JP2018109111A - Method for producing polysilane and method for producing active metal magnesium component used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polysilane, by which a polysilane having a small molecular weight dispersity (Mw/Mn) can be obtained, and to provide a method for producing an active metal magnesium component used therefor.SOLUTION: The method for producing a polysilane according to the present invention includes a step of reacting a halosilane compound by causing a metal magnesium component to act thereon in a solvent containing a cycloalkyl acetate represented by formula (S1). (In the formula (S1), Ris a C1-3 alkyl group; p is an integer of 1-6; and q is an integer of 0 to (p+1).)SELECTED DRAWING: None

Description

  The present invention relates to a method for producing polysilane and a method for producing an active metal magnesium component used therefor.

  Polysilane is used in 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, electroluminescent element materials), and various elements. It is 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, in a reaction system in which a magnesium metal is reacted with a halosilane compound in the presence of a lithium compound and a specific metal halide to form polysilane, the active metal magnesium that is a solid component remaining after the reaction is used. There has been disclosed a method for producing polysilane in which the above raw materials (lithium compound, metal halide, and halosilane compound) are added and reacted to produce polysilane (Patent Document 1).

Japanese Patent No. 4559642

  However, the polysilane obtained in Patent Document 1 has room for improvement in terms of molecular weight distribution. By narrowing the distribution range of the mass average molecular weight of the polysilane, it is expected that the coating film using the polysilane as a raw material, the flatness of the gap fill, etc. are improved.

  The present invention has been made in view of the above problems. An object of this invention is to provide the manufacturing method of the polysilane which can obtain polysilane with small molecular weight dispersion degree (Mw / Mn), and the manufacturing method of the active metal magnesium component used for this.

  The present inventors have found that the molecular weight dispersity of polysilane can be reduced by reacting a halosilane compound by reacting a metal magnesium component in a specific solvent, and the present invention has been completed.

（式（Ｓ１）中、Ｒ^ｓ１は、炭素原子数１〜３のアルキル基であり、ｐは１〜６の整数であり、ｑは０〜（ｐ＋１）の整数である。） 1st aspect of this invention is a polysilane manufacturing method including the process of making a metal magnesium component react and reacting a halosilane compound in the solvent containing the cycloalkyl acetate represented by a following formula (S1).

(In formula (S1), R ^s1 is an alkyl group having 1 to 3 carbon atoms, p is an integer of 1 to 6, and q is an integer of 0 to (p + 1).)

  According to a second aspect of the present invention, in a solvent containing a cycloalkyl acetate represented by the following formula (S1), a halosilane compound, together with a metal magnesium component, (I) an alkali metal compound and a halogen of a metal other than an alkali metal A process for producing an active metal magnesium component, comprising a step A in which a metal halide which is a chemical compound is allowed to act and a reaction, and a step B in which a liquid component is removed from the reaction mixture obtained in the step A.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a polysilane which can obtain polysilane with small molecular weight dispersion degree (Mw / Mn), and the manufacturing method of the active metal magnesium component used for this can be provided.

<Production method of polysilane>
The method for producing a polysilane according to this embodiment includes a step of reacting a halosilane compound with a metal magnesium component acting in a solvent containing a cycloalkyl acetate represented by the above formula (S1).

  According to the method for producing a polysilane according to this embodiment, a polysilane having a low molecular weight dispersity (Mw / Mn), for example, 4 or less, preferably by reacting with a solvent containing a cycloalkyl acetate represented by the formula (S1). Can obtain 1 to 3 polysilanes. In addition, a mass average molecular weight (Mw) can be adjusted with 1000-100000, Preferably it is 5000-80000, More preferably, it is about 6000-60000. In the present specification, the mass average molecular weight (Mw) is a measured value in terms of styrene of gel permeation chromatography (GPC).

Furthermore, in terms of improving reactivity, the polysilane production method according to this embodiment is preferably reacted in the presence of the following (I) or (II) together with the metal magnesium component. Moreover, when making it react in presence of following (II), you may make an alkali metal compound exist further.
(I) an alkali metal compound and a metal halide which is a halide of a metal other than an alkali metal, or (II) an organometallic complex represented by the following general formula (A1)

M ^r L _{r / s} (A1)

(In the general formula (A1), ^Mr represents an r-valent metal cation, L represents an s-valent organic ligand, and r and s each independently represents an integer of 1 or more.)

  Hereinafter, a halosilane compound, a solvent, a metal magnesium component, (I) a metal halide that is a halide of a metal other than an alkali metal compound and an alkali metal, and (II) a general formula used in the production of the polysilane according to the present embodiment Each of the organometallic complexes represented by (A1) will be described in detail. In the present specification, a metal halide that is a halide of a metal other than an alkali metal may be simply referred to as a “metal halide” hereinafter.

[Halosilane compounds]
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 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl groups (preferably alkyl groups having 1 to 10 carbon atoms). , More preferably an alkyl group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms, etc.], a cycloalkyl group (cycloalkyl groups having 5 to 8 carbon atoms such as a cyclohexyl group, particularly 5 to 6 carbon atoms). Cycloalkyl group), alkenyl group [alkenyl group having 2 to 12 carbon atoms such as ethenyl group, propenyl group, butenyl group (preferably alkenyl group having 2 to 10 carbon atoms, especially alkenyl group having 2 to 8 carbon atoms) Etc.]], cycloalkenyl groups [cycloalkenyl groups having 5 to 12 carbon atoms such as 1-cyclopentenyl group and 1-cyclohexenyl group (preferably A cycloalkenyl group having 5 to 10 carbon atoms, particularly a cycloalkenyl group having 5 to 8 carbon atoms)], an aryl group (an aryl group having 6 to 12 carbon atoms such as phenyl or naphthyl group), an aralkyl group [benzyl C _6-10 aryl-C _1-6 alkyl group such as phenethyl group (C _6-10 aryl-C _1-4 alkyl group etc.)], alkoxy group [methoxy, ethoxy, propoxy, isopropoxy, butoxy and t- An alkoxy group having 1 to 12 carbon atoms such as a butoxy group (preferably an alkoxy group having 1 to 6 carbon atoms, particularly an alkoxy group having 1 to 4 carbon atoms), an amino group, an N-substituted amino group (above An N-mono- or di-substituted amino group substituted with an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an acyl group, 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), 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 to tri C _1-4 alkyl- C _6-10 aryl groups, especially 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, etc.).

  The silyl group may be a substituted silyl group substituted with the above alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, aralkyl group, alkoxy group or the like.

  When n is 2 (dihalosilane compound), the organic group combination represented by R (n = 2) is preferably an alkyl group-alkyl group, aryl group-aryl group, alkyl group-aryl group, A combination of group-phenyl group, methyl group-methyl group, and phenyl group-phenyl group is more preferable.

  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.

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

[Alkali metal compounds]
As the alkali metal compound used in the present invention, compounds containing lithium, sodium, potassium, etc. (halides, inorganic acid salts, etc.) can be used, and lithium compounds are preferred.

  Such lithium compounds include lithium halides (lithium chloride, lithium bromide, lithium iodide, etc.), inorganic acid salts (lithium nitrate, lithium carbonate, lithium hydrogen carbonate, lithium sulfate, lithium perchlorate, lithium phosphate) Etc.) can be used. These lithium compounds can be used alone or in combination of two or more. A preferred lithium compound is lithium halide (especially lithium chloride).

[Metal halide]
The metal halide is a halide of a metal other than an alkali metal. Such a metal halide is specifically a polyvalent metal halide, for example, a transition metal (for example, a periodic table group 3A element such as samarium, a periodic table group 4A element such as titanium, or a periodic table such as vanadium. Metals such as Group 5A elements, Group 8 elements of the periodic table such as iron, cobalt, palladium, etc., Group 2B elements of the periodic table such as zinc), Group 3B metals (such as aluminum), and Group 4B metals (such as tin) of the periodic table 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.

Examples of such metal halides include chlorides (iron chlorides such as FeCl ₂ and FeCl ₃ ; AlCl ₃ , ZnCl ₂ , SnCl ₂ , CoCl ₂ , VCl ₂ , TiCl ₄ , PdCl ₂ , SmCl ₂ , CuCl _2. Etc.), bromides (such as iron bromide such as FeBr ₂ and FeBr ₃ ), iodides (such as SmI ₂ ) and the like. Of these metal halides, iron chloride (FeCl ₂ , FeCl ₃ ), zinc chloride (ZnCl ₂ ), and copper chloride (CuCl ₂ ) are particularly preferred.

[Metallic magnesium component]
The magnesium metal component only needs to contain at least magnesium, and may be a magnesium metal simple substance or a magnesium alloy, or a mixture containing the magnesium metal or alloy. 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.). These metal magnesium components can be used alone or in combination of two or more.

  The shape of the metal magnesium component is not particularly limited as long as it does not impair the reactivity of the polymerization reaction of the halosilane compound, but it is powdery (powder, granular, etc.), ribbon-like, cut piece, lump, rod, A flat plate or the like is exemplified, and a shape having a large surface area (powder, granule, ribbon, cut piece, etc.) is particularly preferable. When the metallic magnesium component is granular, the average particle size is about 1 to 10000 μm, preferably about 10 to 5000 μm, and more preferably about 20 to 1000 μm.

  Depending on the storage status of the metal magnesium component, a film (such as an oxide film) may be formed on the metal surface. Since this coating may adversely affect the reaction, it may be removed by cutting or the like, if necessary.

[Organic metal complex]
The organometallic complex represented by the following general formula (A1) in (II) will be described below.
M ^r L _{r / s} (A1)

(In the general formula (A1), ^Mr represents an r-valent metal cation, L represents an s-valent organic ligand, and r and s each independently represents an integer of 1 or more.)

The metal atoms constituting the r-valent metal cation ^Mr include iron, silver, aluminum, bismuth, cerium, cobalt, copper, dysprosium, erbium, europium, gallium, gadolinium, hafnium, holmium, indium, iridium, lanthanum, and 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.
r is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and further preferably 2 or 3.
s is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
Organic ligands such as β-diketonato ligand, olefin, conjugated ketone, nitrile, amine, carboxylate ligand, carbon monoxide, phosphine, phosphinite, phosphonite, phosphite, etc. A child. The s-valent organic ligand L may be a chelate ligand.

（上記一般式（Ａ２）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。ｒは１以上の整数を表す。） The organometallic complex is preferably an organometallic complex represented by the following general formula (A2).

(In the general formula (A2), 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 ^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 r 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, and further, these are a halogen atom (fluorine atom, chlorine atom, bromine atom, iodo atom), alkoxy group (such as those described below), silyl group (described below) Alkyl groups substituted with one or more substituents such as Propyl group, 3,3,3-trifluoropropyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, tridecafluoro-1,1,2,2-tetrahydro Octyl group, heptadecafluoro-1,1,2,2-tetrahydrodecyl group, 3- (heptafluoroisopropoxy) propyl group, trimethylsilylmethyl group, etc .; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, bicycloheptyl Groups, cyclooctyl groups, adamantyl groups and the like, which are monocyclic or polycyclic saturated hydrocarbon groups having 3 to 18 carbon atoms, and these cyclic saturated hydrocarbon groups are alkyl groups (such as those described above), aryl Substituted with one or more substituents such as groups (such as those described above), such as 4-t-butylcyclohexyl An alkyl group having the above cyclic saturated hydrocarbon group (such as those described above), for example, a cyclohexylmethyl group, an adamantylethyl group, and the like.

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 further, an unsaturated hydrocarbon group thereof includes a halogen atom (such as those described above) and an alkoxy group (described below). ), Substituted with one or more substituents of a silyl group (such as those described below) and an aryl group (such as those described below), such as 2-trifluoromethylethenyl Group, 2-trifluoromethylethynyl group, 3-methoxy-1-propenyl group, 3-methoxy-1-propynyl group, 2-trimethyl Ruethenyl 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 r 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.

（式（Ｓ１）中、Ｒ^ｓ１は、炭素原子数１〜３のアルキル基であり、ｐは１〜６の整数であり、ｑは０〜（ｐ＋１）の整数である。） [solvent]
As a solvent used for the reaction, a solvent containing a cycloalkyl acetate represented by the following formula (S1) is used. Cycloalkyl acetate is conventionally used for tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane and the like because it exhibits good solubility in the halosilane compound (particularly hydrophobic compounds such as aryl group-containing halosilane compounds). It is considered suitable for polymerizing a polysilane having a low molecular weight dispersibility as compared with the previously used solvent, and can further enhance the polymerization activity of the halosilane compound.

(In formula (S1), R ^s1 is an alkyl group having 1 to 3 carbon atoms, p is an integer of 1 to 6, and q is an integer of 0 to (p + 1).)

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, cyclooctyl acetate is preferable because it is easily available and the polymerization activity of the halosilane compound is easily improved.
The solvent used for the reaction may contain a combination of two or more cycloalkyl acetates represented by the formula (S1).

  The content of the cycloalkyl acetate represented by the formula (S1) in the solvent used for the reaction is not particularly limited as long as the object of the present invention is not impaired. The content of the cycloalkyl acetate represented by the formula (S1) in the solvent used for the reaction is typically, for example, 30% by mass or more, preferably 50% by mass or more, and more preferably 70% by mass or more. 90 mass% or more is particularly preferable, and may be 100 mass%.

  When the solvent used in the reaction includes a solvent other than the cycloalkyl acetate represented by the formula (S1), the type of the solvent other than the cycloalkyl acetate represented by the formula (S1) is within a range that does not impair the object of the present invention. There is no particular limitation.

  Other usable solvents are preferably aprotic solvents such as ethers (1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, diethyl ether, diisopropyl ether, 1,2-dimethoxy). Ethane, cyclic or chain ethers having 4 to 6 carbon atoms such as bis (2-methoxyethyl) ether), carbonates (such as propylene carbonate), nitriles (acetonitrile, benzonitrile, etc.), amides (dimethylformamide) , Dimethylacetamide), sulfoxides (dimethylsulfoxide, etc.), halogen-containing compounds (halogenated hydrocarbons such as methylene chloride, chloroform, bromoform, chlorobenzene, bromobenzene, etc.), aromatic hydrocarbons (Benzene, toluene, xylene), aliphatic hydrocarbons (hexane, cyclohexane, octane, linear or cyclic hydrocarbons such as cyclooctane), and the like.

If the solvent contains a large amount of water, the halosilane compound reacts with the water, and siloxane bonds (Si-O bonds) are introduced into the resulting polysilane main chain, thereby reducing the quality of the polysilane. . In particular, in order to obtain a polysilane having a low molecular weight dispersion, it is preferable that the amount of water in the solvent is small. Therefore, it is desirable that the solvent to be used is as dry as possible, and it is particularly preferable that the solvent be dried with a desiccant and further distilled for use in the reaction.
For example, the water content in the solvent is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, and 0.3% by mass. It is particularly preferred that it is less than%. The water content in the solvent can be measured by the Karl Fischer measurement method.
The water content of the resulting polysilane is often derived from a solvent. For this reason, it is preferable that the solvent is dehydrated so that the water content of the resulting polysilane is the above amount.

  By the way, although the metal magnesium component used with the manufacturing method of the polysilane which concerns on this invention is as above-mentioned, you may use the active metal magnesium component (solid component) which concerns on this invention at points, such as a reactive improvement.

<Method for producing active metal magnesium component>
Hereinafter, the manufacturing method of the active metal magnesium component which concerns on this embodiment is demonstrated.
In the method for producing an active metal magnesium component according to the present embodiment, a halosilane compound is combined with a metal magnesium component in an aprotic solvent, (I) an alkali metal compound, and a metal halogen which is a halide of a metal other than an alkali metal. A process which makes a chemical compound act, and B process which removes a liquid component from the reaction mixture obtained by A process are included.

  The protic solvent used in the step A is not limited to the solvent containing the cycloalkyl acetate represented by the above formula (S1). For example, the solvents exemplified as the other solvents that can be used in the above-mentioned “solvent” are used. be able to. The cycloalkyl acetate represented by the above formula (S1) is preferably used from the viewpoint of obtaining an active metal magnesium component that becomes metal magnesium having a high active function in the polysilane production method according to the present embodiment described above.

  In particular, in the polysilane production method, when the compound (I) is used together with the metal magnesium component, the metal magnesium component is preferably the active metal magnesium component (solid component) obtained in the above-described Step A and Step B. . In this case, the polysilane is produced by the above formula (S1) in the presence of the halosilane compound in the presence of an alkali metal compound and a metal halide which is a halide of a metal other than an alkali metal. In a solvent containing a cycloalkyl acetate represented by the formula: In the presence of an alkali metal compound and a metal halide, the solid component contains a halosilane compound and metal magnesium in the above solvent (or other solvents other than the solvent containing the cycloalkyl acetate represented by the above formula (S1)). Active metal magnesium obtained by treatment with a protic solvent. That is, when the active metal magnesium component is used as the metal magnesium component, the polysilane production method according to the present invention includes a first step (a solid component production step) for producing a solid component (active metal magnesium) and the obtained solid. A second step of producing polysilane using the component (a step of producing polysilane using a solid component).

  Hereinafter, the first step and the second step will be described.

[First step]
In the first step, the halosilane compound is mixed with a magnesium metal component, (I) an alkali metal compound, and a halide of a metal other than an alkali metal in a solvent containing the cycloalkyl acetate represented by the above formula (S1). A solid component is produced by reacting with a certain metal halide.

  The solid component contained in the reaction mixture obtained in the first step (step A) is considered to be active metal magnesium in which metal magnesium is highly activated. In the second step to be described later, it is presumed that this solid component which is active metal magnesium activates an alkali metal compound which plays a role of a Lewis acid catalyst and improves the polymerization activity of the halosilane compound. Therefore, the first step can be said to be an activation treatment for obtaining polysilane and active metal magnesium. In particular, also in the first step as the solvent, by including the cycloalkyl acetate in the above formula (S1), it is possible to obtain active metal magnesium having a higher active function than in the case of a solvent composed only of other aprotic solvents. it can.

  In the first step (step A), it is sufficient that at least the alkali metal compound, the metal halide, and the halosilane compound can be brought into contact with the metal magnesium component, and can be performed by dipping, stirring treatment (preferably stirring treatment) or the like. When a di to tetrahalosilane compound is used as the halosilane compound, polysilane is generated.

  The ratio of the alkali metal compound is 1 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably about 10 to 40 parts by mass with respect to 100 parts by mass of the metal magnesium component.

  The ratio of the metal halide is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably about 10 to 30 parts by weight with respect to 100 parts by weight of the metal magnesium component.

  The ratio of the metal magnesium component to the halosilane compound may be 0.5 times mol or more (for example, about 0.5 to 10 mol) as magnesium, preferably 1.5 times the halogen atom in the halosilane compound. It is more than mol (for example, about 1.5 to 10 mol), more preferably 2.5 times mol or more (for example, about 2.5 to 10 mol). When only dihalosilane is used as the halosilane compound, it is preferable to use at least 1.5 times mol or more with respect to the halogen atom in order to increase the reactivity.

  The proportion of the solvent is not particularly limited as long as it is an amount capable of homogenizing the alkali metal compound, the metal halide, and the halosilane compound and acting on the metal magnesium component. The amount is 10,000 parts by mass, preferably 10 to 5000 parts by mass, and more preferably about 100 to 4000 parts by mass.

  The activation treatment temperature of the reaction solution in the first step (step A) is, for example, a temperature range from −20 ° C. to the boiling point of the component (solvent, etc.) used, for example, 0 to 100 ° C., preferably 10 to 10 ° C. 70 degreeC, More preferably, it is about 20-50 degreeC. The activation treatment may be performed under reduced pressure or under pressure, but is usually performed at normal pressure.

  The concentration of the halosilane compound in the reaction solution (solvent) is usually 0.05 to 20 mol / l, preferably 0.2 to 15 mol / l, particularly about 0.3 to 13 mol / l. When the concentration is within the above range, the alkali metal compound and the metal halide are sufficiently dissolved, and the treatment (reaction) can be performed efficiently.

  Moreover, the density | concentration of the alkali metal compound in a reaction solution (solvent) is 0.05-5 mol / l normally, Preferably it is 0.1-4 mol / l, Especially about 0.15-3.0 mol / l. When the concentration is within the above range, the reaction can proceed without excessively increasing the polarity of the reaction solution, and the activity of the solid component (active metal magnesium) and the molecular weight dispersion of the polysilane are suppressed from increasing. can do. The ratio of the alkali metal compound is about 0.1 to 30 parts by mass, preferably about 1 to 20 parts by mass, and more preferably about 5 to 20 parts by mass with respect to 100 parts by mass of the halosilane compound.

  The concentration of the metal halide in the reaction solution (solvent) is usually 0.01 to 6 mol / l, preferably 0.02 to 4 mol / l, particularly about 0.03 to 3 mol / l. When the concentration is within the above range, the reaction can be efficiently involved and the reaction can proceed sufficiently. The ratio of the metal halide is about 0.1 to 30 parts by mass, preferably about 1 to 20 parts by mass, and more preferably about 3 to 20 parts by mass with respect to 100 parts by mass of the halosilane compound.

  The reactor (reaction vessel) to be used is not particularly limited in shape and structure as long as it can be sealed. Further, the inside of the reaction vessel may be a dry atmosphere, but a dry inert gas (eg, nitrogen gas, helium gas, argon gas) atmosphere, particularly a deoxygenated and dried inert gas atmosphere is preferable.

  In the activation reaction of the first step (step A), for example, a halosilane compound, an alkali metal compound, a metal halide and a metal magnesium component are accommodated together with a solvent as necessary in a sealable reaction vessel, preferably mechanically or This can be done by magnetic stirring. The addition order of each component is not particularly limited.

  The activation reaction is usually started after about 1 to 7 hours have elapsed from the start of stirring, although it varies depending on the type and concentration of the raw material and the reaction temperature. When the reaction starts, the reaction solution turns black with heat generation. After the heat generation is completed, the solid component composed of active metal magnesium can be obtained together with the polysilane having a low dispersity by further stirring for about 2 to 24 hours.

  When the subsequent second step is performed using the solid component (active metal magnesium) thus obtained, the reaction starts almost simultaneously with the introduction of the halosilane compound, regardless of the type of the raw halosilane compound. Compared to the case of using magnesium, the induction period of the reaction can be greatly shortened, and accordingly, the reaction time can be greatly shortened, so that productivity can be improved.

  In the reaction mixture obtained in the first step, a part of the used metal magnesium reacts with the halosilane compound to become a magnesium halide and exists in the reaction solution. In addition, raw material components other than metallic magnesium and polysilane are present in the reaction solution (liquid component). On the other hand, the active metal magnesium remains in the reaction system in a solid state. Thus, for example, (1) the solid component (active metal magnesium) may be separated from the reaction mixture of the first step, purified if necessary and used for the second step, and (2) separated from the reaction mixture. Alternatively, it may be used in the second step as it is. Alternatively, (3) the liquid component may be removed from the reaction mixture by decantation or filtration (Step B), and the remaining solid component may be used as it is in the second step. When a small amount of solid component is produced in the first step with respect to the volume of the reactor, it may be used as it is without being separated.

[Second step]
In the second step, the solid component (active metal magnesium) obtained in the first step may be used. In the reaction system in which the solid component remains, a halosilane compound, an alkali metal compound, a metal halide and the above formula ( A solvent containing a cycloalkyl acetate represented by S1) is added and reacted to form polysilane. The reaction conditions in the second step may be the same reaction conditions as in the first step. Further, the second step may be repeated.

  When the second step is performed a plurality of times, for example, when the (n + 1) -th second step is performed subsequent to the n-th (n is an integer equal to or greater than 1) second step, This can be carried out in the same manner as the transition to the second step. When performing the second step a plurality of times, the methods (1) to (3) may be used in combination.

  In addition, when taking out a solid component (active metal magnesium) out of a reactor, in order to prevent deactivation and to make it not contact with the water | moisture content in air as much as possible, it is desirable to accommodate in the container substituted with nitrogen. .

  In the second step, raw materials (halosilane compound, alkali metal compound, metal) used in the production of polysilane in the presence of the solid component (active metal magnesium) obtained in the first step in various forms (or aspects). Halide and solvent) can be added and reacted to produce polysilane. In the second step, for example, the raw material is contained in a sealable reaction vessel containing at least a solid component (active metal magnesium), and the reaction can be preferably performed by mechanically or magnetically stirring. The order of addition of each component of the raw material is not particularly limited.

  In this step, the reaction starts with heat generation immediately after charging the raw materials, and a polysilane having a low degree of dispersion can be obtained by stirring for about 30 minutes to 12 hours after the end of heat generation.

  The first step (activation reaction) and the second step (production of polysilane) can be performed under the same conditions. That is, metallic magnesium may be activated under the same or similar conditions as in the second step. For example, a liquid component is removed from the reaction mixture obtained in the first step, and a reaction is performed by adding a halosilane compound, an alkali metal compound, a metal halide and a solvent to a reaction system in which a solid component (active metal magnesium) remains. You may let them.

  The first step and the second step may have the same volume (reaction scale) or may be different. The first step may be performed in a small amount in advance. For example, a solid component (active metal magnesium) in a small amount (1/100 to 1/3, preferably about 1/10 to 1/4) of the volume of the reactor is generated in advance. You may make it react by adding a halosilane compound, an alkali metal compound, a metal halide, and a solvent to the reaction system containing a solid component (the above-mentioned active metal magnesium).

  In the polysilane production method according to the embodiment, by using a solid component (active metal magnesium), the induction time until the start of the reaction and the reaction time can be greatly shortened, so a small amount of solid component (active metal magnesium) in advance. If a method for generating is used, even if a large amount of raw material is added in the second step, polysilane can be produced efficiently.

  In the second step, metallic magnesium may be replenished to supplement the consumed metallic magnesium component. Moreover, you may use the mixture of a solid component (active metal magnesium) and metal magnesium for a 2nd process. In particular, when the magnesium component is added or replenished in the second step while removing the liquid component in the reaction mixture in the first step, each reaction component is allowed to proceed efficiently without being diluted more than necessary. In addition, by newly adding each component, the second step can be repeated a plurality of times without washing the reaction vessel.

  In such a 2nd process, since polysilane can be produced | generated with high efficiency, the usage-amount of metal magnesium can be reduced significantly. The ratio of the solid component (active metal magnesium) in the second step is about 0.5 to 1 mol, preferably about 0.6 to 0.8 mol as magnesium with respect to 1 mol of the halogen atom of the halosilane compound.

  In this way, in the second step, the amount of solid component (active metal magnesium) used can be reduced, so the amount of metal magnesium component used throughout the first and second steps can also be reduced. The amount of the metal magnesium component used in the first and second steps is 1 to 4 mol, preferably 1 to 3 mol, especially 1 to 2 as magnesium with respect to 1 mol of the total amount of halosilane compounds used in all steps. It can be reduced to about a mole. The amount used is 0.5 to 2 mol, preferably 0.5 to 1.5 mol, more preferably about 0.5 to 1 mol in terms of magnesium with respect to 1 mol of the halogen atom of the halosilane compound. It is.

  In the polysilane production method according to this embodiment, the reaction is performed using the solid component (active metal magnesium) obtained in the first step in the second step. It can be reduced, it is excellent in economy, and the amount of waste can be reduced. In addition, polysilane can be produced easily and safely in a general-purpose reactor, and the quality of polysilane (such as molecular weight dispersity) can be stably controlled. In particular, since the cycloalkyl acetate represented by the above formula (S1) is used as the solvent, the polymerization activity of the halosilane compound can be improved and polysilane having a small molecular weight distribution can be obtained.

  In the second step, the concentration of the halosilane compound in the reaction solution (solvent) is usually 0.05 to 20 mol / l, preferably 0.2 to 15 mol / l, particularly about 0.3 to 13 mol / l. . When the concentration is within the above range, the alkali metal compound and metal halide used in the reaction are sufficiently dissolved, and the treatment (reaction) can be performed efficiently.

  The concentration of the alkali metal compound in the solvent (reaction solution) is usually 0.05 to 5 mol / l, preferably 0.1 to 4 mol / l, particularly about 0.15 to 3.0 mol / l. When the concentration is within the above range, the reaction can proceed without excessively increasing the polarity of the reaction solution, and the activity of the solid component (active metal magnesium) and the molecular weight dispersion of the polysilane are suppressed from increasing. can do. The ratio of the alkali metal compound is about 0.1 to 30 parts by mass, preferably about 1 to 20 parts by mass, and more preferably about 5 to 20 parts by mass with respect to 100 parts by mass of the halosilane compound.

  The concentration of the metal halide in the solvent (reaction solution) is usually 0.01 to 6 mol / l, preferably 0.02 to 4 mol / l, particularly about 0.03 to 3 mol / l. When the concentration is within the above range, the reaction can be efficiently involved and the reaction can proceed sufficiently. The ratio of the metal halide is about 0.1 to 30 parts by mass, preferably about 1 to 20 parts by mass, and more preferably about 3 to 20 parts by mass with respect to 100 parts by mass of the halosilane compound.

  The reactor (reaction vessel) to be used is not particularly limited in shape and structure as long as it can be sealed. Further, the inside of the reaction vessel may be a dry atmosphere, but a dry inert gas (eg, nitrogen gas, helium gas, argon gas) atmosphere, particularly a deoxygenated and dried inert gas atmosphere is preferable.

  In the second step, the polymerization reaction of the halosilane compound (polysilane formation reaction) is usually in the temperature range from −20 ° C. to the boiling point of the solvent used, preferably 0 to 70 ° C., more preferably about 10 to 50 ° C. At a temperature of The reaction may be carried out under reduced pressure or increased pressure, but is usually carried out at normal pressure.

（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。 <Polysilane>
The polysilane obtained by the production method according to the present invention such as the first step and the second step is, for example,
Examples include polysilane compounds having 3 to 40 Si atoms, and polysilane compounds having 5 to 30 Si atoms are preferable.
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.

  As described above, the polysilane obtained by the production method according to the present invention such as the first step and the second step has a low molecular weight dispersity (Mw / Mn).

The polysilane obtained in the second step is stable in quality with little variation in molecular weight dispersity and yield even when the second step is repeated a plurality of times. In particular, as described above, since the cycloalkyl acetate represented by the above formula (S1) is used as a solvent, the polymerization activity of the halosilane compound is improved, and a polysilane having a low molecular weight dispersity (Mw / Mn), such as 4 In the following, preferably 1 to 3 polysilanes can be obtained.
Moreover, for example, the mass average molecular weight (Mw) is about 1000 to 100,000, preferably about 5000 to 80000, and more preferably about 6000 to 60000. In the present specification, the mass average molecular weight (Mw) is a measured value in terms of styrene of gel permeation chromatography (GPC). When polysilane is obtained in the first step, the mass average molecular weight of polysilane is approximately the same as that of the polysilane obtained in the second step, and can be selected from the above range.

  The polysilane obtained by the production method according to the present invention may contain a metal such as a solid component (active metal magnesium) or metal magnesium. In that case, it is preferable to separate these metal components. Usually, conventional separation and purification means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography and the like are used. It may be separated and purified by a combined means.

  In the purification by filtration, a separation medium commercially available for liquid filtration can be used. As a form of the filter, a membrane filter, a hollow fiber membrane filter, a pleated membrane filter, and a filter filled with a filter medium such as nonwoven fabric, cellulose, and diatomaceous earth can be used. The filter medium of the membrane filter, the hollow fiber membrane filter, and the pleated membrane filter may be made of polyolefin such as polyethylene, ultrahigh density polyethylene, and polypropylene, made of fluororesin such as polytetrafluoroethylene (PTFE), and made of nylon. preferable. In addition, these filters may contain an ion exchanger such as a cation exchange resin, or a cation charge control agent that generates a zeta potential in the solution to be filtered.

  The nominal pore diameter of the above filter is 1.0 μm or less, preferably 0.5 μm or less, more preferably 0.03 μm or less. The lower limit value of the nominal pore diameter of the filter is not particularly limited, but is usually 0.01 μm. The nominal pore diameter here is a nominal pore diameter indicating the separation performance of the filter, and is determined by a test method determined by the filter manufacturer, such as a bubble point test, a mercury intrusion test, a standard particle supplement test, etc. The hole diameter. When a commercial product is used, the value is described in the catalog data of the manufacturer. By reducing the nominal pore size to about 1.0 μm or less, the total content of the solid component (active metal magnesium) and metal magnesium after the solvent containing polysilane is passed through the filter once is reduced to 300 ppb or less. And the metal content in the polysilane can also be reduced. In order to further reduce the metal content in the solvent and polysilane, the liquid passing step may be performed twice or more. Thus, by reducing the metal content in polysilane, for example, when forming a coating film using polysilane as a raw material, it is easy to reduce outgas during film formation.

  The polysilane obtained by the production method according to the present invention has a low molecular weight dispersity (Mw / Mn) and forms a protective film or an interlayer film that protects various substrates (including metal oxide-containing films and various metal-containing films). It can be used as a composition for the intended use. 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 a photosensor (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). Further, a trench is formed in which a fine groove is formed on the surface of the semiconductor substrate, and the inside of the groove is filled with the composition according to the third aspect to electrically separate elements formed on both sides of the groove. It can be used as an application for forming an insulating film, a passivation film, a planarizing film, a protective film, etc. including an isolation structure.

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

[Comparative Example 1]
1st process; Production process of comparative active metal magnesium 1 and comparative polysilane 1 In a 1000 ml round flask equipped with a three-way cock, 65.9 g (2.71 mol) of granular magnesium (particle size 20-1000 μm) metal magnesium Then, 17.5 g of anhydrous lithium chloride (LiCl) and 11.3 g of anhydrous zinc chloride (ZnCl ₂ ) were charged, and the mixture was heated and reduced to 1 mmHg (= 133 kPa) at 50 ° C., and the mixture was dried. 500 ml of tetrahydrofuran (denoted as THF in the table) previously dried with sodium-benzophenone ketyl was added and stirred at room temperature for about 30 minutes. To this mixture, 115 g (600 mmol) of methylphenyldichlorosilane purified in advance by distillation was added by a syringe. In this case, the amount of magnesium used is 4.5 times the theoretical amount. About 3 hours after the start of stirring, the exotherm accompanying polymerization started and the exotherm continued for about 3 hours. After completion of the exotherm, the mixture was further stirred at room temperature for about 16 hours. After completion of the reaction, the reaction mixture was decanted and separated into a comparative solid component 1 (comparative active metal magnesium 1 component) and a liquid component (including methylphenylpolysilane).

  The obtained liquid component was extracted by adding 200 ml of 1N (= 1 mol / l) hydrochloric acid and 350 ml of toluene. After the toluene layer was washed 4 times with 150 ml of pure water, toluene was distilled off to obtain methylphenylpolysilane containing a low molecular weight substance. Comparative polysilane 1 was obtained by reprecipitation of methylphenylpolysilane with 100 ml of good solvent toluene and 500 ml of poor solvent 2-propanol. The weight average molecular weight Mw and molecular weight dispersity (Mw / Mn) of the comparative polysilane 1 are shown in Table 1.

[Comparative Example 2]
Second Step: Production of Comparative Polysilane 2 Using Comparative Active Metal Magnesium 1 Comparative Solid Component 1 (Comparative Active Metal Magnesium One Component) obtained in Comparative Example 1 was added to anhydrous lithium chloride (LiCl) 17.5 g, anhydrous chloride 11.3 g of zinc (ZnCl ₂ ) and 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl were added and stirred at room temperature for about 30 minutes. To this mixture, 115 g (600 mmol) of methylphenyldichlorosilane purified in advance by distillation was added with a syringe and stirred. Heat generation started immediately after the introduction of methylphenyldichlorosilane, and after 3 hours of heat generation, the mixture was further stirred at room temperature. As a result, it was confirmed that the polysilane polymerization reaction was completed after 8 hours. After completion of the reaction, the reaction mixture was decanted and separated into a comparative solid component 2 (comparative active metal magnesium component 2) and a liquid component (including methylphenylpolysilane).

  About the obtained liquid component, the refinement | purification process was performed like the comparative example 1, and the comparison polysilane 2 was obtained. The weight average molecular weight Mw and molecular weight dispersity (Mw / Mn) of the comparative polysilane 2 are shown in Table 1.

[Example 1]
First step: Production process of active metal magnesium 1 and polysilane 1 Solid component 1 (active metal magnesium 1 component) and liquid component were the same as in Comparative Example 1 except that tetrahydrofuran in Comparative Example 1 was changed to cyclohexyl acetate. (Including methylphenylpolysilane).

  The obtained liquid component was extracted by adding 200 ml of 1N (= 1 mol / l) hydrochloric acid and 350 ml of cyclohexyl acetate. After the cyclohexyl acetate layer was washed 4 times with 150 ml of pure water, cyclohexyl acetate was distilled off to obtain methylphenylpolysilane containing a low molecular weight substance. Polysilane 1 was obtained by reprecipitation of methylphenylpolysilane using 100 ml of a good solvent cyclohexyl acetate and 500 ml of a poor solvent 2-propanol. The weight average molecular weight Mw and the molecular weight dispersity (Mw / Mn) of the polysilane 1 are shown in Table 1.

[Example 2]
Second step: Production of polysilane 2 using comparatively active metal magnesium 1 Solid component 1 (active metal magnesium 1 component) and Comparative Example 2 were the same as in Comparative Example 2 except that tetrahydrofuran in Comparative Example 2 was changed to cyclohexyl acetate. A liquid component (including methylphenylpolysilane) was obtained.

  The liquid component was purified in the same manner as in Example 1 to obtain polysilane 2. The weight average molecular weight Mw and molecular weight dispersity (Mw / Mn) of the polysilane 2 are shown in Table 1.

[Example 3]
Second Step: Production of Polysilane 3 Using Active Metal Magnesium 1 Comparative Solid Component 1 (Comparative Active Metal Magnesium 1 Component) in Comparative Example 2 was obtained as Solid Component 1 (Active Metal Magnesium 1 Component) obtained in Example 1. The solid component 2 (active metal magnesium 2 component) and the liquid component (including methylphenylpolysilane) were obtained in the same manner as in Example 2 except that the change was made.

  The liquid component was purified in the same manner as in Example 1 to obtain polysilane 3. The weight average molecular weight Mw and molecular weight dispersity (Mw / Mn) of the polysilane 3 are shown in Table 1.

[Example 4]
(1) Production process of polysilane 4 In a round flask with an internal volume of 1000 ml equipped with a three-way cock, 65.9 g (2.71 mol) of granular magnesium magnesium (2.71 mol) and 5.53 g of iron triacetate ( 0.023 mol) was added and heated to 50 ° C. under reduced pressure to 1 mmHg (= 133 kPa) to dry the mixture. Then, dry argon gas was introduced into the reactor, and 500 ml of cyclohexyl acetate previously dried with sodium-benzophenone ketyl was added. In addition, the mixture was stirred at room temperature for about 30 minutes. To this mixture, 115 g (600 mmol) of methylphenyldichlorosilane purified in advance by distillation was added by a syringe and stirred at room temperature for about 22 hours.

  After completion of the reaction, 200 ml of 1N (= 1 mol / l) hydrochloric acid and 350 ml of cyclohexyl acetate were added for extraction. After the cyclohexyl acetate layer was washed 4 times with 150 ml of pure water, cyclohexyl acetate was distilled off to obtain methylphenylpolysilane containing a low molecular weight substance. Polysilane 4 was obtained by reprecipitation of methylphenyl polysilane using 100 ml of good solvent cyclohexyl acetate and 500 ml of poor solvent 2-propanol. The weight average molecular weight Mw and molecular weight dispersity (Mw / Mn) of the polysilane 4 are shown in Table 1.

From the results of Table 1, it was confirmed that in Examples 1 to 4 using cyclohexyl acetate as a solvent, a polysilane having a molecular weight dispersity of 2.8 or less was obtained. In particular, in Example 3 in which cyclohexyl acetate was used as a solvent in the first step and the second step, and an alkali metal compound (LiCl ₂ ) and a metal halide (ZnCl ₂ ) were used as catalysts, the effect was great. Similarly, in Example 4 in which cyclohexyl acetate was used as a solvent and an organometallic complex (ferric iron acetate) was used as a catalyst, the effect was great. On the other hand, in Comparative Example 1 in which polysilane was produced using tetrahydrofuran (THF), the molecular weight dispersity was as large as 4.5 or more, and the effect of narrowing the molecular weight distribution width was small.

Claims (4)

A method for producing a polysilane, comprising a step of reacting a metal magnesium component with a halosilane compound in a solvent containing a cycloalkyl acetate represented by the following formula (S1).

(In formula (S1), R ^s1 is an alkyl group having 1 to 3 carbon atoms, p is an integer of 1 to 6, and q is an integer of 0 to (p + 1).) The polysilane production method according to claim 1, wherein the reaction is caused by the presence of the following (I) or (II) together with the metal magnesium component.
(I) An alkali metal compound and a metal halide which is a halide of a metal other than an alkali metal, or (II) an organometallic complex represented by the following general formula (A1): M ^r L _{r / s} (A1)
(In the general formula (A1), ^Mr represents an r-valent metal cation, L represents an s-valent organic ligand, and r and s each independently represents an integer of 1 or more.)   The polysilane production method according to claim 1, wherein the metal magnesium component is an active metal magnesium component. A metal halide which is a halide of a metal other than (I) an alkali metal compound and an alkali metal is allowed to act on the halosilane compound together with the metal magnesium component in a solvent containing a cycloalkyl acetate represented by the following formula (S1). Process A to be reacted,
A process for removing the liquid component from the reaction mixture obtained by the process A, and a process for producing an active metal magnesium component.

(In formula (S1), R ^s1 is an alkyl group having 1 to 3 carbon atoms, p is an integer of 1 to 6, and q is an integer of 0 to (p + 1).)