group, N-substituted amino group (the above alkyl group, cycloalkyl group, aryl group, aralkyl group, acyl group, etc.) Substituted N-mono or disubstituted amino groups, etc.). The aryl group constituting the alkyl group, cycloalkyl group, aryl group or aralkyl group may have one or more substituents. Examples of such a substituent include the above-exemplified alkyl groups (particularly alkyl groups having 1 to 6 carbon atoms). Examples of the organic group having such a substituent include C _1-6 alkyl-C _6-10 aryl such as tolyl group (methylphenyl group), xylenyl group (dimethylphenyl group), ethylphenyl group, and methylnaphthyl group. A group (preferably a mono, di or tri C _1-4 alkyl-C _6-10 aryl group, especially a mono or di C _1-4 alkylphenyl group) and the like.

  Examples of the silyl group include substituted silyl groups substituted with the above alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, aralkyl group, alkoxy group and the like.

In the case where 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.
Conventionally, when the silyl radical cation has an organic group such as an alkyl group or an aryl group (particularly an aryl group) directly connected to a silicon atom, the organic group is likely to be detached and may cause outgassing.
On the other hand, in the method for producing a polysilane compound according to the first aspect, even when the silyl radical cation has an organic group directly connected to a silicon atom (when R is an organic group (particularly an aryl group)). It is presumed that the nitroxy compound spin-charges the silyl radical cation to reduce the silyl radical cation, so that the organic group is hardly detached and the outgas generation can be suppressed.

As a typical dihalosilane compound, for example, dialkyldihalosilane (diC _1-10 alkyldihalosilane such as dimethyldichlorosilane, preferably diC _1-6 alkyldihalosilane, more preferably diC _1-4 Alkyl dihalosilanes), monoalkyl monoaryl dihalosilanes (mono C _1-10 alkyl mono C _6-12 aryl dihalosilanes such as methylphenyldichlorosilane, preferably mono C _1-6 alkyl mono C 6-10 aryl) Dihalosilanes, more preferably mono-C _1-4 alkyl mono-C _6-8 aryl dihalosilanes, etc., diaryl dihalosilanes (di-C _6-12 aryl dihalosilanes such as diphenyldichlorosilane, preferably di-C _{6 -10} aryl dihalo silane, more preferably di _{C 6-8} A Rujiharoshiran, etc.), and the like. As the dihalosilane compound, dialkyldihalosilane or monoalkylmonoaryldihalosilane is preferable. A dihalosilane compound can be used individually or in combination of 2 or more types.

In the case where n is 3 (trihalosilane compound), R is preferably a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group which may have a substituent, or an aralkyl group, particularly an alkyl group or an aryl group. Group is preferred, and an aryl group is more preferred.
As described above, in the method for producing a polysilane compound according to the first aspect, the silyl radical cation has an organic group directly connected to a silicon atom (when R is an organic group (particularly an aryl group)). However, due to the action of the nitroxy compound, the elimination of the organic group is difficult to occur and the outgas generation can be suppressed.

Typical trihalosilane compounds include alkyltrihalosilanes (C _1-10 alkyltrihalosilanes such as methyltrichlorosilane, butyltrichlorosilane, t-butyltrichlorosilane, hexyltrichlorosilane, preferably C _1-6 alkyltrihalosilanes, More preferably C _1-4 alkyltrihalosilane, etc., cycloalkyltrihalosilane (mono C _6-10 cycloalkyltrihalosilane such as cyclohexyltrihalosilane), aryltrihalosilane (phenyltrichlorosilane, tolyltrichlorosilane, xylyltrichlorosilane) C _6-12 aryltrihalosilane, preferably C _6-10 aryltrihalosilane, more preferably C _6-8 aryltrihalosilane). . The trihalosilane compound is preferably alkyltrihalosilane or aryltrihalosilane.
A trihalosilane compound can be used individually or in combination of 2 or more types.

Specific examples of when n is 4 (tetrahalosilane compound) include, for example, tetrachlorosilane, dibromodichlorosilane, and tetrabromosilane. The tetrahalosilane compounds may be used alone or in combination of two or more.
The tetrahalosilane compound is preferably used in combination with a mono-, di- or trihalosilane compound.

The halosilane compound may be a monohalosilane compound. Representative monohalosilanes include, for example, trialkylmonohalosilanes (tri-C _1-10 alkyl monohalosilanes such as trimethylchlorosilane, preferably tri-C _1-6 alkyl monohalosilanes, more preferably tri-C _1-4 alkyls. Monohalosilanes, etc.), dialkyl monoaryl monohalosilanes (diC _1-10 alkyl mono C _6-12 aryl monohalosilanes such as dimethylphenylchlorosilane, preferably diC _1-6 alkyl mono C _6-10 aryl monohalo silane, more preferably such di _{C 1-4} alkyl mono- _{C 6-8} aryl monohaloalkyl silane), mono _{C 1-10} alkyl di _{C 6-12} aryl monohaloalkyl silane such as monoalkyl diaryl monohaloalkyl silane (methyl diphenyl chlorosilane, preferably mono _{C 1 6} alkyl di _{C 6-10} aryl monohaloalkyl silane, more preferably such mono _{C 1-4} alkyl di _{C 6-8} aryl monohaloalkyl silane), tri _{C 6-12} aryl monohaloalkyl such triaryl monohaloalkyl silane (triphenyl chlorosilane Silane, preferably tri-C _6-10 aryl monohalosilane, more preferably tri-C _6-8 aryl monohalosilane). A monohalosilane compound can be used individually or in combination of 2 or more types.

  These halosilane compounds can be used alone or in combination of two or more.

  The halosilane compound preferably contains at least one selected from dihalosilane compounds and trihalosilane compounds.

In addition, when a halosilane compound contains a trihalosilane compound and / or a tetrahalosilane compound, a network-like (network-like or branched) polysilane compound can be generated. When obtaining a network-like polysilane compound, representative halosilanes (or combinations thereof) include (a) alkyltrihalosilanes (for example, alkyltrihalosilanes alone, combinations of methyltrihalosilanes and _C2-10 alkyltrihalosilanes, C _2-10 alkyltrihalosilane, etc.), (b) aryltrihalosilane (eg, aryltrihalosilane alone), (c) combination of aryltrihalosilane and dihalosilane (eg, monoalkylmonoaryldihalosilane), etc. Can be mentioned.

  In the halosilane compound, the ratio (use ratio) of at least one selected from dihalosilane compounds and trihalosilane compounds is 50 mol% or more (for example, 60 mol% or more), preferably 70 mol% or more, based on the entire halosilane. (For example, 80 mol% or more), more preferably 90 mol% or more (for example, 95 mol% or more).

  In the case of obtaining a network-like polysilane, the proportion (use ratio) of the trihalosilane compound is 30 mol% or more (for example, 40 mol% or more), preferably 50 mol% or more (for example, 60 mol%) of the entire halosilane compound. Mol% or more), more preferably 70 mol% or more (for example, 75 mol% or more), particularly 80 mol% or more.

  Moreover, when combining a dihalosilane compound and a trihalosilane compound, these ratios are dihalosilane compound / trihalosilane compound (molar ratio) = 99/1 to 1/99, preferably 90/10 to 2/98 (for example, 85 / 15 to 2/98), more preferably 80/20 to 3/97 (for example 70/30 to 4/96), in particular 60/40 to 5/95 (for example 50/50 to 7/93). It may be 50 / 50-5 / 95 (for example, 45 / 55-7 / 93, preferably 40 / 60-10 / 90, more preferably 30 / 70-88 / 12). .

  The halosilane compound is preferably as pure as possible. For example, liquid halosilane compounds are preferably dried and dried using a desiccant such as calcium hydride, and solid halosilane compounds are purified and used by recrystallization or the like. Is preferred.

  In addition, the density | concentration (substrate concentration) of the halosilane compound in a raw material mixture (reaction liquid) is about 0.05-20 mol / l, for example, Preferably it is about 0.1-15 mol / l, More preferably, it is 0.2-5 mol / L may be sufficient.

The method for producing a polysilane compound according to the first aspect may apply a method for producing a polysilane compound such as the following (a) to (c) including reacting a halosilane compound.
(A) A method of dehalogenating polycondensation of a halosilane compound using magnesium as a reducing agent (“magnesium reduction method”, a method described in WO 98/29476, JP 2003-277507 A, etc.)
(B) A method of dehalogenating polycondensation of a halosilane compound in the presence of an alkali metal such as metallic sodium, metallic lithium, metallic potassium, etc. (preferably metallic sodium) (“Kipping method”, J. Am. Chem. Soc., 110 , 124 (1988), Macromolecules, 23, 3423 (1990), etc.)
(C) Dehalogenation condensation polymerization of halosilane 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 according to the first aspect includes a magnesium reduction method in which the halosilane compound is reacted in the presence of magnesium together with a nitroxy compound, or a metal sodium, metal lithium, metal potassium, etc. (preferably metal A kipping method in which the halosilane compound is reacted in the presence of an alkali metal (sodium) is preferred, and a magnesium reduction method in which the halosilane compound is reacted in the presence of magnesium together with a nitroxy compound is more preferred.

Magnesium may be in the form of metallic magnesium (magnesium alone), a magnesium alloy, or a mixture thereof (hereinafter also referred to as “magnesium component”).
The kind of magnesium alloy is not particularly limited, and examples thereof include conventional magnesium alloys such as magnesium alloys containing components such as aluminum, zinc, 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, but is in the form of powder (powder, granule, etc.), ribbon, cut piece, lump, rod, plate ( Flat form etc.) etc. are illustrated, and it is preferable that they are a powder, a granular material, a ribbon-like body, a cutting piece-like body etc. especially. The average particle diameter of magnesium (for example, granular magnesium) may 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).
A magnesium component and an alkali metal may be used independently and may be used in combination of 2 or more type.

The amount of the magnesium component or alkali metal used is preferably 1 to 20 equivalents, more preferably 1.1 to 14 equivalents, in terms of magnesium or alkali metal, relative to the halogen atom of the halosilane compound. More preferably, it is 1.2-10 equivalent, and it is especially preferable that it is 1.2-5 equivalent.
Further, the amount of the magnesium component or alkali metal used is preferably 1 to 20 times, more preferably 1.1 to 14 times as magnesium or alkali metal in terms of the number of moles relative to the halosilane compound. 2 to 10 times is more preferable, and 1.2 to 5 times is particularly preferable.

In the method for producing a polysilane compound according to the first aspect, the halosilane compound may be reacted with the nitroxy compound and the magnesium component or the alkali metal in the presence of an organometallic complex represented by the following general formula (Z1). Good.

M ^p L _{p / q} (Z1)

(In the general formula (Z1), M ^p represents a p-valent metal cation, L represents a q-valent organic ligand, and p and q each independently represents an integer of 1 or more.)

The metal atoms constituting the p-valent metal cation M ^p, iron, silver, aluminum, bismuth, cerium, cobalt, copper, dysprosium, erbium, europium, gallium, gadolinium, hafnium, holmium, indium, iridium, lanthanum, lutetium , Manganese, molybdenum, neodymium, nickel, osmium, palladium, promethium, praseodymium, platinum, rhenium, rhodium, ruthenium, samarium, scandium, tin, terbium, titanium, thulium, vanadium, chromium, tantalum, ytterbium, gold, mercury tungsten, Examples include metals selected from the group consisting of yttrium, zinc and zirconium.
p is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 2 or 3.
q is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
As the q-valent organic ligand L, organic coordination such as β-diketonato ligand, olefin, conjugated ketone, nitrile, amine, carboxylate ligand, carbon monoxide, phosphine, phosphinite, phosphonite, phosphite, etc. A child. The q-valent organic ligand L may be a chelate ligand.

（上記一般式（Ｚ２）中、Ｍは、鉄、銀、アルミニウム、ビスマス、セリウム、コバルト、銅、ジスプロシウム、エルビウム、ユーロピウム、ガリウム、ガドリニウム、ハフニウム、ホルミウム、インジウム、イリジウム、ランタン、ルテチウム、マンガン、モリブデン、ネオジム、ニッケル、オスミウム、パラジウム、プロメチウム、プラセオジム、白金、レニウム、ロジウム、ルテニウム、サマリウム、スカンジウム、スズ、テルビウム、チタン、ツリウム、バナジウム、クロム、タンタル、イッテルビウム、金、水銀タングステン、イットリウム、亜鉛及びジルコニウムよりなる群から選択される金属を表し、Ｒ^ｚ１は、各々独立して、飽和炭化水素基、不飽和炭化水素基、芳香族炭化水素基、アラルキル基、アルコキシ基、アリールオキシ基、アラルキルオキシ基又はアリールオキシアルキル基を表し、Ｒ^ｚ２は、水素原子、飽和炭化水素基、不飽和炭化水素基、芳香族炭化水素基又はアラ上記ルキル基を表わす。ｐは１以上の整数を表す。） The organometallic complex is preferably an organometallic complex represented by the following general formula (Z2).

(In the general formula (Z2), M represents iron, silver, aluminum, bismuth, cerium, cobalt, copper, dysprosium, erbium, europium, gallium, gadolinium, hafnium, holmium, indium, iridium, lanthanum, lutetium, manganese, Molybdenum, neodymium, nickel, osmium, palladium, promethium, praseodymium, platinum, rhenium, rhodium, ruthenium, samarium, scandium, tin, terbium, titanium, thulium, vanadium, chromium, tantalum, ytterbium, gold, mercury tungsten, yttrium, zinc And R ^z1 each independently represents a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an aralkyl group, an alkoxy group, an aryl group, or an aryl group selected from the group consisting of zirconium and zirconium. Represents an oxy group, an aralkyloxy group or an aryloxyalkyl group, and R ^z2 represents a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or an aralkyl group, and p is 1 or more. Represents an integer.)

Examples of the saturated hydrocarbon group represented by R ^z1 and R ^z2 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl. Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, docosyl group, 2-dodecylhexadecyl group, triacontyl group, dotriacontyl group, tetracontyl group, etc. A linear or branched alkyl group of 1 to 40, further, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodo atom), an alkoxy group (such as those described below), a silyl group (described below) Alkyl groups substituted with one or more substituents, such as those described), for example Chloropropyl group, 3,3,3-trifluoropropyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, tridecafluoro-1,1,2,2- Tetrahydrooctyl group, heptadecafluoro-1,1,2,2-tetrahydrodecyl group, 3- (heptafluoroisopropoxy) propyl group, trimethylsilylmethyl group, etc .; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, bicyclo C3-C18 monocyclic or bicyclic or higher polycyclic saturated hydrocarbon groups such as heptyl group, cyclooctyl group, adamantyl group, etc., and these cyclic saturated hydrocarbon groups are alkyl groups (such as those described above), Substituted with one or more substituents such as an aryl group (such as those described above), such as 4-t-butyl Examples thereof include a cyclohexyl group, a 4-phenylcyclohexyl group and the like; or an alkyl group having the above cyclic saturated hydrocarbon group (such as those described above), such as a cyclohexylmethyl group and an adamantylethyl group.

Examples of the unsaturated hydrocarbon group represented by R ^z1 and R ^z2 include vinyl group, ethynyl group, allyl group, 1-propenyl group, propargyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, decanyl group, dodecanyl group In addition, a linear or branched alkenyl group having 2 to 18 carbon atoms such as an octadecanyl group, an alkynyl group, and an unsaturated hydrocarbon group thereof may be a halogen atom (such as those described above) or an alkoxy group (described below). ), Silyl groups (such as those described below), aryl groups (such as those described below) substituted with one or more substituents such as 2-trifluoromethylethenyl Group, 2-trifluoromethylethynyl group, 3-methoxy-1-propenyl group, 3-methoxy-1-propynyl group, 2-trimethyl Rusilylethenyl group, 2-trimethylsilylethynyl group, 2-phenylethenyl group, 2-phenylethynyl group, etc .; C3-C18 cyclic unsaturated hydrocarbon group such as cyclopropenyl group, cyclohexenyl group, cyclooctenyl group; Examples thereof include an alkyl group having an unsaturated hydrocarbon group (such as those described above), such as a cyclohexenylethyl group.

Examples of the aromatic hydrocarbon group represented by R ^z1 and R ^z2 include one or more of a phenyl group, an alkyl group such as a tolyl group, a butylphenyl group, and a butoxyphenyl group, an alkoxy group, and an amino group. Examples include substituted phenyl groups.

^Examples of the aralkyl group represented by R ^z1 and R ^z2 include a benzyl group, a phenethyl group, a methylphenethyl group, a butylphenethyl group, a phenylpropyl group, a methoxyphenylpropyl group, and the heteroaralkyl group includes a pyridylmethyl group, A pyridylethyl group etc. are mentioned.

^Examples of the alkoxy group represented by R ^z1 include alkoxy groups having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, an octyloxy group, and the aryloxy group includes a phenoxy group. And a substituted phenoxy group substituted with a substituent such as an alkyl group such as a tolyloxy group and a butylphenoxy group.

Examples of the aralkyloxy group represented by R ^z1 include a benzyloxy group and a phenethyloxy group, and examples of the aryloxyalkyl group include a phenoxypropyl group and a phenoxybutyl group.

R ^z1 is preferably a saturated hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group, or the like, and more preferably an alkyl group having 1 to 15 carbon atoms, a phenyl group, or the like. Preferred is a methyl group.

R ^z2 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, phenyl Group, phenylethyl group and the like, and particularly preferred is a hydrogen atom.
Preferred examples of p are as described above.

As a metal complex, various metal complexes are mentioned by the combination of said metal M, ^Rz1, and ^Rz2 . Illustrative examples include acetylacetonato silver (I), tris (acetylacetonato) aluminum (III), tris (2,2,6,6-tetramethyl-3,5-heptanedionato) aluminum (III), tris (2,2,6,6-tetramethyl-3,5-heptanedionato) bismuth (III), tris (acetylacetonato) cerium (III), bis (acetylacetonato) cobalt (II), tris (acetylacetonato ) Cobalt (III), Tris (1,3-diphenyl-1,3-propanedionato) cobalt (III), Tris (3-methyl-2,4-pentanedionato) cobalt (III), Tris (3- Phenyl-2,4-pentanedionato) cobalt (III), tris (3- (1-phenylethyl) -2,4-pe Tandionato) cobalt (III), bis (benzoylacetone) cobalt (II) bis (hexafluoroacetylacetonato) cobalt (II), tris (2,2,6,6-tetramethyl-3,5-heptanedionato) cobalt ( III), bis (acetylacetonato) copper (II), bis (2,2,6,6-tetramethyl-3,5-heptadionato) copper (II), tris (2,2,4,6,6- Pentamethyl-3,5-heptanedionato) cobalt (III), tris (2,2,6,6-tetramethyl-4- (1-phenylethyl) -3,5-heptaneedionato) cobalt (III), tris (2, 2,6,6-tetramethyl-4-phenyl-3,5-heptanedionato) cobalt (III), bis (hexafluoroacetylacetonate Copper (II), bis (trifluoroacetylacetonato) copper (II), tris (acetylacetonato) dysprosium (III), tris (acetylacetonato) erbium (III), tris (2,2,6,6, -Tetramethyl-3,5-heptanedionato) erbium (III), tris (acetylacetonato) europium (III), bis (acetylacetonato) iron (II), tris (acetylacetonato) iron (III), tris ( 1,3-diphenyl-1,3-propanedionato) iron (III), tris (3-methyl-2,4-pentanedionato) iron (III), tris (3-phenyl-2,4-pentanedio) Nato) iron (III), tris (3- (1-phenylethyl) -2,4-pentanedionato) iron (III), tris (2,2 , 6,6-tetramethyl-3,5-heptanedionato) iron (III), tris (2,2,4,6,6-pentamethyl-3,5-heptaneedionato) iron (III), tris (2,2, 6,6-tetramethyl-4- (1-phenylethyl) -3,5-heptanedionato) iron (III), tris (2,2,6,6-tetramethyl-4-phenyl-3,5-heptaneedionato) Iron (III), tetrakis (acetylacetonato) hafnium (IV), tris (acetylacetonato) gallium (III), tris (acetylacetonato) gadolinium (III), tris (acetylacetonato) holmium (III), tris (Acetylacetonato) indium (III), tris (acetylacetonato) iridium (III), tris (acetylacetate) Nato) lanthanum (III), tris (acetylacetonato) lutetium (III), bis (acetylacetonato) manganese (II), tris (acetylacetonato) manganese (III), bis (hexafluoroacetylacetonato) manganese ( II), bis (acetylacetonato) dioxomolybdenum (IV), tris (acetylacetonato) neodymium (III), tris (2,2,6,6-tetramethyl-3,5-heptadionato) neodymium (III) Bis (acetylacetonato) nickel (II), bis (2,2,6,6-tetramethyl-3,5-heptadionato) nickel (II), bis (hexafluoroacetylacetonato) nickel (II), bis (1,3-diphenyl-1,3-propanedionato) nickel (II), bis 3-methyl-2,4-pentanedionato) nickel (II), bis (3-phenyl-2,4-pentandionato) nickel (II), bis (3- (1-phenylethyl) -2,4 -Pentandionato) nickel (II), bis (2,2,4,6,6-pentamethyl-3,5-heptanedionate) nickel (II), bis (2,2,6,6-tetramethyl-4- (1-phenylethyl) -3,5-heptanedionato) nickel (II), bis (2,2,6,6-tetramethyl-4-phenyl-3,5-heptaneedionato) nickel (II), bis (acetylacetate) Nato) palladium (II), bis (hexafluoroacetylacetonato) palladium (II), bis (1,3-diphenyl-1,3-propanedionato) palladium (II), bis (3-methyl-2,4-pentanedionato) palladium (II), bis (3-phenyl-2,4-pentandionato) palladium (II), bis (3- (1-phenylethyl) -2, 4-Pentandionato) palladium (II), bis (2,2,4,6,6-pentamethyl-3,5-heptanedionate) palladium (II), bis (2,2,6,6-tetramethyl-4) -(1-phenylethyl) -3,5-heptanedionato) palladium (II), bis (2,2,6,6-tetramethyl-4-phenyl-3,5-heptaneedionato) palladium (II), tris (acetyl) Acetonato) promethium (III), tris (acetylacetonato) praseodymium (III), tris (hexafluoroacetylacetonato) praseodymium (III) Bis (acetylacetonato) platinum (II), tris (acetylacetonato) rhodium (III), tris (acetylacetonato) ruthenium (III), tris (acetylacetonato) scandium (III), tris (hexafluoroacetylacetate) Nato) scandium (III), tris (2,2,6,6-tetramethyl-3,5-heptadionato) scandium (III), tris (acetylacetonato) samarium (III), tris (2,2,6, 6-tetramethyl-3,5-heptanedionato) samarium (III), bis (acetylacetonato) tin (II), tris (acetylacetonato) terbium (III), tris (2,2,6,6-tetramethyl -3,5-heptanedionato) terbium (III), tris (2 2,6,6-tetramethyl-3,5-heptanedionato) thulium (III), tris (acetylacetonato) vanadium (III), tris (acetylacetonato) yttrium (III), tris (hexafluoroacetylacetonato) Yttrium (III), tris (2,2,6,6-tetramethyl-3,5-heptanedionato) yttrium (III), bis (acetylacetonato) zinc (II), bis (hexafluoroacetylacetonato) zinc ( II), bis (2,2,6,6-tetramethyl-3,5-heptanedionato) zinc (II), tetrakis (acetylacetonato) zirconium (IV), tetrakis (2,2,6,6-tetramethyl) -3,5-heptanedionato) zirconium (IV), tetrakis (trifluoro) Acetylacetonato) zirconium (IV) and the like.
These organometallic complexes can be used alone or in combination of two or more. As the organometallic complex, a metal complex synthesized in advance may be used, or a metal complex produced in the system may be used.

  The amount of the organometallic complex used is preferably in the range of 0.001 to 10 mol times, more preferably in the range of 0.001 to 1 mol times, particularly preferably 0.001 to 0.1 mol, relative to the halosilane compound. It is the range of mole times.

(Metal halide)
In the method for producing a polysilane compound according to the first aspect, the halosilane compound may be reacted with a nitroxy compound and magnesium or an alkali metal in the presence of a metal halide.
Examples of the metal halide include polyvalent metal halides such as transition metals (for example, periodic table group 3A elements such as samarium, periodic table group 4A elements such as titanium, periodic table group 5A elements such as vanadium, iron, nickel, Periodic table group 8 elements such as cobalt and palladium, periodic table group 1B elements such as copper, periodic table group 2B elements such as zinc), periodic table group 3B metals (such as aluminum), periodic table group 4B metals (such as tin) Metal halides such as chloride, bromide or iodide. The valence of the metal constituting the metal halide is not particularly limited, but is preferably 2 to 4, more preferably 2 or 3. 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 iron, aluminum, zinc, copper, tin, nickel, cobalt, vanadium, titanium, palladium, samarium and the like.

Examples of such metal halides include chlorides (iron chloride such as FeCl ₂ and FeCl ₃ ; AlCl ₃ , ZnCl ₂ , SnCl ₂ , CoCl ₂ , VCl ₂ , TiCl ₄ , PdCl ₂ , and SmCl ₂ ). Examples thereof include bromides (such as iron bromide such as FeBr ₂ and FeBr ₃ ) and iodides (such as SmI ₂ ). Of these metal halides, chlorides (for example, iron chlorides such as iron (II) chloride and iron (III), zinc chloride, etc.) and bromides are preferred. Usually, iron chloride and / or zinc chloride, especially zinc chloride and the like are used.

  The amount of the metal halide used is preferably in the range of 0.001 to 10 mol times, more preferably in the range of 0.001 to 1 mol times, particularly preferably 0.001 to 0.1 mol, relative to the halosilane compound. It is the range of mole times.

  The concentration of the metal halide in the solvent (reaction solution) is usually about 0.001 to 6 mol / L, preferably 0.005 to 4 mol / L, more preferably 0.01 to 3 mol. It may be about / L.

(Aprotic solvent)
The reaction of the halosilane compound in the presence of the nitroxy compound in the method for producing the polysilane compound according to the first aspect is preferably performed in a solvent (reaction solvent), more preferably in an aprotic solvent.
Examples of the aprotic solvent as the solvent (reaction solvent) include ethers (1,4-dioxane, tetrahydrofuran, tetrahydropyran, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl). Cyclic or linear C4-6 ethers such as ether), carbonates (such as propylene carbonate), nitriles (acetonitrile, benzonitrile, etc.), amides (dimethylformamide, dimethylacetamide, etc.), sulfoxides (such as dimethyl sulfoxide), Aromatic hydrocarbons (benzene, toluene, xylene, etc.), aliphatic hydrocarbons (for example, chain or cyclic hydrocarbons such as hexane, cyclohexane, octane, cyclooctane) and the like are included.

  These aprotic solvents can be used alone or in combination of two or more as a mixed solvent. Among these solvents, at least polar solvents [for example, ethers [for example, tetrahydrofuran, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,4-dioxane, etc. (especially tetrahydrofuran, 1,2- Dimethoxyethane)] is preferably used. A polar solvent may be used individually or in combination of 2 or more types, and may combine a polar solvent and a nonpolar solvent.

In the method for producing a polysilane compound according to the first aspect, the polysilane is purified by bringing the solution after the reaction (reaction solution) into contact with an aqueous solution containing at least one selected from the group consisting of a base and an acid. It may further comprise obtaining the compound.
By purifying the polysilane compound in contact with a base or acid, impurities such as halogen atoms (for example, halogen ions (chloride ions, etc.) and Si—Cl remaining in the polysilane compound) can be removed. In addition, the molecular weight reduction of the polysilane compound can be promoted, and the solvent solubility of the polysilane compound can be improved.
The acid can also function as a quencher for the reaction of the halosilane compound.
Moreover, the metal atom (for example, Mg, Zn, etc.) remaining in the polysilane compound can be removed by bringing the polysilane compound into contact with the following metal halide for purification.
The treatment temperature is preferably from −50 ° C. to the boiling point of the solvent, more preferably from room temperature to 100 ° C.

Various bases can be used as long as they are basic compounds. For example, sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia, tetramethylammonium hydroxide, sodium carbonate, hydrogen carbonate. Inorganic bases such as sodium, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, calcium hydride, alkyl metals such as methyl lithium, n-butyl lithium, methyl magnesium chloride, ethyl magnesium bromide, Cr, Metals such as Ga, Fe (Fe (II), Fe (III)), Cd, Co, Ni, Sn, Pb, Cu (Cu (II), Cu (I)), Ag, Pd, Pt, Au, etc. (or Metal halide), sodium methoxide, sodium ethoxide, potassium t Alkoxides such as butoxide, triethylamine, diisopropylethylamine, N, N-dimethylaniline, pyridine, 4-dimethylaminopyridine, may be used diazabicycloundecene (DBU) organic bases such as.
Various acids can be used as the acid to be used, and inorganic acids such as hydrogen chloride can be used.

  Here, various solvents can be used as the base or acid treatment, for example, hydrocarbon solvents such as benzene, toluene and xylene, glycol solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, Ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, ethanol, isopropyl alcohol, One or more selected from alcohol solvents such as butanol can be used.

（式（Ｓ１）中、Ｒ^ｓ１は、それぞれ独立に、アルキル基であり、ｐは１〜６の整数であり、ｑは０〜（ｐ＋１）の整数である。）
Ｒ^ｓ１で表されるアルキル基としては炭素原子数１〜３のアルキル基が挙げられ、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基が挙げられる。 In addition, an acetate compound containing a cyclic skeleton can also be preferably used as a solvent used for the treatment under the above basic 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, but is preferably a cycloalkyl acetate represented by the following formula (S1).

(In formula (S1), R ^s1 is each independently an alkyl group, p is an integer of 1 to 6, and q is an integer of 0 to (p + 1).)
^Examples of the alkyl group represented by R ^s1 include alkyl groups having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.

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.
Among these, cyclohexyl acetate is preferable from the viewpoint of availability.

The reaction of the halosilane compound may be quenched by acid treatment.
Various acids can be used as the acid to be used, and inorganic acids such as hydrogen chloride can be used.

  According to the method for producing a polysilane compound according to the first aspect, the polysilane compound can be obtained in a yield of 50% or more, and the yield is preferably 70% or more.

<Polysilane compound>
According to the method for producing a polysilane compound according to the first aspect, as described above, generation of by-products such as a siloxane bond and a silanol group can be suppressed. Therefore, a siloxane bond (Si— The abundance of O) can be reduced.
According to the method for producing a polysilane compound according to the first aspect, a spectrum having a maximum detection peak height in a binding energy range of 99 eV or more and 104 eV or less measured by X-ray photoelectron spectroscopy in the polysilane compound is separated. The ratio represented by the following formula (3X), which is the ratio of the following (2X) to the sum of the areas of the following (1X) and (2X) peaks obtained, can be 0.4 or less, and 0.35 Is preferably 0.3 or less, more preferably 0.2 or less, particularly preferably 0.1 or less, and most preferably 0.05 or less.

(1X): The area of the peak having the maximum peak height in the range where the binding energy is 99.0 eV or more and 99.5 eV or less (2X): The maximum peak height is set in the range where the binding energy is 100 eV or more and 104 eV or less. Peak area (3X) ... (2X) / [(1X) + (2X)]

  The peak area obtained by measuring the intensity of the peak (Intensity) and separating the peaks in the above (1X) and (2X) binding energy ranges, the maximum (2X) binding energy is in the range of 100 eV to 104 eV. From the area of the peak having the peak height, the content ratio of Si—O and Si—C can be seen. In addition, the content ratio of Si—Si is found from the area of the peak having the maximum peak height in the range where the bond energy of (1X) is 99.0 eV or more and 99.5 eV or less.

When the polysilane compound contains not only Si—C but also Si—O, peaks having two maximum peak heights appear in the range of 100 eV or more and 104 eV or less after peak separation, but according to the second aspect In the polysilane compound, it is preferable that only a peak having one maximum peak height appears after peak separation in the range of 100 eV or more and 104 eV or less, and ideally only one peak appears. O-bonds are not considered to be included.
In addition, when the conventional polysilane compound contains not only Si—C but also Si—O, the area ratio is 100 pV or more and 104 eV or less because, after peak separation, two peaks having the maximum peak height appear. Therefore, the ratio represented by the above formula exceeds 0.4.

（上記一般式（Ｔ−２）中、Ｒ^ｔ１６及びＲ^ｔ１７は、それぞれ独立に、水素原子、水酸基又は有機基を表す。Ｕは３〜２０の整数を表す。）、
Ｒ^ｔ１０〜Ｒ^ｔ１７で表される有機基としては、Ｒで表される有機基として前述した具体例及び好ましい例と同様のものが挙げられる。
Ｒ^ｔ１０〜Ｒ^ｔ１７で表される有機基としては、例えば、特開２００３−２６１６８１号公報段落００３１に記載の方法により任意の有機基を導入することもできる。 The polysilane compound according to the second aspect is a polysilane compound produced by the production method according to the first aspect described above.
Examples of the polysilane compound according to the second aspect manufactured by the manufacturing method according to the first aspect include polysilane compounds having 3 to 40 Si atoms, and are polysilane compounds having 5 to 30 Si atoms. Is preferred.
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 each independently a hydrogen atom, a hydroxyl group or an organic group. T1, t2, t3 and t4 are each independently The molar fraction is t1 + t2 + t3 + t4 = 1, 0 ≦ t1 ≦ 1, 0 ≦ t2 ≦ 1, 0 ≦ t3 ≦ 1, and 0 ≦ t4 ≦ 1.)

(In the general formula (T-2), R ^t16 and R ^t17 each independently represents a hydrogen atom, a hydroxyl group or an organic group. U represents an integer of 3 to 20).
Examples of the organic group represented by R ^{t10 to} R ^t17 include the same examples as the specific examples and preferred examples described above as the organic group represented by R.
As the organic group represented by R ^{t10 to} R ^t17 , any organic group can be introduced by, for example, the method described in paragraph 0031 of JP-A No. 2003-261681.

The mass average molecular weight (Mw) of the polysilane compound is not particularly limited as long as the object of the present invention is not impaired, but is preferably 500 to 10,000, more preferably 1000 to 7000, and further preferably 2000 to 5000.
In the present specification, the mass average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) in terms of polystyrene.

<Composition>
The composition which concerns on a 3rd aspect is a composition containing the polysilane compound which concerns on the 2nd aspect manufactured by the manufacturing method which concerns on a 1st aspect.

Moreover, it is preferable that the composition which concerns on a 3rd aspect further contains the said nitroxy compound from a viewpoint of suppressing generation | occurrence | production of an outgas and a microcrack.
The method according to the third aspect further includes the nitroxy compound as long as the effects of the present invention are not impaired, but the nitroxy compound used in the production method according to the first aspect is not limited. It may be achieved by remaining in the composition according to the third aspect, or may be achieved by adding the nitroxy compound to the composition containing the polysilane compound according to the second aspect. Also good.
The said nitroxy compound may be used independently and may be used in combination of 2 or more type.

The content of the nitroxy compound in the composition according to the third aspect is preferably 0.005% by mass or more based on the total mass of components other than the solvent of the composition according to the third aspect. 009 mass% or more is more preferable.
Further, the content of the nitroxy compound in the composition according to the third aspect is preferably 2% by mass or less, preferably 1% by mass with respect to the total mass of components other than the solvent of the composition according to the third aspect. The following is more preferable.

Further, the composition according to the third aspect may be a thermosetting composition or may not be a thermosetting composition.
The composition according to the third aspect may be a radiation-sensitive composition or not a radiation-sensitive composition, and is a positive-type radiation-sensitive composition that is solubilized in a developer upon exposure. Or a negative radiation-sensitive composition that becomes insoluble in a developer upon exposure.
Examples of the radiation light source include an active energy ray such as ultraviolet light and excimer laser light, a light source that emits ultraviolet light such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a carbon arc lamp.

(solvent)
The composition according to the third aspect preferably contains a solvent. Examples of the solvent include the above-mentioned cyclic skeleton acetate-containing compounds such as cycloalkyl acetate represented by the above formula (S1),
Alcohols such as methanol, ethanol, propanol, n-butanol;
Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol;
Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone;
a lactone ring-containing organic solvent such as γ-butyrolactone;
Compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, monomethyl ether, monoethyl ether, monopropyl of the polyhydric alcohols or the compound having an ester bond Derivatives of polyhydric alcohols such as ether, monoalkyl ether such as monobutyl ether or compounds having an ether bond such as monophenyl ether;
Cyclic ethers such as dioxane and esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate;
Aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, amylbenzene, isopropylbenzene, toluene, xylene, cymene, 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 formamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-ethylpyrrolidone;
Is mentioned.

Among them, the cycloalkyl acetate represented by the above formula (S1), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), N, N, N ′, N′-tetramethylurea (TMU), and Butanol is preferable, cyclopropyl acetate, cyclobutyl acetate, cyclopentyl acetate, cyclohexyl acetate, cycloheptyl acetate or cyclooctyl acetate is more preferable, and cyclohexyl acetate is more preferable.
Two or more of these solvents may be used in combination.

The water content of the composition according to the third aspect is preferably 1.0% by mass or less and 0.5% by mass or less in that the composition according to the third aspect suppresses microcracks. More preferably, it is more preferably 0.3% by mass or less, and particularly preferably less than 0.3% by mass. The water content in the solvent can be measured by the Karl Fischer measurement method.
The water content of the composition according to the third aspect is often derived from a solvent. For this reason, it is preferable that the solvent is dehydrated so that the water content of the composition according to the third aspect is the above amount.

  The usage-amount of a solvent is not specifically limited in the range which does not inhibit the objective of this invention. From the viewpoint of film forming property, the solvent is used so that the solid content concentration of the composition according to the third aspect is preferably 1 to 50% by mass, more preferably 10 to 40% by mass.

(Other ingredients)
The composition according to the third aspect may include a polysilane other than the polysilane compound according to the second aspect. For example, a polysilane compound having a high Mw (hereinafter also simply referred to as “high molecular weight polysilane”) in terms of improving chemical resistance and the like, and the Mw of the high molecular weight polysilane is, for example, more than 5,000 and less than 100,000, preferably It is about 6000-60000.

The composition according to the third aspect may contain a silicon-containing resin other than the polysilane compound in terms of improving processability. Examples of the silicon-containing resin other than the polysilane compound include a polysiloxane resin or a polysilane-polysiloxane resin having a polysilane structure (I-1) and a polysiloxane structure (I-2). As Mw of silicon-containing resin other than a polysilane compound, 500-20000 are preferable, 1000-10000 are more preferable, and 2000-8000 are still more preferable.
In addition, the said polysilane polysiloxane resin is the following general formula (A-1-1)-(A-) after processing the polysilane compound which concerns on a 2nd aspect in the solvent on the basic conditions mentioned above, for example. 1-4) at least one silicon compound selected from the group consisting of silicon compounds and at least one selected from the group consisting of hydrolysates, condensates and hydrolysis condensates of the above silicon compounds; Can be produced by hydrolytic condensation reaction.
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, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or An organic group, and a hydrogen atom in the organic group may be substituted with a halogen atom.)

Examples of the hydrolyzable group represented by X ^{1 to} X ⁴ include an alkoxy group, a halogen atom or an isocyanate group (NCO), and an alkoxy group is preferable.
As said alkoxy group, a C1-C6 alkoxy group is mentioned, Specifically, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, Examples include a pentoxy group.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, A chlorine atom is preferable.

Examples of the organic group represented by R ^{1 to} R ⁶ include an organic group having 1 to 30 carbon atoms, and an alkyl group [methyl, ethyl, n-propyl, i-propyl, n-butyl group, and t-butyl group. An alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms)], a cycloalkyl group (5 to 5 carbon atoms such as a cyclohexyl group). 8 cycloalkyl groups, particularly cycloalkyl groups having 5 to 6 carbon atoms), alkenyl groups [alkenyl groups having 2 to 10 carbon atoms such as ethenyl group, propenyl group and butenyl group (preferably having 2 to 6 carbon atoms) Alkenyl groups, especially alkenyl groups having 2 to 4 carbon atoms, etc.]], cycloalkenyl groups [1-cyclopentenyl groups, 1-cyclohexenyl groups, etc., having 5 to 10 carbon atoms. A group (preferably a cycloalkenyl group having 5 to 8 carbon atoms, particularly a cycloalkenyl group having 5 to 7 carbon atoms)], an aryl group (an aryl group having 6 to 10 carbon atoms such as phenyl or naphthyl group), Aralkyl groups [C _6-10 aryl-C _1-6 alkyl groups such as benzyl and phenethyl groups (C _6-10 aryl-C _1-4 alkyl groups)], amino groups, N-substituted amino groups (the above alkyl groups) , A cycloalkyl group, an aryl group, an aralkyl group, an N-mono- or di-substituted amino group substituted with an acyl group, and the like. The aryl group constituting the alkyl group, cycloalkyl group, aryl group or aralkyl group may have one or more substituents. Examples of such a substituent include the above-exemplified alkyl groups (particularly, alkyl groups having 1 to 6 carbon atoms), the above-exemplified alkoxy groups, and the like. Examples of the organic group having such a substituent include C _1-6 alkyl-C _6-10 aryl groups such as tolyl, xylenyl, ethylphenyl, and methylnaphthyl groups (preferably mono, di, or tri C _1-4). Alkyl-C _6-10 aryl groups, particularly mono- or di-C _1-4 alkylphenyl groups); C _1-10 alkoxy C _6-10 aryl groups such as methoxyphenyl, ethoxyphenyl, _{methoxynaphthyl} groups (preferably C _{1 -6} alkoxy C _6-10 aryl group, especially C _1-4 alkoxyphenyl group and the like.

Further, the silicon compound represented by the general formula (A-1-3) may be a silicon compound represented by the following formula (A-3).

HOOC-U-Z-Y-Si (OR ^a ) ₃ (A-3)

(In the general formula (A-3), U represents a divalent group or branched chain formed by removing one hydrogen atom of each of two ring carbon atoms from an aromatic ring group or an alicyclic group. And / or an alkylene group which may have a double bond, Z represents —NHCO— or —CONH—, and Y represents a single bond, an alkylene group, an arylene group or —R ^Y1 —NH—R ^Y2. -(Wherein R ^Y1 and R ^Y2 each independently represents an alkylene group), and R ^a each independently represents a hydrocarbon group, provided that U and / or Y is a (meth) acryl group, (It may have at least one group selected from the group consisting of a vinyl group and an epoxy group as a substituent.)

Examples of the aromatic ring in U include an aromatic ring having 6 to 10 carbon atoms which may have a substituent having 1 to 2 carbon atoms (for example, a benzene ring, a naphthalene ring, a tolyl group, a xylyl group, etc.). be able to.
Examples of the alicyclic ring in U include an alicyclic group having 5 to 10 carbon atoms (for example, a monocyclic cycloalkyl group, a monocyclic cycloalkenyl group, a bicyclic alkyl group, a cage alkyl group, and the like. For example, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a dicyclopentadiene ring, a norbornane ring, a norbornene ring, a cubane ring, and a basuketan ring.
Examples of the alkylene group that may have a branched chain and / or a double bond in U include an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a vinylene group, ( Examples include alkylene groups such as 2-octenyl) ethylene group, (2,4,6-trimethyl-2-nonenyl) ethylene group, alkylene groups having a double bond, or alkylene groups having 1 to 9 carbon atoms. Can do.

As said alkylene group in Y, a C1-C6 alkylene group is mentioned, For example, a methylene group, ethylene group, a propylene group, a butylene group etc. can be mentioned. As said arylene group in Y, a C6-C10 thing is preferable. As such a thing, a phenylene group (ortho, meta, para, etc.), a naphthylene group (1,4-, 1,5-, 2,6-, etc.) etc. can be mentioned, for example. Specific examples of —R ^Y1 —NH—R ^Y2 — in ^Y include, for example, —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. be able to.

  The polysiloxane resin is a hydrolyzate or condensate of at least one silicon compound selected from the group consisting of silicon compounds represented by the general formulas (A-1-1) to (A-1-4). And at least one selected from the group consisting of hydrolysis condensates.

Resins other than the polysilane compound according to the first aspect (hereinafter referred to as other Si resins) may be used singly or in combination.
When the other Si resin is included, the blending ratio (mass ratio) of the polysilane compound according to the first aspect and the other Si resin in the composition according to the third aspect may be appropriately changed according to the application. For example, it is 1:99 to 99: 1, preferably 10:90 to 90:10.

The composition which concerns on a 3rd aspect may contain the organic compound which has a 2 or more hydroxyl group or carboxyl group in 1 molecule as a solubility promoter to alkaline aqueous solution or a solution. Examples of such an organic compound include the following compounds.

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 of 1 to 3, nb represents a natural number of 1 or more, nc represents a natural number of 2 to 4, and nd represents a natural number of 2 or more.
The structural formula may include enantiomers and diastereoisomers, and each structural formula represents all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

The said organic compound can be used individually by 1 type or in combination of 2 or more types. The amount used is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass, based on the total solid content excluding the solvent of the composition according to the third aspect.
By adding such an organic compound, when the resin composition film is removed during processing in the manufacturing process or when lithography performance is imparted to the resin composition, the film formed using the composition is collapsed. Is accelerated and peeling becomes easy.

  The composition according to the third aspect may contain a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms in order to improve stability. Acids added at this time include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid , Phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid Diethyl malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, citric acid and the like. Among these, oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid and the like are particularly preferable. In order to maintain stability, two or more kinds of acids may be mixed and used. The organic acid is blended so that it is preferably 0 ≦ pH ≦ 7, more preferably 0.3 ≦ pH ≦ 6.5, and even more preferably 0.5 ≦ pH ≦ 6, in terms of the pH of the composition. It is good.

  Moreover, the composition which concerns on a 3rd aspect may contain the monovalent | monohydric or bivalent or more alcohol or ether compound which has cyclic ether as a substituent as a stabilizer. Specific examples of the stabilizer that can be used include the stabilizers described in paragraphs (0180) to (0184) of JP2009-126940A.

  The composition according to the third aspect may contain water. Lithography performance is improved by adding water. The content of water in the solvent component of the composition according to the third aspect is preferably more than 0% by mass and less than 50% by mass, more preferably 0.3 to 30% by mass, still more preferably 0.5 to 20% by mass. It is.

  The composition according to the third aspect may contain a photoacid generator. Specific examples of the photoacid generator that can be used include the photoacid generators described in paragraphs (0160) to (0179) of JP2009-126940A.

  The composition which concerns on a 3rd aspect may contain surfactant as needed. Specific examples of the surfactant that can be used include surfactants described in paragraph (0185) of JP2009-126940A.

The composition according to the third aspect may contain a thermal crosslinking accelerator. Specific examples of thermal crosslinking accelerators that can be used include thermal crosslinking accelerators described in JP-A-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, tetrabutylammonium borate, and sulfonium salts such as triphenylsulfonium borate.
In addition, the said thermal crosslinking accelerator can be used individually by 1 type or in combination of 2 or more types. The amount of the thermal crosslinking accelerator added is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, based on the total amount of the solid content excluding the solvent of the composition.

The composition which concerns on a 3rd aspect may contain the other various hardening | curing agent.
Examples of the curing agent include Bronsted acids; imidazoles; organic amines; organic phosphorus compounds and complexes thereof; organic amine complexes of Lewis acids; amidines; curing agents that generate a base component by light or heat. It is done.

(Use)
The composition which concerns on a 3rd aspect can be used as a use which forms the protective film or interlayer film which protects various board | substrates (a metal oxide containing film and various metal containing films are included).
Examples of the various substrates include semiconductor substrates, liquid crystal displays, organic light emitting displays (OLEDs), electrophoretic displays (electronic paper), touch panels, color filters, backlights, and other display material substrates (metal oxide-containing films, various metal-containing materials). Including a film), a substrate for a solar cell (including a metal oxide-containing film and various metal-containing films), a substrate for a photoelectric conversion element such as an optical sensor (including a metal oxide-containing film and various metal-containing films). And substrates of photoelectric devices (including metal oxide-containing films and various metal-containing films).

<Substrate provided with cured product and the cured product>
The cured product according to the fourth aspect is a cured product of the composition of the third aspect.
The board | substrate which concerns on a 5th aspect is a board | substrate provided with the hardened | cured material of a 4th aspect.
The method for forming the cured product according to the fourth aspect is not particularly limited as long as the effect of the present invention is not impaired, but contact transfer type coating such as roll coater, reverse coater, bar coater, etc. on any substrate as necessary. Examples thereof include a coating method using a non-contact type coating apparatus such as an apparatus, a spinner (rotary coating apparatus), or a curtain flow coater.
Although there is no restriction | limiting in particular as a board | substrate, For example, a glass substrate, a quartz substrate, a transparent or translucent resin substrate (For example, heat-resistant materials, such as a polycarbonate, a polyethylene terephthalate, a polyether sulfone, a polyimide, a polyamide imide, etc.), a metal And a silicon substrate.
Semiconductor substrates, liquid crystal displays, organic light emitting displays (OLED), electrophoretic displays (electronic paper), substrates for display materials such as touch panels, color filters, backlights (including metal oxide-containing films and various metal-containing films), Substrates for solar cells (including metal oxide-containing films and various metal-containing films), substrates for photoelectric conversion elements such as optical sensors (including metal oxide-containing films and various metal-containing films), substrates for photoelectric elements ( Various substrates such as metal oxide-containing films and various metal-containing films may be used.
The thickness of a board | substrate is not specifically limited, According to the usage condition of a pattern formation body, it can select suitably.

  The coated film after application is preferably dried (pre-baked). The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at 80 to 120 ° C., preferably 90 to 100 ° C. for 60 to 120 seconds, (2) several hours at room temperature Examples include a method of leaving for several days, and (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several tens of minutes to several hours.

The dried coating film may or may not be exposed to irradiation with active energy rays such as ultraviolet rays and excimer laser light. Although there is no restriction | limiting in particular in the energy dose to irradiate, For example, about 30-2000 mJ / cm < ² > is mentioned. You may perform the process of exposing together with the process of baking instead of the process of baking mentioned later. Further, in the exposure step, for example, the formed coating film may be selectively exposed, and in the case of including a selective exposure step, a developing step may be included. Further, for example, imprint lithography may be performed on the formed coating film. When performing imprint lithography, for example;
Applying the composition of the third aspect on a substrate to form a coating film;
A step of pressing a mold having a concavo-convex structure of a predetermined pattern against a coating film;
And a step of exposing.
The exposing step is performed on the coating film made of the composition of the third aspect in a state where the mold is pressed against the coating film. After the curing by exposure, the cured product according to the fourth aspect patterned according to the shape of the mold can be obtained by peeling the mold.

The dried, exposed or developed coating film is preferably baked (post-baked) from the viewpoint of improving film properties.
The firing temperature depends on the lower substrate and the intended use, but is, for example, in the range of 200 to 1000 ° C, preferably 200 to 500 ° C, and more preferably 200 to 250 ° C. The firing 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 may be under air or the oxygen concentration may be controlled appropriately. The firing time may be appropriately changed and is about 10 minutes to 120 minutes.

  The cured product according to the fourth aspect is preferably a protective film that protects the various substrates (including metal oxide-containing films and various metal-containing films).

  When the cured product is a film, the thickness is preferably 10 nm to 10000 nm, more preferably 50 to 5000 nm, and still more preferably 100 to 3000 nm.

<Anionic polymerization selective accelerator in production of polysilane compound>
The anionic polymerization selective accelerator according to the sixth aspect is an anionic polymerization selective accelerator in the production of a polysilane compound containing a nitroxy compound containing the structure represented by the general formula (A).
The anionic polymerization selective accelerator according to the sixth aspect can selectively accelerate the anionic polymerization by the silyl radical anion by spin-charging the silyl radical cation generated during the production of the polysilane compound to convert it into a silyl radical anion. Thereby, generation | occurrence | production of side reactions, such as a siloxane bond and a silanol group which causes a microcrack, can be suppressed, and generation | occurrence | production of outgas can also be suppressed.

Specific examples and preferred examples of the nitroxy compound containing the structure represented by the general formula (A) are as described above in the method for producing a polysilane compound according to the first aspect.
The amount of the anionic polymerization selective accelerator according to the sixth aspect is preferably in the range of 0.0001 to 10 mol times, more preferably 0.001 to 5 mol times, relative to the halosilane compound used for the production of the polysilane compound. More preferably, it is the range of 0.001-1 mol times, Most preferably, it is the range of 0.001-0.1 mol times.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Example 1] Production of polysilane compound In a round flask with an internal volume of 1000 ml equipped with a three-way cock, 25 g of granular (particle size 20 to 1000 μm) magnesium and tris (acetylacetonato) iron (III) as a catalyst. 1 g, 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical) 0.61 mmol (0.10 g) is charged and 1 mmHg (= 133 kPa) at 50 ° C. After heating and reducing the pressure and drying the inside of the reactor (flask), dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran (THF) previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at 25 ° C. for about 60 minutes. did. To this reaction mixture, 63.5 g (0.3 mol) of methylphenyldichlorosilane purified in advance by distillation was added by a syringe and 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 layer was washed 10 times with 200 ml of pure water, the toluene layer was dried over anhydrous magnesium sulfate, and then toluene was distilled off to obtain 28.4 g of methylphenylsilane polymer (mass average molecular weight 2000) (yield). Rate 63%).

[Examples 2 to 4 and Comparative Examples 1 and 2] Production of polysilane compounds Table 1 shows the types of halosilane compounds, the types of organometallic complexes or metal halides, the presence or absence of nitroxy compounds, and the types of polysilane compounds produced. The polysilane compounds of Examples 2 to 4 and Comparative Examples 1 and 2 were produced in the same manner as in Example 1 except that the above was changed. In addition, Example 5 manufactured according to the method as described in JACS, 110,124 (1998) and Macromolecules, 23,3423 (1990) except adding a nitroxy compound.

[Preparation Examples 1 to 4 and Comparative Preparation Examples 1 and 2] Preparation of Compositions Each of the polysilane compounds obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were mixed in a solvent of the type described in Table 2 with a solid content. The compositions of Preparation Examples 1 to 4 and Comparative Preparation Examples 1 and 2 were prepared by dissolving so as to have a concentration of 30% by mass and filtering with a fluororesin filter having a pore size of 0.1 μm.

[Formation of film]
On the sample substrate, the composition of each of the obtained preparation examples and comparative preparation examples was applied using a spin coater to form a coating film having a film thickness capable of forming a film having a film thickness of 5.0 μm.
After pre-baking the coating film at 100 ° C. for 2 minutes, the coating film is baked at 350 ° C. for 30 minutes using a vertical baking furnace (TS8000MB, manufactured by Tokyo Ohka Kogyo Co., Ltd.) to form a coating film having a thickness of 5.0 μm. Obtained.
The formed film was evaluated for the presence or absence of microcracks and the occurrence of outgas according to the following method.

<Evaluation of microcracks>
The surface of the formed coating after standing for 24 hours was observed using an optical microscope (magnification 100 times) to evaluate the presence or absence of microcracks. The results are shown in Table 2.

<Evaluation of outgas>
Further, the degree of outgas generation was evaluated based on the temperature programmed desorption gas analysis method (TDS). The film formed using the compositions of Comparative Preparation Examples 1 and 2 has an outgas generation amount of any of the compositions of Preparation Examples 1 to 5 containing the polysilane compounds of Examples 1 to 5. Many were also confirmed for the coating.

As is apparent from the results shown in Table 2, the film formed using the composition of Comparative Preparation Examples 1 and 2 containing the polysilane compound of Comparative Examples 1 and 2 produced without using the nitroxy compound was microscopic. Cracks and outgassing occurred.
On the other hand, none of the films formed using the compositions of Preparation Examples 1 to 5 containing the polysilane compounds of Examples 1 to 5 manufactured using the nitroxy compound show any microcracks, and the outgassing is also generated. It was suppressed.

Claims (11)

  A method for producing a polysilane compound, comprising reacting a halosilane compound in the presence of a nitroxy compound. The manufacturing method of Claim 1 whose said nitroxy compound is a compound containing the structure represented by the following general formula (A).

(In 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 are bonded to each other to form a ring. R ^a3 and R ^a4 may be bonded to each other to form a ring.)   Furthermore, the manufacturing method of Claim 1 or 2 with which the said halosilane compound is made to react in presence of an alkali metal or magnesium. The manufacturing method of any one of Claims 1-3 whose said halosilane compound is a compound represented by following formula (1).

X _n SiR _4-n (1)

(Wherein n is an integer of 2 to 4, n Xs are each independently a halogen atom, and (4-n) Rs are each independently a hydrogen atom, an organic group or a silyl group. Group.) Furthermore, the said halosilane compound is made to react in presence of the organometallic complex represented with the following general formula (B), The manufacturing method of any one of Claims 1-5.

(In the above general formula (B), M is iron, silver, aluminum, bismuth, cerium, cobalt, copper, dysprosium, erbium, europium, gallium, gadolinium, hafnium, holmium, indium, iridium, lanthanum, lutetium, manganese, Molybdenum, neodymium, nickel, osmium, palladium, promethium, praseodymium, platinum, rhenium, rhodium, ruthenium, samarium, scandium, tin, terbium, titanium, thulium, vanadium, chromium, tantalum, ytterbium, gold, mercury tungsten, yttrium, zinc And R ^b1 each independently represents a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an aralkyl group, an alkoxy group, an aryl group, or an aryl group. Represents a xyl group, an aralkyloxy group or an aryloxyalkyl group, and R ^b2 represents a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or an aralkyl group, and p represents an integer of 1 or more. Represents.)   It is a manufacturing method of the composition containing a polysilane compound, Comprising: The said polysilane compound is manufactured by the method of any one of Claims 1-5.   The method of claim 6, wherein the composition further comprises a nitroxy compound.   A method for producing a cured product of a composition, wherein the composition is produced by the method according to claim 6 or 7.   The manufacturing method of a board | substrate provided with hardened | cured material, Comprising: The said hardened | cured material is manufactured by the method of Claim 8. An anionic polymerization selective accelerator in the production of a polysilane compound, comprising a nitroxy compound containing 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 are bonded to each other to form a ring. R ^a3 and R ^a4 may be bonded to each other to form a ring.)   The accelerator according to claim 12, wherein the silyl radical cation generated during production of the polysilane compound is spin-charged.