JP2005343892A - Silicon compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new silicon compound having the ability to initiate a living radical polymerization of an addition-polymerizable monomer, to provide a polymer obtained using the silicon compound, and to obtain an organic-inorganic composite material with definite structure through offering the polymer. <P>SOLUTION: The new silicon compound is represented by formula(1)( wherein, R<SP>1</SP>is H, an alkyl, aryl or arylalkyl; R<SP>2</SP>and R<SP>3</SP>are each an alkyl, phenyl or cyclohexyl; and A is a group having the ability to initiate a polymerization of a monomer ). The polymer obtained by using this silicon compound is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a novel silicon compound having a polymerization initiating ability with respect to an addition polymerizable monomer, a method for producing the same, and a polymer obtained using the same.

Polymers have been used in various fields not only as general-purpose structure-forming materials but also as high-value-added materials having advanced functions and performance. Along with this, the importance of manufacturing polymer materials based on precise design is increasing. As an organic-inorganic composite material containing silsesquioxane as an inorganic component, a cage-type silsesquioxane derivative having a dimethylsiloxy group has attracted attention. This is because it is expected to be used as a precursor of an organic / inorganic hybrid material, a low dielectric material, an optical crystal, a material for forming a liquid crystal display element, etc., because the silsesquioxane derivative is silica. And having a structure similar to zeolite. A cage-type silsesquioxane in which a hydroxyl group (Non-Patent Document 1), an epoxy group (Non-Patent Document 2) or a methacryloyloxy group (Non-Patent Document 3) is bonded to a dimethylsiloxy group has been reported. Using these functional groups, so-called organic-inorganic composite materials of an organic polymer and silsesquioxane have been prepared. An organic-inorganic composite material can be obtained by radical polymerization of a cage-type silsesquioxane having a methacryloyloxy group alone or in the presence of another acrylic monomer.

In order to optimize the function of a polymer material according to the purpose, it is necessary to precisely analyze the molecular properties of the polymer and the properties of the molecular assembly. You must use coalescence. However, conventional organic-inorganic composite materials, including the above-described composite materials, do not contain a structure-controlled polymer as an organic component. Many of them are obtained by mechanical blending of silsesquioxane and an organic polymer, and therefore it is extremely difficult to control the structure of the complex as a molecular assembly. Thus, attempts have been made to control the structure of the polymer by using a polymerization initiator. Non-Patent Document 4 discloses that an α-haloester group is a good initiator for living radical polymerization with respect to a styrene monomer and a methacrylic acid monomer. Silsesquioxane derivatives having a group have not been known to date.
J. Am. Chem. Soc., 122 (2000), 6979- Chemistry of Materials, 8 (1996), 1592- Macromolecules, 29 (1996), 2327- Chem. Rev., 101 (2001), 2921-

The object of the present invention is to provide a novel silicon compound having a living radical polymerization initiating ability with respect to a wide range of addition polymerizable monomers, and a polymer obtained by using the same, thereby providing a conventional organic-inorganic It is to solve the above-mentioned problems concerning the composite material.

The present inventors have disclosed a double-decker (octacylsesquioxane cage represented by the following formula (1)) having a functional group having a living radical polymerization initiating ability for a wide range of addition polymerizable monomers. A silicon compound having a silsesquioxane skeleton having a structure in which two corners of the mold structure are broken was found. And it discovered that this silicon compound was effective in order to solve said problem, and completed this invention based on this knowledge. That is, the present invention has the following configuration.

ここに、それぞれのＲ^１は水素、炭素原子の数が１〜４５であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレン、またはシクロアルケニレンで置き換えられてもよいアルキル、置換もしくは非置換のアリール、および置換もしくは非置換のアリール基と任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるアリールアルキルから独立して選択される基であり；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；そして、Ａは単量体に対する重合開始能を有する基である。 [1] Silicon compound represented by formula (1):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; and A is a group capable of initiating polymerization on a monomer. .

[2] Each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyls composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; and A is the ability to initiate living radical polymerization on monomers A group having [1] The silicon compound according to claim.

ここに、Ｚ^１は２〜２０個の炭素原子を有するアルキレンまたは３〜８個の炭素原子を有するアルケニレンであり、そしてこれらのアルキレンおよびアルケニレンにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；Ｒ^４は水素、１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリール、または７〜２０個の炭素原子を有するアリールアルキルであり；Ｒ^５は１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリールまたは７〜２０個の炭素原子を有するアリールアルキルであり；そして、Ｘ^１はハロゲンである；

ここに、Ｚ^３は２〜１０個の炭素原子を有するアルキレンであり、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、または−ＣＯＯ−で置き換えられてもよく；Ｒ^６は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；Ｘ^２はハロゲンであり；ベンゼン環への−ＳＯ_２Ｘ^２の結合位置は、Ｚ^３の結合位置に対して、オルト位、メタ位またはパラ位であり、Ｒ^６の結合位置は、Ｚ^３および−ＳＯ_２Ｘ^２のそれぞれの結合位置を除く任意の位置である；

ここに、Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｚ^７は炭素原子の数が２〜１０であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり；Ｒ^７は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；Ｘ^３はハロゲンであり；そして、ベンゼン環へのＺ^５の結合位置はＺ^７の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^７のそれぞれの結合位置を除く任意の位置である；

ここに、Ｒ^８およびＲ^９は独立して水素、１〜１２個の炭素原子を有するアルキル、５〜１０個の炭素原子を有するシクロアルキルまたは６〜１０個の炭素原子を有するアリールであり、そしてＲ^８およびＲ^９は互いに結合してＮと共に環を形成してもよく；Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｚ^７は炭素原子の数が２〜１０であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり；Ｒ^７は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；そして、ベンゼン環へのＺ^５の結合位置はＺ^７の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^７のそれぞれの結合位置を除く任意の位置である。 [3] Each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Is a group independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl having carbon atoms, phenyl and cyclohexyl; and A is a formula (2-1), formula (2-2), formula (2-3) And a group represented by any one of formulas (2-4), [1] The silicon compound according to claim:

Where Z ¹ is alkylene having 2 to 20 carbon atoms or alkenylene having 3 to 8 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is replaced by —O—. R ⁴ is hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; R ⁵ is 1 Alkyl having -20 carbon atoms, aryl having 6-20 carbon atoms or arylalkyl having 7-20 carbon atoms; and X ¹ is halogen;

Here, Z ³ is an alkylene having 2 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or —COO—; R ⁶ is 1 to 3 A is an integer of 0 to 2; X ² is a halogen; the bonding position of —SO ₂ X ² to the benzene ring is relative to the bonding position of Z ³ ; In the ortho-position, meta-position or para-position, and the bonding position of R ⁶ is an arbitrary position excluding the bonding positions of Z ³ and —SO ₂ X ² ;

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁷ is 2 to 10 carbon atoms. Any alkylene —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁷ is alkyl having 1 to 3 carbon atoms; X ³ is a halogen; and the bonding position of Z ⁵ to the benzene ring is the meta position or the para position with respect to the bonding position of Z ⁷ , and the bonding position of R ⁷ is Z ⁵ and Z Any position except for each of the ⁷ binding positions;

Where R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms; R ⁸ and R ⁹ may be bonded to each other to form a ring with N; Z ⁵ may have 1 to 3 carbon atoms and any —CH ₂ — may be replaced by —O—. Z ⁷ is alkylene having 2 to 10 carbon atoms in which any —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁷ is Alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; and the bonding position of Z ⁵ to the benzene ring is meta or para with respect to the bonding position of Z ⁷ , R ⁷ is bonded to each of Z ⁵ and Z ⁷ It is an arbitrary position excluding the coupling position.

[4] Each R ¹ has ¹ to 30 hydrogen and carbon atoms, any hydrogen may be replaced with fluorine, and any —CH ₂ — is replaced with —O— or cycloalkylene The silicon compound according to item [3], which is a group independently selected from alkyls that may be present.

[5] Each R ¹ has 2 to 20 carbon atoms, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene. is the number of an alkenyl and carbon atoms is 1 to 20, optional hydrogen may be replaced by fluorine, and at least one -CH 2 _- is a radical independently selected from alkyl is replaced by cycloalkenylene The silicon compound according to item [3].

[6] each R ¹ is a group independently selected from phenyl and unsubstituted naphthyl in which any hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms; In the group alkyl, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O—, —CH═CH—, cycloalkylene, or phenylene; and When the phenyl has a plurality of substituents, the substituents may be the same group or different groups, and the silicon compound according to item [3].

[7] Each R ¹ is optionally substituted with any hydrogen or an alkyl having 1 to 12 carbon atoms, a phenyl group and the number of carbon atoms is 1 to 12, and any hydrogen is fluorine A group independently selected from phenylalkyl which may be substituted and composed of any —CH ₂ — with an alkylene group optionally substituted with —O—, —CH═CH— or cycloalkylene. Yes; in the alkyl that is the substituent of the phenyl group, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, —CH═CH—, cycloalkylene, or phenylene. And when the phenyl group has a plurality of substituents, these substituents may be the same group or different groups, [3] Silicon compound as described in.

[8] Each R ¹ has ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl and any hydrogen substituted with fluorine, 1 to 4 carbon atoms The phenyl group which may be substituted with alkyl, vinyl or methoxy has 1 to 8 carbon atoms and any —CH ₂ — may be replaced with —O—, —CH═CH— or cycloalkylene. A group independently selected from phenylalkyl composed of an alkylene group; and a plurality of phenyl or phenylalkyl phenyl groups When having a substituent, the substituents may be different groups may be the same group, [3] The silicon compound according to claim.

[9] All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl and any hydrogen substituted with fluorine, 1 to 4 carbon atoms The phenyl group which may be substituted with alkyl, vinyl or methoxy has 1 to 8 carbon atoms and any —CH ₂ — may be replaced with —O—, —CH═CH— or cycloalkylene. And the same group selected from phenylalkyls composed of alkylene groups; and phenyl or phenylalkyl phenyl groups When having a group, those substituents may be different groups may be the same group, [3] The silicon compound according to claim.

[10] The silicon compound according to item [3], wherein all R ¹ are phenyl.

[11] The silicon compound according to item [3], wherein all R ¹ is phenyl, and R ² and R ³ are methyl.

ここに、Ｚ^１は２〜２０個の炭素原子を有するアルキレンまたは３〜８個の炭素原子を有するアルケニレンであり、そしてこれらのアルキレンおよびアルケニレンにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；Ｒ^４は水素、１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリール、または７〜２０個の炭素原子を有するアリールアルキルであり；Ｒ^５は１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリールまたは７〜２０個の炭素原子を有するアリールアルキルであり；そして、Ｘ^１はハロゲンである。 [12] All R ^{1 s} have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl and any hydrogen substituted with fluorine, 1 to 4 carbon atoms The phenyl group which may be substituted with alkyl, vinyl or methoxy has 1 to 8 carbon atoms and any —CH ₂ — may be replaced with —O—, —CH═CH— or cycloalkylene. The same group selected from the group consisting of an alkylene group and a phenylalkyl; The substituents may be the same or different groups; and A is a group represented by the formula (2-1), according to item [3] Silicon compounds:

Where Z ¹ is alkylene having 2 to 20 carbon atoms or alkenylene having 3 to 8 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is replaced by —O—. R ⁴ is hydrogen, alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, or arylalkyl having 7-20 carbon atoms; R ⁵ is 1 Alkyl having -20 carbon atoms, aryl having 6-20 carbon atoms or arylalkyl having 7-20 carbon atoms; and X ¹ is halogen.

[13] All R ^{1 's} are phenyl; A is a group represented by the formula (2-1); and Z ¹ in the formula (2-1) has 2 to 10 carbon atoms, The silicon compound according to item [3], wherein any —CH ₂ — is alkylene which may be replaced by —O—.

[14] All R ¹ is phenyl; R ² and R ³ are methyl; A is a group represented by the formula (2-1); and in the formula (2-1), Z ¹ is —C ₂ H ₄ —, —C ₃ H ₆ — or —C ₂ H ₄ —O—C ₃ H ₆ —, R ⁴ and R ⁵ are methyl, and X ¹ is bromine [3 ] The silicon compound of a term.

ここに、Ｚ^３は２〜１０個の炭素原子を有するアルキレンであり、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、または−ＣＯＯ−で置き換えられてもよく；Ｒ^６は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；Ｘ^２はハロゲンであり；ベンゼン環への−ＳＯ_２Ｘ^２の結合位置は、Ｚ^３の結合位置に対して、オルト位、メタ位またはパラ位であり、Ｒ^６の結合位置は、Ｚ^３および−ＳＯ_２Ｘ^２のそれぞれの結合位置を除く任意の位置である。 [15] All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl and any hydrogen substituted with fluorine, 1 to 4 carbon atoms The phenyl group which may be substituted with alkyl, vinyl or methoxy has 1 to 8 carbon atoms and any —CH ₂ — may be replaced with —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; phenyl or phenylalkyl of phenylalkyl is a plurality of substituents When they are present, the substituents may be the same or different; and A is a group represented by the formula (2-2), according to the item [3] Silicon compounds:

Here, Z ³ is an alkylene having 2 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or —COO—; R ⁶ is 1 to 3 A is an integer of 0 to 2; X ² is a halogen; the bonding position of —SO ₂ X ² to the benzene ring is relative to the bonding position of Z ³ ; In the ortho-position, meta-position or para-position, the bond position of R ⁶ is an arbitrary position excluding the bond positions of Z ³ and —SO ₂ X ² .

[16] All R ¹ is phenyl; A is a group represented by the formula (2-2); Z ³ in the formula (2-2) is —C ₂ H ₄ —Z ⁹ ; Z ⁹ is a single bond, or the number of carbon atoms is 1 to 8, and any —CH ₂ — is alkylene which may be replaced by —O— or —COO—, Silicon compound.

[17] All R ¹ is phenyl; R ² and R ³ are methyl; A is a group represented by formula (2-2); and in formula (2-2), Z ³ is The silicon compound according to item [3], which is —C ₂ H ₄ —, X ² is chlorine or bromine, and a is 0.

ここに、Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｚ^７は炭素原子の数が２〜１０であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり；Ｒ^７は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；Ｘ^３はハロゲンであり；そして、ベンゼン環へのＺ^５の結合位置はＺ^７の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^７のそれぞれの結合位置を除く任意の位置である。 [18] All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl and any hydrogen substituted with fluorine, 1 to 4 carbon atoms The phenyl group which may be substituted with alkyl, vinyl or methoxy has 1 to 8 carbon atoms and any —CH ₂ — may be replaced with —O—, —CH═CH— or cycloalkylene. The same group selected from the group consisting of an alkylene group and a phenylalkyl; The substituents may be the same group or different groups; and A is a group represented by the formula (2-3), according to item [3] Silicon compounds:

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁷ is 2 to 10 carbon atoms. Any alkylene —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁷ is an alkyl having 1 to 3 carbon atoms; X ³ is a halogen; and the bonding position of Z ⁵ to the benzene ring is the meta position or the para position with respect to the bonding position of Z ⁷ , and the bonding position of R ⁷ is Z ⁵ and Z ^{7 is} an arbitrary position excluding each coupling position.

[19] all R ¹ is phenyl; A is a group represented by formula (2-3); Z ⁷ in formula (2-3) is —C ₂ H ₄ —Z ¹⁰ ; and The item [3], wherein Z ¹⁰ is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — may be replaced by —O—, —COO— or —OCO—. The silicon compound as described in.

[20] All R ¹ is phenyl; R ² and R ³ are methyl; A is a group represented by formula (2-3); and in formula (2-3), Z ⁵ is The silicon compound according to item [3], which is —CH ₂ —, Z ⁷ is —C ₂ H ₄ —, X ³ is chlorine or bromine, and a is 0.

ここに、Ｒ^８およびＲ^９は独立して水素、１〜１２個の炭素原子を有するアルキル、５〜１０個の炭素原子を有するシクロアルキルまたは６〜１０個の炭素原子を有するアリールであり、そしてＲ^８およびＲ^９は互いに結合してＮと共に環を形成してもよく；Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｚ^７は炭素原子の数が２〜１０であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり；Ｒ^７は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；そして、ベンゼン環へのＺ^５の結合位置はＺ^７の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^７のそれぞれの結合位置を除く任意の位置である。 [21] All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl and any hydrogen substituted with fluorine, 1 to 4 carbon atoms The phenyl group which may be substituted with alkyl, vinyl or methoxy has 1 to 8 carbon atoms and any —CH ₂ — may be replaced with —O—, —CH═CH— or cycloalkylene. The same group selected from the group consisting of an alkylene group and phenylalkyl; the phenyl group of phenyl or phenylalkyl has a plurality of substituents; The substituents may be the same group or different groups; and A is a group represented by the formula (2-4), according to item [3] Silicon compounds:

Where R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms; R ⁸ and R ⁹ may be bonded to each other to form a ring with N; Z ⁵ may have 1 to 3 carbon atoms and any —CH ₂ — may be replaced by —O—. Z ⁷ is alkylene having 2 to 10 carbon atoms in which any —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁷ is Alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; and the bonding position of Z ⁵ to the benzene ring is meta or para with respect to the bonding position of Z ⁷ , R ⁷ is bonded to each of Z ⁵ and Z ⁷ It is an arbitrary position excluding the coupling position.

[22] All R ¹ are phenyl; A is a group represented by the formula (2-4); and in the formula (2-4), Z ⁷ is —C ₂ H ₄ —Z ¹⁰ , Z ¹⁰ is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — may be replaced by —O—, —COO— or —OCO—, [3] The silicon compound as described in.

[23] All R ¹ is phenyl; R ² and R ³ are methyl; A is a group represented by formula (2-4); and in formula (2-4), R ⁸ and The silicon compound according to item [3], wherein R ⁹ is ethyl, Z ⁵ is —CH ₂ —, Z ⁷ is —C ₂ H ₄ —, and a is 0.

ここに、それぞれのＲ^１は水素、炭素原子の数が１〜４５であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレン、またはシクロアルケニレンで置き換えられてもよいアルキル、置換もしくは非置換のアリール、および置換もしくは非置換のアリール基と任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるアリールアルキルから独立して選択される基であり；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；そして、Ａ^１は式（２−１−１）で示される基である：

ここに、Ｚ^２は単結合、または１〜１８個の炭素原子を有するアルキレン、または２〜６個の炭素原子を有するアルケニレンであり、そしてこれらのアルキレンおよびアルケニレンにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；Ｒ^４は水素、１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリール、または７〜２０個の炭素原子を有するアリールアルキルであり；Ｒ^５は１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリールまたは７〜２０個の炭素原子を有するアリールアルキルであり；そして、Ｘ^１はハロゲンである；
＜工程（ａ）＞
式（３−１）で示される化合物に式（４）で示される化合物を反応させることにより、式（５）で示される化合物を得る工程：

ここに、これらの式において、Ｒ^１、Ｒ^２およびＲ^３は式（１−１）におけるこれらの記号と同一の意味を有し；Ｍは１価のアルカリ金属原子である；
＜工程（ｂ）＞
遷移金属触媒の存在下で、式（５）で示される化合物に式（６）で示される化合物を反応させ、式（７）で示されるケイ素化合物を得る工程：

ここに、これらの式におけるＺ^２は式（２−１−１）におけるＺ^２と同一の意味を有し、式（７）におけるＲ^１、Ｒ^２およびＲ^３は式（１−１）におけるこれらの記号と同一の意味を有する；
＜工程（ｃ）＞
式（７）で示される化合物に、式（８）で示される化合物を反応させ、式（１−１）で示されるケイ素化合物を得る工程：

ここに、Ｒ^４、Ｒ^５およびＸ^１は式（２−１−１）におけるこれらの記号と同一の意味を有し；Ｘはハロゲンである。 [24] A silicon compound represented by the formula (1-1), wherein the compound represented by the formula (5) is obtained by the step (a), and the step (c) is carried out after the step (b). Manufacturing method:

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; and A ¹ is a group of formula (2-1-1):

Here, Z ² is a single bond, or alkylene having 1 to 18 carbon atoms, or alkenylene having 2 to 6 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is — May be replaced by O-; R ⁴ is hydrogen, alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, or arylalkyl having 7-20 carbon atoms R ⁵ is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms or arylalkyl having 7 to 20 carbon atoms; and X ¹ is halogen;
<Process (a)>
A step of obtaining a compound represented by the formula (5) by reacting the compound represented by the formula (3-1) with the compound represented by the formula (4):

Here, in these formulas, R ¹ , R ² and R ³ have the same meaning as those symbols in formula (1-1); M is a monovalent alkali metal atom;
<Step (b)>
A step of reacting a compound represented by the formula (5) with a compound represented by the formula (6) in the presence of a transition metal catalyst to obtain a silicon compound represented by the formula (7):

Here, ^{Z 2} in these formulas have the same meanings as ^{Z 2} in Formula ^{(2-1-1), R 1, R} 2 and ^{R 3} in the formula (7) in Formula (1-1) Has the same meaning as these symbols;
<Step (c)>
A step of reacting a compound represented by the formula (7) with a compound represented by the formula (8) to obtain a silicon compound represented by the formula (1-1):

Here, R ⁴ , R ⁵ and X ¹ have the same meaning as these symbols in formula (2-1-1); X is halogen.

[25] All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms A phenyl group which may be substituted with alkyl, vinyl or methoxy having 1 to 8 carbon atoms and any —CH ₂ — may be replaced with —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; phenyl or phenylalkyl of phenylalkyl is a plurality of substituents When having, those substituents same group in a well be a different group may be; independently alkyl, cyclohexyl, phenyl and cycloalkyl having R ² and R ³ to 8 carbon atoms The production method according to item [24], which is a group selected as above.

[26] The production method of the item [24], wherein all R ¹ is phenyl; and R ² and R ³ are methyl.

ここに、それぞれのＲ^１は水素、炭素原子の数が１〜４５であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレン、またはシクロアルケニレンで置き換えられてもよいアルキル、置換もしくは非置換のアリール、および置換もしくは非置換のアリール基と任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるアリールアルキルから独立して選択される基であり；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；そして、Ａ^１は式（２−１−１）で示される基である：

ここに、Ｚ^２は単結合、または１〜１８個の炭素原子を有するアルキレン、または２〜６個の炭素原子を有するアルケニレンであり、そしてこれらのアルキレンおよびアルケニレンにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；Ｒ^４は水素、１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリール、または７〜２０個の炭素原子を有するアリールアルキルであり；Ｒ^５は１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリールまたは７〜２０個の炭素原子を有するアリールアルキルであり；そして、Ｘ^１はハロゲンである；
＜工程（ｄ）＞
式（３−２）で示される化合物に式（４）で示される化合物を反応させることにより、式（５）で示される化合物を得る工程：

ここに、これらの式におけるＲ^１、Ｒ^２およびＲ^３は、式（１−１）におけるこれらの記号と同一の意味を有する。
＜工程（ｂ）＞
遷移金属触媒の存在下で、式（５）で示される化合物に式（６）で示される化合物を反応させ、式（７）で示されるケイ素化合物を得る工程：

ここに、これらの式におけるＺ^２は式（２−１−１）におけるＺ^２と同一の意味を有し、式（７）におけるＲ^１、Ｒ^２およびＲ^３は式（１−１）におけるこれらの記号と同一の意味を有する；
＜工程（ｃ）＞
式（７）で示される化合物に、式（８）で示される化合物を反応させ、式（１−１）で示されるケイ素化合物を得る工程：

ここに、Ｒ^４、Ｒ^５およびＸ^１は式（２−１−１）におけるこれらの記号と同一の意味を有し；Ｘはハロゲンである。 [27] A silicon compound represented by the formula (1-1), wherein the compound represented by the formula (5) is obtained by the step (d), and the step (c) is carried out after the step (b). Manufacturing method:

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; and A ¹ is a group of formula (2-1-1):

Here, Z ² is a single bond, or alkylene having 1 to 18 carbon atoms, or alkenylene having 2 to 6 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is — May be replaced by O-; R ⁴ is hydrogen, alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, or arylalkyl having 7-20 carbon atoms R ⁵ is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms or arylalkyl having 7 to 20 carbon atoms; and X ¹ is halogen;
<Step (d)>
A step of obtaining a compound represented by the formula (5) by reacting a compound represented by the formula (3-2) with a compound represented by the formula (4):

Here, R ¹ , R ² and R ³ in these formulas have the same meaning as those symbols in formula (1-1).
<Step (b)>
A step of reacting a compound represented by the formula (5) with a compound represented by the formula (6) in the presence of a transition metal catalyst to obtain a silicon compound represented by the formula (7):

Here, ^{Z 2} in these formulas have the same meanings as ^{Z 2} in Formula ^{(2-1-1), R 1, R} 2 and ^{R 3} in the formula (7) in Formula (1-1) Has the same meaning as these symbols;
<Step (c)>
A step of reacting a compound represented by the formula (7) with a compound represented by the formula (8) to obtain a silicon compound represented by the formula (1-1):

Here, R ⁴ , R ⁵ and X ¹ have the same meaning as these symbols in formula (2-1-1); X is halogen.

[28] All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, phenyl optionally substituted with halogen, methyl or methoxy, unsubstituted naphthyl, and optionally hydrogen substituted with fluorine, 1 to 4 carbon atoms The number of carbon atoms is 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; phenyl or phenylalkyl of phenylalkyl is a plurality of substituents When having, those substituents same group in a well be a different group may be; independently alkyl, cyclohexyl, phenyl and cycloalkyl having R ² and R ³ to 8 carbon atoms The production method according to item [27], which is a group selected as above.

[29] The production method according to item [27], wherein all R ¹ is phenyl; and R ² and R ³ are methyl.

ここに、それぞれのＲ^１は水素、炭素原子の数が１〜４５であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレンまたはシクロアルケニレンで置き換えられてもよいアルキル、置換もしくは非置換のアリール、および置換もしくは非置換のアリール基と任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるアリールアルキルから独立して選択される基であり；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；そして、Ａ^３は式（２−３−１）で示される基である：

ここに、Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｚ^６は単結合、または炭素原子の数が１〜８であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり；Ｒ^７は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；Ｘ^３はハロゲンであり；そして、ベンゼン環へのＺ^５の結合位置はＺ^６の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^６のそれぞれの結合位置を除く任意の位置である；
＜工程（ｅ）＞
式（４）で示される化合物と、式（３−１）で示される化合物、または式（３−２）で示される化合物を反応させて、式（５）で示されるケイ素化合物を得る工程：

ここに、これらの式におけるＲ^１、Ｒ^２およびＲ^３は式（１−３）におけるこれらの記号と同一の意味を有し；Ｍは１価のアルカリ金属原子である；
＜工程（ｆ）＞
式（５）で示される化合物と式（２−３−２）で示される化合物を反応させ、式（１−３）で示されるケイ素化合物を得る工程：

ここに、Ｚ^５、Ｚ^６、Ｒ^７、ａおよびＸ^３は式（２−３−１）におけるこれらの記号と同一の意味を有し；ベンゼン環へのＺ^５およびＲ^７の結合位置は式（２−３−１）におけるこれらの結合位置と同一である。 [30] A method for producing a silicon compound represented by the formula (1-3), wherein the step (f) is performed after the step (e):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Alkyl which may be replaced with cycloalkylene or cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — —O—, —CH═CH— or a group independently selected from arylalkyl composed of an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 carbons; A group independently selected from alkyl, phenyl and cyclohexyl having an atom; and A ³ is a group of formula (2-3-1):

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁶ is a single bond or 1 carbon atom. a 8 arbitrary -CH ₂ - -O -, - COO- or -OCO- in be replaced may be alkylene; ^{R 7} is alkyl having 1-3 carbon atoms; a Is an integer from 0 to 2; X ³ is a halogen; and the bonding position of Z ⁵ to the benzene ring is meta or para to the bonding position of Z ⁶ , and the bonding position of R ⁷ is Any position except for the respective bonding positions of Z ⁵ and Z ⁶ ;
<Process (e)>
A step of reacting a compound represented by the formula (4) with a compound represented by the formula (3-1) or a compound represented by the formula (3-2) to obtain a silicon compound represented by the formula (5):

Wherein R ¹ , R ² and R ³ in these formulas have the same meaning as these symbols in formula (1-3); M is a monovalent alkali metal atom;
<Step (f)>
A step of reacting a compound represented by the formula (5) with a compound represented by the formula (2-3-2) to obtain a silicon compound represented by the formula (1-3):

Here, Z ⁵ , Z ⁶ , R ⁷ , a and X ³ have the same meaning as these symbols in formula (2-3-1); the bonding position of Z ⁵ and R ⁷ to the benzene ring is These bond positions are the same as those in formula (2-3-1).

[31] All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms The phenyl group which may be substituted with alkyl, vinyl or methoxy having 1 to 8 carbon atoms and —CH ₂ — may be replaced with —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; the phenyl group of phenyl or phenylalkyl is a plurality of substituents When having, those substituents same group in a well be a different group may be; independently alkyl, cyclohexyl, phenyl and cycloalkyl having R ² and R ³ to 8 carbon atoms [30] The production method according to item [30], wherein

[32] The production method according to the item [30], wherein all R ¹ is phenyl; and R ² and R ³ are methyl.

ここに、それぞれのＲ^１は水素、炭素原子の数が１〜４５であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレン、またはシクロアルケニレンで置き換えられてもよいアルキル、置換もしくは非置換のアリール、および置換もしくは非置換のアリール基と任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるアリールアルキルから独立して選択される基であり；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；Ａ^４は式（２−４−１）で示される基である：

ここに、Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｚ^６は単結合、または炭素原子の数が１〜８であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり；Ｒ^８およびＲ^９は独立して水素、１〜１２個の炭素原子を有するアルキル、５〜１０個の炭素原子を有するシクロアルキルまたは６〜１０個の炭素原子を有するアリールであり、そしてＲ^８およびＲ^９は互いに結合してＮと共に環を形成してもよく；Ｒ^７は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；そして、ベンゼン環へのＺ^５の結合位置はＺ^６の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^６のそれぞれの結合位置を除く任意の位置である；

ここに、Ｒ^１、Ｒ^２およびＲ^３は式（１−４）におけるこれらの記号と同一の意味を有し；Ａ^３は式（２−３−１）で示される基である；

ここに、Ｚ^５、Ｚ^６、Ｒ^７およびａは式（２−４−１）におけるこれらの記号と同一の意味を有し；Ｘ^３はハロゲンであり；ベンゼン環へのＺ^５およびＲ^７の結合位置は式（２−４−１）におけるこれらの結合位置と同一である；

ここに、Ｒ^８およびＲ^９は式（２−４−１）におけるこれらの記号と同一の意味を有し；Ｍ^１は周期律表第１族または第２族の金属元素であり；そして、ｐはＭ^１の原子価と同じ値である。 [33] A method for producing a silicon compound represented by formula (1-4), comprising reacting a silicon compound represented by formula (1-3) with a compound represented by formula (9):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having carbon atoms; A ⁴ is a group of formula (2-4-1):

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms and any —CH ₂ — may be replaced by —O—; Z ⁶ is a single bond or 1 carbon atom. a 8 arbitrary -CH ₂ - -O -, - COO-, or replaced by -OCO- be alkylene be; ^{R 8} and ^{R 9} are independently hydrogen, 1 to 12 carbons Alkyl having atoms, cycloalkyl having 5 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms, and R ⁸ and R ⁹ may be bonded together to form a ring with N R ⁷ is alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; and the bond position of Z ⁵ to the benzene ring is meta-position to the bond position of Z ⁶ or In the para position, the bonding position of R ⁷ is Z ⁵ and Z Any position except for each of the ⁶ binding positions;

Here, R ¹ , R ² and R ³ have the same meaning as these symbols in formula (1-4); A ³ is a group represented by formula (2-3-1);

Where Z ⁵ , Z ⁶ , R ⁷ and a have the same meaning as these symbols in formula (2-4-1); X ³ is halogen; Z ⁵ and R ⁷ to the benzene ring Are the same as those in formula (2-4-1);

Where R ⁸ and R ⁹ have the same meaning as these symbols in formula (2-4-1); M ¹ is a metal element of Group 1 or Group 2 of the Periodic Table; p is the same value as the valence of M ¹ .

[34] All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, phenyl optionally substituted with halogen, methyl or methoxy, unsubstituted naphthyl, and optionally hydrogen substituted with fluorine, 1 to 4 carbon atoms The number of carbon atoms is 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; the phenyl group of phenyl or phenylalkyl is a plurality of substituents When having, those substituents same group in a well be a different group may be; independently alkyl, cyclohexyl, phenyl and cycloalkyl having R ² and R ³ to 8 carbon atoms The production method according to the item [33], which is a group selected as above.

[35] The production method of the item [33], wherein all R ¹ is phenyl; and R ² and R ³ are methyl.

ここに、それぞれのＲ^１は水素、炭素原子の数が１〜４５であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレン、またはシクロアルケニレンで置き換えられてもよいアルキル、置換もしくは非置換のアリール、および置換もしくは非置換のアリール基と任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるアリールアルキルから独立して選択される基であり；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；Ａ^１は式（２−１−１）で示される基である：

ここに、Ｚ^２は単結合、または１〜１８個の炭素原子を有するアルキレン、または２〜６個の炭素原子を有するアルケニレンであり、そしてこれらのアルキレンおよびアルケニレンにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；Ｒ^４は水素、１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリール、または７〜２０個の炭素原子を有するアリールアルキルであり；Ｒ^５は１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリールまたは７〜２０個の炭素原子を有するアリールアルキルであり；そして、Ｘ^１はハロゲンである；
＜工程（ｇ）＞
遷移金属触媒の存在下で、式（４）で示される化合物と式（２−１−２）で示される化合物とを反応させて、式（２−１−３）で示される化合物を得る工程：

ここに、これらの式におけるＲ^２およびＲ^３は、式（１−１）におけるこれらの記号と同一の意味を有し；Ｚ^２、Ｒ^４、Ｒ^５およびＸ^１は式（２−１−１）におけるこれらの記号と同一の意味を有する；
＜工程（ｈ）＞
式（２−１−３）で示される化合物と、式（３−１）で示される化合物または式（３−２）で示される化合物とを反応させることにより式（１−１）で示されるケイ素化合物を得る工程：

ここに、これらの式におけるＲ^１は、式（１−１）におけるＲ^１と同一の意味を有し；Ｍは１価のアルカリ金属原子である。 [36] A method for producing a silicon compound represented by the formula (1-1), wherein the step (h) is performed after the step (g):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; A ¹ is a group of formula (2-1-1):

Here, Z ² is a single bond, or alkylene having 1 to 18 carbon atoms, or alkenylene having 2 to 6 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is — May be replaced by O-; R ⁴ is hydrogen, alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, or arylalkyl having 7-20 carbon atoms R ⁵ is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms or arylalkyl having 7 to 20 carbon atoms; and X ¹ is halogen;
<Process (g)>
A step of obtaining a compound represented by the formula (2-1-3) by reacting a compound represented by the formula (4) with a compound represented by the formula (2-1-2) in the presence of a transition metal catalyst. :

Here, R ² and R ³ in these formulas have the same meaning as those symbols in formula (1-1); Z ² , R ⁴ , R ⁵ and X ¹ are the formulas (2-1-1- Have the same meaning as these symbols in 1);
<Step (h)>
By reacting the compound represented by the formula (2-1-3) with the compound represented by the formula (3-1) or the compound represented by the formula (3-2), it is represented by the formula (1-1). Obtaining a silicon compound:

Here, R ¹ in these formulas has the same meaning as R ¹ in formula (1-1); M is a monovalent alkali metal atom.

[37] All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms The number of carbon atoms is 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; phenyl or phenylalkyl of phenylalkyl is a plurality of substituents When having, those substituents same group in a well be a different group may be; independently alkyl, cyclohexyl, phenyl and cycloalkyl having R ² and R ³ to 8 carbon atoms The production method according to item [36], which is a group selected as above.

[38] The production method according to the item [36], wherein all R ¹ is phenyl; and R ² and R ³ are methyl.

ここに、それぞれのＲ^１は水素、炭素原子の数が１〜４５であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレン、またはシクロアルケニレンで置き換えられてもよいアルキル、置換もしくは非置換のアリール、および置換もしくは非置換のアリール基と任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるアリールアルキルから独立して選択される基であり；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；そして、Ａ^２は式（２−２−１）で示される基である：

ここに、Ｚ^４は単結合または１〜８個の炭素原子を有するアルキレンであり、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、または−ＣＯＯ−で置き換えられてもよく；Ｒ^６は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；Ｘ^２はハロゲンであり；ベンゼン環への−ＳＯ_２Ｘ^２の結合位置は、Ｚ^４の結合位置に対して、オルト位、メタ位またはパラ位であり、Ｒ^６の結合位置は、Ｚ^４および−ＳＯ_２Ｘ^２のそれぞれの結合位置を除く任意の位置である；
＜工程（ｉ）＞
遷移金属触媒の存在下で、式（４）で示される化合物と式（２−２−２）で示される化合物とを反応させ、式（２−２−３）で示される化合物を得る工程：

ここに、これらの式におけるＲ^２およびＲ^３は、式（１−２）におけるこれらの記号と同一の意味を有し；Ｚ^４、Ｒ^６、ａおよびＸ^２は、式（２−２−１）におけるこれらの記号と同一の意味を有し；ベンゼン環への−ＳＯ_２Ｘ^２およびＲ^６の結合位置は式（２−２−１）におけるこれらの結合位置と同一である；
＜工程（ｊ）＞
式（２−２−３）で示される化合物と、式（３−１）で示される化合物または式（３−２）で示される化合物とを反応させて、式（１−２）で示されるケイ素化合物を得る工程：

ここに、これらの式におけるＲ^１は、式（１−１）におけるＲ^１と同一の意味を有し；Ｍは１価のアルカリ金属原子である。 [39] A method for producing a silicon compound represented by formula (1-2), wherein step (j) is performed after step (i):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having carbon atoms; and A ² is a group of formula (2-2-1):

Here, Z ⁴ is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or —COO—; R ⁶ is An alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; X ² is a halogen; and the bonding position of —SO ₂ X ² to the benzene ring is the bonding position of Z ^4. On the other hand, in the ortho-position, meta-position or para-position, the bonding position of R ⁶ is an arbitrary position excluding the bonding positions of Z ⁴ and —SO ₂ X ² ;
<Process (i)>
A step of reacting a compound represented by the formula (4) with a compound represented by the formula (2-2-2) in the presence of a transition metal catalyst to obtain a compound represented by the formula (2-2-3):

Here, R ² and R ³ in these formulas have the same meaning as those symbols in formula (1-2); Z ⁴ , R ⁶ , a and X ² are the formulas (2-2-2- Have the same meaning as these symbols in 1); the bonding positions of —SO ₂ X ² and R ⁶ to the benzene ring are the same as these bonding positions in formula (2-2-1);
<Process (j)>
A compound represented by the formula (2-2-3) is reacted with a compound represented by the formula (3-1) or a compound represented by the formula (3-2), thereby being represented by the formula (1-2). Obtaining a silicon compound:

Here, R ¹ in these formulas has the same meaning as R ¹ in formula (1-1); M is a monovalent alkali metal atom.

[40] All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkyl which may be replaced with alkylene or cycloalkenylene, phenyl where optional hydrogen may be replaced with halogen, methyl or methoxy, unsubstituted naphthyl, and optional hydrogen having fluorine, 1 to 4 carbon atoms The phenyl group which may be substituted with alkyl, vinyl or methoxy has 1 to 8 carbon atoms and any —CH ₂ — may be replaced with —O—, —CH═CH— or cycloalkylene. The same group selected from the group consisting of an alkylene group and a phenylalkyl; When, those substituents same group in a well be a different group may be; independently alkyl, cyclohexyl, phenyl and cycloalkyl having R ² and R ³ to 8 carbon atoms The production method according to the item [39], which is a group selected as above.

[41] The production method of the item [39], wherein all R ¹ is phenyl; and R ² and R ³ are methyl.

ここに、それぞれのＲ^１は水素、炭素原子の数が１〜４５であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレン、またはシクロアルケニレンで置き換えられてもよいアルキル、置換もしくは非置換のアリール、および置換もしくは非置換のアリール基と任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるアリールアルキルから独立して選択される基であり；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；そして、Ａ^３は式（２−３−１）で示される基である：

ここに、Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｚ^６は単結合、または炭素原子の数が１〜８であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり；Ｒ^７は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；Ｘ^３はハロゲンであり；そして、ベンゼン環へのＺ^５の結合位置はＺ^６の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^６のそれぞれの結合位置を除く任意の位置である；
＜工程（ｋ）＞
遷移金属触媒の存在下で、式（４）で示される化合物と式（２−３−２）で示される化合物とを反応させて、式（２−３−３）で示される化合物を得る工程：

ここに、これらの式におけるＲ^２およびＲ^３は、式（１−３）におけるこれらの記号と同一の意味を有し；Ｚ^５、Ｚ^６、Ｒ^７、ａ、およびＸ^３は、式（２−３−１）におけるこれらの記号と同一の意味を有し；ベンゼン環へのＺ^５およびＲ^７の結合位置は式（２−３−１）におけるこれらの結合位置と同一である；
＜工程（ｌ）＞
式（２−３−３）で示される化合物と、式（３−１）で示される化合物または式（３−２）で示される化合物とを反応させることで、式（１−３）で示されるケイ素化合物を得る工程：

ここに、これらの式におけるＲ^１は、式（１−３）におけるＲ^１と同一の意味を有し；Ｍは１価のアルカリ金属原子である。 [42] A method for producing a silicon compound represented by formula (1-3), wherein step (l) is performed after step (k):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; and A ³ is a group of formula (2-3-1):

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁶ is a single bond or 1 carbon atom. a 8 arbitrary -CH ₂ - -O -, - COO- or -OCO- in be replaced may be alkylene; ^{R 7} is alkyl having 1-3 carbon atoms; a Is an integer from 0 to 2; X ³ is a halogen; and the bonding position of Z ⁵ to the benzene ring is meta or para to the bonding position of Z ⁶ , and the bonding position of R ⁷ is Any position except for the respective bonding positions of Z ⁵ and Z ⁶ ;
<Process (k)>
A step of reacting a compound represented by the formula (4) with a compound represented by the formula (2-3-2) in the presence of a transition metal catalyst to obtain a compound represented by the formula (2-3-3). :

Here, R ² and R ³ in these formulas have the same meaning as these symbols in formula (1-3); Z ⁵ , Z ⁶ , R ⁷ , a, and X ³ are represented by the formula ( Have the same meaning as these symbols in 2-3-1); the bonding positions of Z ⁵ and R ⁷ to the benzene ring are the same as these bonding positions in formula (2-3-1);
<Step (l)>
By reacting the compound represented by the formula (2-3-3) with the compound represented by the formula (3-1) or the compound represented by the formula (3-2), it is represented by the formula (1-3). Obtaining a silicon compound:

Here, R ¹ in these formulas has the same meaning as R ¹ in formula (1-3); M is a monovalent alkali metal atom.

[43] All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms The number of carbon atoms is 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; the phenyl group of phenyl or phenylalkyl is a plurality of substituents When having, those substituents same group in a well be a different group may be; independently alkyl, cyclohexyl, phenyl and cycloalkyl having R ² and R ³ to 8 carbon atoms The production method according to item [42], which is a group selected as above.

[44] The production method of the item [42], wherein all R ¹ is phenyl; and R ² and R ³ are methyl.

[45] A polymer obtained by polymerizing an addition polymerizable monomer using the silicon compound according to the item [1] as an initiator and a transition metal complex as a catalyst.

[46] A polymer obtained by polymerizing an addition polymerizable monomer using the silicon compound according to the item [3] as an initiator and a transition metal complex as a catalyst.

ここに、すべてのＲ^１１は炭素原子の数が１〜８であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレン、またはシクロアルケニレンで置き換えられてもよいアルキル、任意の水素がハロゲン、メチルまたはメトキシで置き換えられてもよいフェニル、非置換のナフチル、および任意の水素がフッ素、１〜４個の炭素原子を有するアルキル、ビニルまたはメトキシで置き換えられてもよいフェニル基と炭素原子の数が１〜８であって任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるフェニルアルキルから選択される同一の基であり；フェニルまたはフェニルアルキルのフェニル基が複数の置換基を有するときは、それらの置換基は同一の基であってもよいし異なる基であってもよく；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；そして、Ｂ^１は式（２−１−Ｐ）で示される基である：

ここに、Ｚ^１は２〜２０個の炭素原子を有するアルキレンまたは３〜８個の炭素原子を有するアルケニレンであり、これらのアルキレンおよびアルケニレンにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；Ｒ^４は水素、１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリールまたは７〜２０個の炭素原子を有するアリールアルキルであり；Ｒ^５は１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリールまたは７〜２０個の炭素原子を有するアリールアルキルであり；Ｘ^１はハロゲンであり；そして、Ｐ^１は付加重合性単量体の重合によって得られる構成単位の連鎖である。 [47] A polymer represented by the formula (P-1):

Here, all R ¹¹ have 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms The number of carbon atoms is 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; the phenyl or phenylalkyl phenyl group is substituted more than once When having, those substituents may be the same group in a may be different groups; R ² and R ³ are alkyl having 1 to 8 carbon atoms, from cyclohexyl phenyl and cycloalkyl An independently selected group; and B ¹ is a group of formula (2-1-P):

Here, Z ¹ is alkylene having 2 to 20 carbon atoms or alkenylene having 3 to 8 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is replaced by —O—. R ⁴ is hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; R ⁵ is 1 to 20 Alkyl having 6 carbon atoms, aryl having 6-20 carbon atoms or arylalkyl having 7-20 carbon atoms; X ¹ is halogen; and P ¹ is an addition polymerizable monomer It is a chain of structural units obtained by polymerization of the body.

ここに、すべてのＲ^１１は炭素原子の数が１〜８であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレン、またはシクロアルケニレンで置き換えられてもよいアルキル、任意の水素がハロゲン、メチルまたはメトキシで置き換えられてもよいフェニル、非置換のナフチル、および任意の水素がフッ素、１〜４個の炭素原子を有するアルキル、ビニルまたはメトキシで置き換えられてもよいフェニル基炭素原子の数が１〜８であってと任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるフェニルアルキルから選択される同一の基であり；フェニルまたはフェニルアルキルのフェニル基が複数の置換基を有するときは、それらの置換基は同一の基であってもよいし異なる基であってもよく；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；そして、Ｂ^２は式（２−２−Ｐ）で示される基である：

ここに、Ｚ^３は２〜１０個の炭素原子を有するアルキレンであり、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、または−ＣＯＯ−で置き換えられてもよく；Ｒ^６は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；Ｘ^２はハロゲンであり；ベンゼン環への−ＳＯ_２−の結合位置は、Ｚ^３の結合位置に対して、オルト位、メタ位またはパラ位であり、Ｒ^６の結合位置は、Ｚ^３および−ＳＯ_２−のそれぞれの結合位置を除く任意の位置であり；そして、Ｐ^２は付加重合性単量体の重合によって得られる構成単位の連鎖である。 [48] A polymer represented by the formula (P-2):

Here, all R ¹¹ have 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms The number of carbon atoms of the phenyl group which may be replaced by alkyl, vinyl or methoxy having 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; the phenyl or phenylalkyl phenyl group is substituted more than once When having, those substituents may be the same group in a may be different groups; R ² and R ³ are alkyl having 1 to 8 carbon atoms, from cyclohexyl phenyl and cycloalkyl An independently selected group; and B ² is a group of formula (2-2P):

Here, Z ³ is an alkylene having 2 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or —COO—; R ⁶ is 1 to 3 Alkyl having 1 carbon atom; a is an integer of 0 to 2; X ² is halogen; the bonding position of —SO ₂ — to the benzene ring is ortho to the bonding position of Z ^3. In the position, meta position or para position, and the bonding position of R ⁶ is any position except the bonding positions of Z ³ and —SO ₂ —; and P ² is the polymerization of the addition polymerizable monomer Is a chain of structural units obtained by

ここに、すべてのＲ^１１は炭素原子の数が１〜８であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレン、またはシクロアルケニレンで置き換えられてもよいアルキル、任意の水素がハロゲン、メチルまたはメトキシで置き換えられてもよいフェニル、非置換のナフチル、および任意の水素がフッ素、１〜４個の炭素原子を有するアルキル、ビニルまたはメトキシで置き換えられてもよいフェニル基と炭素原子の数が１〜８であって任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるフェニルアルキルから選択される同一の基であり；フェニルまたはフェニルアルキルのフェニル基が複数の置換基を有するときは、それらの置換基は同一の基であってもよいし異なる基であってもよく；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；そして、Ｂ^３は式（２−３−Ｐ）で示される基である：

ここに、Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｚ^７は炭素原子の数が２〜１０であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり；Ｒ^７は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；Ｘ^３はハロゲンであり；ベンゼン環へのＺ^５の結合位置はＺ^７の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^７のそれぞれの結合位置を除く任意の位置であり；そして、Ｐ^３は付加重合性単量体の重合によって得られる構成単位の連鎖である。 [49] A polymer represented by the formula (P-3):

Here, all R ¹¹ have 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms The number of carbon atoms is 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; the phenyl or phenylalkyl phenyl group is substituted more than once When having, those substituents may be the same group in a may be different groups; R ² and R ³ are alkyl having 1 to 8 carbon atoms, from cyclohexyl phenyl and cycloalkyl An independently selected group; and B ³ is a group of formula (2-3-P):

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁷ is 2 to 10 carbon atoms. Any alkylene —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁷ is alkyl having 1 to 3 carbon atoms; X ³ is a halogen; the bonding position of Z ⁵ to the benzene ring is the meta position or the para position with respect to the bonding position of Z ⁷ , and the bonding position of R ^{7 is} the position of Z ⁵ and Z ⁷ P ³ is a chain of structural units obtained by polymerization of addition polymerizable monomers.

ここに、すべてのＲ^１１は炭素原子の数が１〜８であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレン、またはシクロアルケニレンで置き換えられてもよいアルキル、任意の水素がハロゲン、メチルまたはメトキシで置き換えられてもよいフェニル、非置換のナフチル、および任意の水素がフッ素、１〜４個の炭素原子を有するアルキル、ビニルまたはメトキシで置き換えられてもよいフェニル基と炭素原子の数が１〜８であって任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−またはシクロアルキレンで置き換えられてもよいアルキレン基とで構成されるフェニルアルキルから選択される同一の基であり；フェニルまたはフェニルアルキルのフェニル基が複数の置換基を有するときは、それらの置換基は同一の基であってもよいし異なる基であってもよく；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基であり；そして、Ｂ^４は式（２−４−Ｐ）で示される基である：

ここに、Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｚ^７は炭素原子の数が２〜１０であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり；Ｒ^８およびＲ^９は独立して水素、１〜１２個の炭素原子を有するアルキル、５〜１０個の炭素原子を有するシクロアルキルまたは６〜１０個の炭素原子を有するアリールであり、そしてＲ^８およびＲ^９は互いに結合してＮと共に環を形成してもよく；Ｒ^７は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；ベンゼン環へのＺ^５の結合位置はＺ^７の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^７のそれぞれの結合位置を除く任意の位置であり；そして、Ｐ^４は付加重合性単量体の重合によって得られる構成単位の連鎖である。 [50] A polymer represented by the formula (P-4):

Here, all R ¹¹ have 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms The number of carbon atoms is 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; the phenyl or phenylalkyl phenyl group is substituted more than once When having, those substituents may be the same group in a may be different groups; R ² and R ³ are alkyl having 1 to 8 carbon atoms, from cyclohexyl phenyl and cycloalkyl Independently selected groups; and B ⁴ is a group of formula (2-4-P):

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁷ is 2 to 10 carbon atoms. Any —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbon atoms , aryl having a cycloalkyl or 6-10 carbon atoms having 5 to 10 carbon atoms, and R ⁸ and R ⁹ may be bonded to each other to form a ring with N; R ⁷ is An alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; the bonding position of Z ⁵ to the benzene ring is meta or para to the bonding position of Z ⁷ , R ⁷ bond positions are Z ⁵ and Z ⁷ bond positions. And P ⁴ is a chain of structural units obtained by polymerization of an addition polymerizable monomer.

[51] The polymer according to item [47], wherein the addition polymerizable monomer is at least one selected from the group of (meth) acrylic acid derivatives and the group of styrene derivatives.

[52] The polymer according to item [48], wherein the addition polymerizable monomer is at least one selected from the group of (meth) acrylic acid derivatives and the group of styrene derivatives.

[53] The polymer according to item [49], wherein the addition polymerizable monomer is at least one selected from the group of (meth) acrylic acid derivatives and the group of styrene derivatives.

[54] The polymer according to item [50], wherein the addition polymerizable monomer is at least one selected from the group of (meth) acrylic acid derivatives and the group of styrene derivatives.

The silicon compound provided by the present invention is a silsesquioxane derivative and has an excellent living polymerizable radical polymerization initiating function. The silicon compound of the present invention exhibits an excellent living radical polymerization promoting function, particularly with respect to (meth) acrylic acid derivatives and styrene derivatives. For example, it is possible to start polymerization of a (meth) acrylic monomer with the silicon compound of the present invention and form a (meth) acrylic polymer starting from four points of the silsesquioxane structure of the present invention. is there. With respect to the polymer having an organic group having a silsesquioxane structure at the center thus obtained, the interaction between the organic groups having the silsesquioxane structure can be positively utilized. As a result, an organic-inorganic composite material with a clear structure can be obtained, and the structure of the polymer as a molecular assembly can be controlled. And the silicon compound of this invention has also characteristics other than the function as a polymerization initiator. For example, since α-haloesters have strong electrophilicity, it is possible to synthesize various silsesquioxane derivatives according to the nucleophilic reagent by reacting the silicon compound of the present invention with a nucleophilic reagent. is there. Therefore, the silicon compound of the present invention is also useful as an intermediate in organic synthesis.

First, terms used in the present invention will be described. “Arbitrary” means that not only the position but also the number can be arbitrarily selected, but the case where the number is 0 is not included. The description that any —CH ₂ — may be replaced by —O— does not include the case where a plurality of consecutive —CH ₂ — are replaced by —O—. For example, alkyl in which any —CH ₂ — may be replaced by —O— or —CH═CH— includes alkyl, alkoxy, alkoxyalkyl, alkenyl, alkyloxyalkenyl and alkenyloxyalkyl. Alkyl and alkylene may both be straight-chain groups or branched groups. This also applies when any —CH ₂ — is replaced by another divalent group. For example, all of alkyl, alkenylene, alkenyl and alkylene in the above-mentioned alkyloxyalkenyl and alkenyloxyalkyl may be a straight-chain group or a branched group. Both cycloalkyl and cycloalkenyl may or may not be a bridged ring structure group. A (meth) acrylic acid derivative is used as a general term for an acrylic acid derivative and a methacrylic acid derivative. (Meth) acrylate is used as a general term for acrylate and methacrylate. (Meth) acryloyloxy is used as a general term for acryloyloxy and methacryloyloxy.

式（１）におけるそれぞれのＲ^１は、水素、炭素原子の数が１〜４５のアルキル、置換もしくは非置換のアリールおよび置換もしくは非置換のアリールアルキルから独立して選択される基である。すべてのＲ^１が同じ１つの基であることが好ましいが、異なる２つ以上の基で構成されていてもよい。８個のＲ^１が異なる基で構成される場合の例は、２つ以上のアルキルで構成される場合、２つ以上のアリールで構成される場合、２つ以上のアリールアルキルで構成される場合、水素と少なくとも１つのアリールとで構成される場合、少なくとも１つのアルキルと少なくとも１つのアリールとで構成される場合、少なくとも１つのアルキルと少なくとも１つのアリールアルキルとで構成される場合、少なくとも１つのアリールと少なくとも１つのアリールアルキルとで構成される場合等である。これらの例以外の組み合わせでもよい。少なくとも２つの異なるＲ^１を有する化合物（１）は、これを製造する際に２つ以上の原料を用いることにより得ることができる。この原料については後に述べる。 The silicon compound of the present invention is represented by the formula (1). In the following description, the compound represented by formula (1) may be referred to as compound (1). The compounds represented by other formulas may be represented by the same simplification method.

Each R ¹ in formula (1) is a group independently selected from hydrogen, alkyl having 1 to 45 carbon atoms, substituted or unsubstituted aryl and substituted or unsubstituted arylalkyl. All R ¹ are preferably the same group, but may be composed of two or more different groups. Examples of the case where eight R ¹ are composed of different groups are composed of two or more alkyls, composed of two or more aryls, or composed of two or more arylalkyls , When composed of hydrogen and at least one aryl, when composed of at least one alkyl and at least one aryl, when composed of at least one alkyl and at least one arylalkyl, at least one For example, it is composed of aryl and at least one arylalkyl. Combinations other than these examples may be used. The compound (1) having at least two different R ¹ can be obtained by using two or more raw materials when producing the compound (1). This raw material will be described later.

When R ¹ is alkyl, the number of carbon atoms is 1-45. The preferred number of carbon atoms is 1-30. The number of carbon atoms is more preferably 1-8. The optional hydrogen may be replaced with fluorine, and the optional —CH ₂ — may be replaced with —O—, —CH═CH—, cycloalkylene, or cycloalkenylene. Preferred examples of alkyl are unsubstituted alkyl having 1 to 30 carbon atoms, alkoxyalkyl having 2 to 29 carbon atoms, 1 to 8 carbon atoms, and one —CH ₂ —. Is substituted with cycloalkylene, alkenyl having 2 to 20 carbon atoms, alkenyloxyalkyl having 3 to 20 carbon atoms, alkyloxyalkenyl having 3 to 20 carbon atoms, the number of carbon atoms Alkyls in which 1 to 8 and one —CH ₂ — is replaced by cycloalkenylene, and groups in which any hydrogen in these groups listed here is replaced by fluorine. The preferred number of carbon atoms in cycloalkylene and cycloalkenylene is 3-8.

Examples of unsubstituted alkyl having 1 to 30 carbon atoms are methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 1,1, 2-trimethylpropyl, heptyl, octyl, 2,4,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, triacontyl and the like.

Examples of fluorinated alkyls having 1 to 30 carbon atoms are 2-fluoroethyl, 2,2-difluoroethyl, 3,3,3-trifluoropropyl, hexafluoropropyl, nonafluoro-1,1,2, 2-tetrahydrohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl, perfluoro -1H, 1H, 2H, 2H-tetradecyl and the like.

Examples of alkoxyalkyl having 2 to 29 carbon atoms and fluorinated alkoxyalkyl are 3-methoxypropyl, methoxyethoxyundecyl, 2-fluoroethyloxypropyl, 2,2,2-trifluoroethyloxypropyl, 2 -Fluoro-1-fluoromethylethyloxypropyl, 2,2,3,3-tetrafluoropropyloxypropyl, 2,2,3,3,3-pentafluoropropyloxypropyl, hexafluoroisopropyloxypropyl, heptafluoroisopropyl Oxypropyl, hexafluorobutyloxypropyl, heptafluorobutyloxypropyl, octafluoroisobutyloxypropyl, octafluoropentyloxypropyl, 2-fluoroethyloxybutyl, 2,2,2-trif Oroethyloxybutyl, 2-fluoro-1-fluoromethylethyloxybutyl, 2,2,3,3-tetrafluoropropyloxybutyl, 2,2,3,3,3-pentafluoropropyloxybutyl, hexafluoroisopropyl Oxybutyl, hexafluorobutyloxybutyl, heptafluorobutyloxybutyl, octafluoroisobutyloxybutyl, octafluoropentyloxybutyl, 2-fluoroethyloxyisobutyl, 2,2,2-trifluoroethyloxyisobutyl, 2-fluoro- 1-fluoromethylethyloxyisobutyl, 2,2,3,3-tetrafluoropropyloxyisobutyl, 2,2,3,3,3-pentafluoropropyloxyisobutyl, hexafluoroisopropyloxyisobutyl Hexafluorobutyl oxy isobutyl, heptafluorobutyl oxy isobutyl, octafluoroisobutyl oxy isobutyl, a octafluoropentyloxy isobutyl and the like.

Examples of alkyl having 1 to 8 carbon atoms and wherein one —CH ₂ — is replaced by cycloalkylene are cyclohexylmethyl, adamantaneethyl, cyclopentyl, cyclohexyl, 2-bicycloheptyl, cyclooctyl and the like. Cyclohexyl is an example where methyl —CH ₂ — is replaced by cyclohexylene. Cyclohexylmethyl is an example in which —CH ₂ — in the β-position of ethyl is replaced by cyclohexylene.

Examples of alkenyl having 2 to 20 carbon atoms are vinyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl, 10-undecenyl, 21-docosenyl and the like. An example of an alkenyloxyalkyl having 3 to 20 carbon atoms is allyloxyundecyl. Examples of alkyl having 1 to 8 carbon atoms and wherein one —CH ₂ — is replaced by cycloalkenylene are 2- (3-cyclohexenyl) ethyl, 5- (bicycloheptenyl) ethyl, 2- And cyclopentenyl, 3-cyclohexenyl, 5-norbornen-2-yl, 4-cyclooctenyl and the like.

Examples where R ¹ in formula (1) is substituted or unsubstituted aryl are phenyl and unsubstituted naphthyl where any hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms. is there. Preferred examples of halogen are fluorine, chlorine and bromine. In alkyl, which is a phenyl substituent, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, —CH═CH— or phenylene. That is, specific examples of preferred aryl include phenyl, unsubstituted naphthyl, alkylphenyl, alkyloxyphenyl, alkenylphenyl, phenyl having at least one —CH ₂ — substituted with phenylene as a substituent, and these In this group, any hydrogen is replaced with a halogen. In the present invention, when simply expressed as phenyl without particular notice, it means unsubstituted phenyl.

Examples of halogenated phenyl are pentafluorophenyl, 4-chlorophenyl, 4-bromophenyl and the like.

Examples of alkylphenyl are 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentylphenyl, 4-heptylphenyl, 4-octylphenyl, 4-nonylphenyl, 4-decylphenyl. 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 4- (1-methylethyl) phenyl, 4- (1,1-dimethylethyl) phenyl, 4- (2-ethylhexyl) phenyl, 2,4,6-tris (1-methylethyl) phenyl and the like.

Examples of alkyloxyphenyl are (4-methoxy) phenyl, (4-ethoxy) phenyl, (4-propoxy) phenyl, (4-butoxy) phenyl, (4-pentyloxy) phenyl, (4-heptyloxy) phenyl , (4-decyloxy) phenyl, (4-octadecyloxy) phenyl, 4- (1-methylethoxy) phenyl, 4- (2-methylpropoxy) phenyl, 4- (1,1-dimethylethoxy) phenyl and the like. . Examples of alkenylphenyl are 4-vinylphenyl, 4- (1-methylvinyl) phenyl, 4- (3-butenyl) phenyl, and the like.

Examples of phenyl having as substituent an alkyl in which at least one —CH ₂ — is replaced by phenylene are 4- (2-phenylvinyl) phenyl, 4-phenoxyphenyl, 3- (phenylmethyl) phenyl, biphenyl, terphenyl Etc. 4- (2-phenylvinyl) phenyl, in ethyl ethyl phenyl, one -CH ₂ - is replaced by phenylene, another -CH ₂ - is an example for which it is replaced by -CH = CH-.

Examples of phenyl in which some of the hydrogens on the benzene ring are replaced by halogens and other hydrogens are replaced by alkyl, alkyloxy or alkenyl include 3-chloro-4-methylphenyl, 2,5-dichloro-4-methyl Phenyl, 3,5-dichloro-4-methylphenyl, 2,3,5-trichloro-4-methylphenyl, 2,3,6-trichloro-4-methylphenyl, 3-bromo-4-methylphenyl, 2, 5-dibromo-4-methylphenyl, 3,5-dibromo-4-methylphenyl, 2,3-difluoro-4-methylphenyl, 3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl, 3 , 5-Dibromo-4-methoxyphenyl, 2,3-difluoro-4-methoxyphenyl, 2,3-difluoro-4-ethoxyphenyl Le, 2,3-difluoro-4-propoxy-phenyl, 4-vinyl-2,3,5,6-tetrafluorophenyl, and the like.

Next, examples of a case where R ¹ in Formula (1) is a substituted or unsubstituted arylalkyl. In the arylalkyl alkylene group, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, —CH═CH—, or cycloalkylene. A preferred example of arylalkyl is phenylalkyl. At this time, any hydrogen in the phenyl group may be replaced by halogen or alkyl having 1 to 12 carbon atoms. In this alkyl, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, —CH═CH—, cycloalkylene, or phenylene. And the preferable carbon number of an alkylene group is 1-12, and a more preferable carbon number is 1-8.

Examples of unsubstituted phenylalkyl are phenylmethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, 11-phenylundecyl, 1-phenylethyl, 2-phenyl Phenylpropyl, 1-methyl-2-phenylethyl, 1-phenylpropyl, 3-phenylbutyl, 1-methyl-3-phenylpropyl, 2-phenylbutyl, 2-methyl-2-phenylpropyl, 1-phenylhexyl, etc. It is.

Examples of phenylalkyl in which at least one hydrogen of the phenyl group is replaced by fluorine are 4-fluorophenylmethyl, 2,3,4,5,6-pentafluorophenylmethyl, 2- (2,3,4,5, 6-pentafluorophenyl) ethyl, 3- (2,3,4,5,6-pentafluorophenyl) propyl, 2- (2-fluorophenyl) propyl, 2- (4-fluorophenyl) propyl and the like.

Examples of phenylalkyl in which at least one hydrogen of the phenyl group is replaced by chlorine are 4-chlorophenylmethyl, 2-chlorophenylmethyl, 2,6-dichlorophenylmethyl, 2,4-dichlorophenylmethyl, 2,3,6-trichlorophenyl Methyl, 2,4,6-trichlorophenylmethyl, 2,4,5-trichlorophenylmethyl, 2,3,4,6-tetrachlorophenylmethyl, 2,3,4,5,6-pentachlorophenylmethyl, 2- (2-chlorophenyl) ethyl, 2- (4-chlorophenyl) ethyl, 2- (2,4,5-chlorophenyl) ethyl, 2- (2,3,6-chlorophenyl) ethyl, 3- (3-chlorophenyl) propyl 3- (4-Chlorophenyl) propyl, 3- (2,4,5-trichlorophenyl) pro 3- (2,3,6-trichlorophenyl) propyl, 4- (2-chlorophenyl) butyl, 4- (3-chlorophenyl) butyl, 4- (4-chlorophenyl) butyl, 4- (2,3,3) 6-trichlorophenyl) butyl, 4- (2,4,5-trichlorophenyl) butyl, 1- (3-chlorophenyl) ethyl, 1- (4-chlorophenyl) ethyl, 2- (4-chlorophenyl) propyl, 2- (2-chlorophenyl) propyl, 1- (4-chlorophenyl) butyl and the like.

Examples of phenylalkyl in which at least one hydrogen of the phenyl group is replaced by bromine are 2-bromophenylmethyl, 4-bromophenylmethyl, 2,4-dibromophenylmethyl, 2,4,6-tribromophenylmethyl, 2 , 3,4,5-tetrabromophenylmethyl, 2,3,4,5,6-pentabromophenylmethyl, 2- (4-bromophenyl) ethyl, 3- (4-bromophenyl) propyl, 3- ( 3-bromophenyl) propyl, 4- (4-bromophenyl) butyl, 1- (4-bromophenyl) ethyl, 2- (2-bromophenyl) propyl, 2- (4-bromophenyl) propyl and the like.

Examples of phenylalkyl in which at least one hydrogen of the phenyl group is replaced by alkyl having 1 to 12 carbon atoms are 2-methylphenylmethyl, 3-methylphenylmethyl, 4-methylphenylmethyl, 4-dodecylphenylmethyl 3,5-dimethylphenylmethyl, 2- (4-methylphenyl) ethyl, 2- (3-methylphenyl) ethyl, 2- (2,5dimethylphenyl) ethyl, 2- (4-ethylphenyl) ethyl, 2- (3-ethylphenyl) ethyl, 1- (4-methylphenyl) ethyl, 1- (3-methylphenyl) ethyl, 1- (2-methylphenyl) ethyl, 2- (4-methylphenyl) propyl, 2- (2-methylphenyl) propyl, 2- (4-ethylphenyl) propyl, 2- (2-ethylphenyl) propyl 2- (2,3-dimethylphenyl) propyl, 2- (2,5-dimethylphenyl) propyl, 2- (3,5-dimethylphenyl) propyl, 2- (2,4-dimethylphenyl) propyl, 2- (3,4-dimethylphenyl) propyl, 2- (2,5-dimethylphenyl) butyl, (4- (1-methylethyl) phenyl) methyl, 2- (4- (1,1-dimethylethyl) phenyl) And ethyl, 2- (4- (1-methylethyl) phenyl) propyl, 2- (3- (1-methylethyl) phenyl) propyl, and the like.

Examples of phenylalkyl having 1 to 12 carbon atoms and having at least one hydrogen substituted with fluorine as a substituent of the phenyl group include 3- (trifluoromethyl) phenylmethyl, 2- (4 -Trifluoromethylphenyl) ethyl, 2- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexylphenyl) ethyl, 2- (4-heptadecafluorooctylphenyl) ethyl, 1- (3 -Trifluoromethylphenyl) ethyl, 1- (4-trifluoromethylphenyl) ethyl, 1- (4-nonafluorobutylphenyl) ethyl, 1- (4-tridecafluorohexylphenyl) ethyl, 1- (4- Heptadecafluorooctylphenyl) ethyl, 2- (4-nonafluorobutylphenyl) Propyl, 1-methyl-1- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexylphenyl) propyl, 1-methyl-1- (4-tridecafluorohexylphenyl) ethyl, 2- (4-heptadecafluorooctylphenyl) propyl, 1-methyl-1- (4-heptadecafluorooctylphenyl) ethyl and the like.

An example of a phenylalkyl having 1 to 12 carbon atoms and an alkyl in which one —CH ₂ — is replaced by —CH═CH— as a substituent of the phenyl group is 2- (4-vinylphenyl) And ethyl, 1- (4-vinylphenyl) ethyl, 1- (2- (2-propenyl) phenyl) ethyl and the like.

Examples of phenylalkyl having 1 to 12 carbon atoms and an alkyl in which one —CH ₂ — is replaced by —O— as a substituent of the phenyl group include 4-methoxyphenylmethyl, 3-methoxyphenyl Methyl, 4-ethoxyphenylmethyl, 2- (4-methoxyphenyl) ethyl, 3- (4-methoxyphenyl) propyl, 3- (2-methoxyphenyl) propyl, 3- (3,4-dimethoxyphenyl) propyl, 11- (4-methoxyphenyl) undecyl, 1- (4-methoxyphenyl) ethyl, 2- (3- (methoxymethyl) phenyl) ethyl, 3- (2-nonadecafluorodecenyloxyphenyl) propyl and the like is there.

Alkyl having 1 to 12 carbon atoms, one —CH ₂ — substituted with cycloalkylene, and another —CH ₂ — replaced with —O— as a substituent of the phenyl group Examples of phenylalkyl having are cyclopentylphenylmethyl, cyclopentyloxyphenylmethyl, cyclohexylphenylmethyl, cyclohexylphenylethyl, cyclohexylphenylpropyl, cyclohexyloxyphenylmethyl and the like.

The number of carbon atoms is 1 to 12, and one —CH ₂ — is substituted with phenylene, and the other —CH ₂ — may be substituted with —O— as an alkyl substituent. Examples of phenylalkyl are 2- (4-phenoxyphenyl) ethyl, 2- (4-phenoxyphenyl) propyl, 2- (2-phenoxyphenyl) propyl, 4-biphenylylmethyl, 3-biphenylylethyl, 4- Biphenylylethyl, 4-biphenylylpropyl, 2- (2-biphenylyl) propyl, 2- (4-biphenylyl) propyl and the like.

Examples of phenylalkyl in which at least two hydrogens of the phenyl group are replaced by different groups are 3- (2,5-dimethoxy-3,4,6-trimethylphenyl) propyl, 3-chloro-2-methylphenylmethyl, 4 -Chloro-2-methylphenylmethyl, 5-chloro-2-methylphenylmethyl, 6-chloro-2-methylphenylmethyl, 2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmethyl, 2 , 3-dichloro-4-methylphenylmethyl, 2,5-dichloro-4-methylphenylmethyl, 3,5-dichloro-4-methylphenylmethyl, 2,3,5-trichloro-4-methylphenylmethyl, 2, , 3,5,6-tetrachloro-4-methylphenylmethyl, (2,3,4,6-tetrachloro-5-methylphenyl Methyl, 2,3,4,5-tetrachloro-6-methylphenylmethyl, 4-chloro-3,5-dimethylphenylmethyl, 2-chloro-3,5-dimethylphenylmethyl, 2,4-dichloro-3 , 5-dimethylphenylmethyl, 2,6-dichloro-3,5-dimethylphenylmethyl, 2,4,6-trichloro-3,5-dimethylphenylmethyl, 3-bromo-2-methylphenylmethyl, 4-bromo 2-methylphenylmethyl, 5-bromo-2-methylphenylmethyl, 6-bromo-2-methylphenylmethyl, 3-bromo-4-methylphenylmethyl, 2,3-dibromo-4-methylphenylmethyl, 2 , 3,5-tribromo-4-methylphenylmethyl, 2,3,5,6-tetrabromo-4-methylphenylmethyl, 11- (3-chloro -4-methoxyphenyl) undecyl and the like.

The most preferred examples of the phenyl group in phenylalkyl are an unsubstituted phenyl group and a phenyl group having at least one of fluorine, alkyl having 1 to 4 carbon atoms, vinyl and methoxy as a substituent.

Examples of phenylalkyl in which at least one of —CH ₂ — in the alkylene group constituting phenylalkyl is replaced by —O—, —CH═CH— or cycloalkylene are 3-phenoxypropyl, 1-phenylvinyl, 2- Phenyl vinyl, 3-phenyl-2-propenyl, 4-phenyl-4-pentenyl, 13-phenyl-12-tridecenyl, phenylcyclohexyl, phenoxycyclohexyl and the like.

Examples of phenylalkenyl in which the hydrogen of the phenyl group is replaced by fluorine or methyl are 4-fluorophenylvinyl, 2,3-difluorophenylvinyl, 2,3,4,5,6-pentafluorophenylvinyl, 4-methylphenyl For example, vinyl.

More preferred specific examples of R ¹ are ethyl, 2-fluoroethyl, 2,2-difluoroethyl, propyl, 3,3,3-trifluoropropyl, hexafluoropropyl, 2-methylpropyl, 2,4,4- Trimethylpentyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, cyclopentyl, cyclohexyl, phenyl, phenyl halide, methylphenyl, dimethylphenyl, methoxyphenyl, unsubstituted naphthyl, phenylmethyl, phenylethyl, phenylbutyl 2-phenylpropyl, 1-methyl-2-phenylethyl, pentafluorophenylpropyl, 4-ethylphenylethyl, 3-ethylphenylethyl, 4- (1,1-dimethylethyl) phenylethyl, 4-vinylphenylethyl , 1- (4-Vinyl vinyl Enyl) ethyl, 4-methoxyphenylpropyl, phenoxypropyl.

A more preferred specific example of R ¹ is phenyl.

In the present invention, R ¹ may be a group used for liquid crystal alignment control. Such an example is shown below.

A group having a steroid skeleton may be present in the group used for orientation control. Examples of the group having such a steroid skeleton include cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, erygosteryl, estolyl, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl, melatranyl, methyltestosteryl, noretisteryl, pregnenoyl. , Β-sitosteryl, stigmasteryl, testosteryl, acetic acid cholesterol ester, and the like. These groups may be bonded to silicon via phenyl, or may be groups bonded directly to silicon.

R ² and R ³ in formula (1) are independently alkyl, phenyl or cyclohexyl having 1 to 8 carbon atoms. Examples of alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, 2-methylbutyl, hexyl, 2-methylpentyl, heptyl, 2-methylhexyl, octyl, 2-methylheptyl, and 2-ethylhexyl. . The preferred alkyl is methyl.

A in Formula (1) is a group having a polymerization initiating ability for a monomer, preferably a living radical polymerization initiating ability. Examples of such A have a group having an α-haloester group, a group having a halogenated sulfonyl group, a group having a haloalkylphenyl group, a group having an MgBr group, a group having a dithiocarbamate group, and a nitroxyl group. It is a group. A group having a haloalkylphenyl group generates a radical in the presence of a copper chloride / amine complex, and becomes a cationic polymerization initiator in the presence of silver perchlorate. Examples of haloalkylphenyl groups are chloromethylphenyl, bromomethylphenyl, iodomethylphenyl, and the like.

The MgBr group can be introduced as follows. First, a silsesquioxane derivative having a double bond such as a styryl group or a vinyl group is synthesized. Next, hydroboration of the double bond site of this derivative is performed using a borane-dimethyl sulfide complex to obtain a silsesquioxane derivative having boron. An MgBr group can be introduced by reacting this boron-containing silsesquioxane derivative with pentane-1,5-diyl-di (magnesium bromide). The obtained Grignard type silsesquioxane derivative can be used as an anionic polymerization initiator of styrene or methyl (meth) acrylate.

The nitroxyl group can be introduced as follows. First, a silsesquioxane derivative having a styryl group is synthesized. Nitroxide compounds that generate stable radicals that do not participate in polymerization, such as di-t-butyl nitroxide, 2,2,6,6-tetramethylpiperidinyl-1-oxy, Nt-butyl- 1-diethylphosphone-2,2-dimethylpropyl nitroxide and the like are added, and further (N, N′-bis (3,5-di-t-butylsalicylidene) -1,2-cyclohexanediaminate) Manganese (III) chloride (Jacobsen catalyst) is introduced. Next, as a radical generator, for example, styryl radicals can be generated by coexisting di-t-butyl peroxide and sodium borohydride to introduce a target nitroxyl group. The obtained silsesquioxane derivative can be used as a polymerization initiator for styrene or methyl (meth) acrylate.

A in formula (1) also includes an exchange chain transfer radical polymerization initiating group represented by reversible addition-fragmentation chain transfer (RAFT). An example of such A is a group having a dithioester group.

The dithioester group can be introduced as follows. Benzyl bromide and metal magnesium are reacted to form magnesium bromide phenyl, and carbon disulfide is added thereto to form magnesium bromide dithiophenyl. The target dithioester group can be introduced by reacting the compound with a silsesquioxane derivative having a haloalkylphenyl group or an α-haloester group. The obtained silsesquioxane derivative is obtained by using a polymerization active catalyst such as benzoyl peroxide or azobisisobutyronitrile, so that styrene, acrylate, methyl (meth) acrylate, acrylic acid, styrene sulfonic acid, methyl (meta ) It can be used as an initiator for exchange chain transfer radical polymerization of acrylamide and N-isopropylacrylamide.

Preferred examples of A are a group having an α-haloester group, a group having a halogenated sulfonyl group, a group having a haloalkylphenyl, and a group having a dithiocarbamate group.

The group having an α-haloester group means a group having α-halocarbonyloxy at the terminal. As a polymerization method using this α-halocarbonyloxy as a radical polymerization initiation group, an atom transfer radical polymerization method is known. The polymerization catalyst used in this method is a metal complex having a group 8, 9, 10, or 11 element in the periodic table as a central metal atom. In this atom transfer radical polymerization, it is known that a group having α-halocarbonyloxy has an excellent polymerization initiating ability. It is also well known that this polymerization is a living polymerization. That is, the silicon compound of the present invention having an α-haloester group has excellent polymerization initiating ability in the presence of a transition metal complex, and can continue to maintain living polymerizability. And it is possible to start superposition | polymerization with respect to all radically polymerizable monomers. In particular, it is possible to develop excellent living polymerizability for (meth) acrylic acid derivatives or styrene derivatives.

In addition, since the silicon compound of the present invention having an α-haloester group has α-halocarbonyloxy at the terminal, it can be derived into many derivatives by applying various organic reactions. For example, by reacting lithium, magnesium, zinc or the like with this silicon compound, a silsesquioxane derivative having an organometallic functional group can be derived. Specifically, the silicon compound of the present invention having an α-haloester group is reacted with zinc to lead to a silsesquioxane derivative having an organozinc functional group, and then an aldehyde or a ketone is added thereto to form an alcohol. Can be converted into a kind. Therefore, silsesquioxane derivatives having an organozinc functional group are useful as intermediate raw materials used in so-called reformate reactions.

Since the α-halocarbonyloxy group has strong electrophilicity, it can be converted into an amino group, a mercapto group, or the like using various nucleophilic reagents. Furthermore, the α-halocarbonyloxy group can be converted to a ketone by treating with an enamine to give an imine salt and hydrolyzing the imine salt. That is, the silicon compound of the present invention having an α-halocarbonyloxy group is also useful as an intermediate material used for the Stoke-enamine reaction. By reacting this silicon compound with an aliphatic or aromatic Grignard reagent, it is possible to obtain silsesquioxane derivatives having various organic functional groups and polymerizable functional groups. Therefore, the silicon compound of the present invention having an α-halocarbonyloxy group can be used not only as a polymerization initiator but also as an intermediate useful for various organic syntheses.

式（１−１）におけるＲ^１、Ｒ^２およびＲ^３は、式（１）におけるこれらの記号と同一の意味を有し、Ａ^１は式（２−１）で示される基である。

A preferred example of the silicon compound of the present invention having an α-haloester group is a compound represented by the formula (1-1).

R ¹ , R ² and R ³ in formula (1-1) have the same meaning as those symbols in formula (1), and A ¹ is a group represented by formula (2-1).

In the formula (2-1), X ¹ is halogen, and examples thereof are chlorine, bromine and iodine. As the initiator group for atom transfer radical polymerization, chlorine and bromine are most preferred. R ⁴ is hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. Preferred examples of R ⁴ are hydrogen, alkyl having 1 to 20 carbon atoms, phenyl in which any hydrogen may be replaced with alkyl having 1 to 14 carbon atoms, and 1 to 14 optional hydrogens A phenylalkyl which is composed of a phenyl group which may be replaced by an alkyl having 1 to 14 carbon atoms and an alkylene group having 1 to 14 carbon atoms, and the total number of carbon atoms of these groups is 7 to 20 It is. More preferred examples of R ⁴ are hydrogen and alkyl having 1 to 20 carbon atoms. More preferred examples of R ⁴ are hydrogen, methyl and ethyl, and the most preferred example is methyl. R ⁵ is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. Preferred examples of R ⁵ are alkyl having 1 to 20 carbon atoms, phenyl in which any hydrogen may be replaced with alkyl having 1 to 14 carbon atoms, and any hydrogen having 1 to 14 carbons. It is composed of a phenyl group which may be replaced by an alkyl having an atom and an alkylene group having 1 to 14 carbon atoms, and the total number of carbon atoms of these groups is 7 to 20 . A more preferred example of R ⁵ is alkyl having 1 to 20 carbon atoms. More preferred examples of R ⁵ are methyl and ethyl, and the most preferred example is methyl. Z ¹ is alkylene having 2 to 20 carbon atoms or alkenylene having 3 to 8 carbon atoms. Any —CH ₂ — in these alkylene and alkenylene may be replaced by —O—.

式（２−１−４）において、Ｚ^８は単結合、または１〜８個の炭素原子を有するアルキレンであり、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよい。 In bonding an organic group to a Si atom, typical methods for obtaining a non-hydrolyzed derivative include a method in which a Grignard reagent is reacted with Si-halogen and an aliphatic unsaturated bond with Si-H. This is a method of reacting a compound. The latter is usually referred to as a hydrosilylation reaction method. In the present invention, the hydrosilylation reaction method is easier to apply in terms of the availability of raw materials. That is, a preferred method for introducing a functional group into a silsesquioxane derivative is a method in which a Si—H functional silsesquioxane derivative and a compound having an unsaturated bond at a terminal are bonded by a hydrosilylation reaction. Therefore, a preferred example of Z ¹ in the formula (2-1) is a group represented by —C ₂ H ₄ —Z ⁸ . That is, a preferred example of the formula (2-1) is the formula (2-1-4).

In formula (2-1-4), Z ⁸ is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O—.

That is, a preferred example of Z ¹ is alkylene having 2 to 10 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—. Examples of such _{alkylene, -C 2 H 4 -, -} C 3 H 6 -, - C 4 H 8 -, - C 5 H 10 -, - C 2 H 4 -O-C 3 H 6 - and _{-C 3 H 6 -O-C 3} H 6 - it is. More preferred examples of Z ¹ are —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₅ H ₁₀ — and —C ₂ H ₄ —O—C ₃ H ₆ —. However, the selection Z ¹ is not limited thereto. Symbols other than ^{Z 8} in the formula (2-1-4) have the same meanings as those of these codes in Formula (2-1).

As a polymerization method using a halogenated sulfonyl group as an initiation group for radical polymerization, an atom transfer radical polymerization method is known. In this method, a metal complex having, as a catalyst, an element of Group 8, 9, 10, or 11 of the periodic table is used as a catalyst. In this atom transfer radical polymerization, it is known that a halogenated sulfonyl has an excellent polymerization initiating ability. It is also well known that this polymerization is a living polymerization. That is, the silicon compound of the present invention having a halogenated sulfonyl has excellent polymerization initiating ability in the presence of a transition metal catalyst, and can continue to maintain living polymerizability. And it is possible to start superposition | polymerization with respect to all radically polymerizable monomers. In particular, it is possible to develop excellent living polymerizability for (meth) acrylic acid derivatives.

In addition, since a halogenated sulfonyl group has strong electrophilicity, various derivatives can be synthesized using various nucleophilic reagents on the silicon compound of the present invention having a halogenated sulfonyl group. For example, conversion to sulfonic acid by hydrolysis under acidic conditions, conversion to sulfonic acid by hydrolysis, conversion to sulfonates by treatment with sodium hydroxide, various alcohols under basic conditions Conversion to a sulfonic acid ester by treatment, or conversion to a sulfonic acid amide by treatment with ammonia or an amine is possible. From these characteristics, the silicon compound of the present invention can be used as a protecting group, and some of the sulfonic acid amide derivatives can be used as sulfa drugs, for example, as antibacterial drugs. It is also possible to perform conversion to a mercapto group using various reducing agents such as lithium aluminum hydride as a reducing agent, and it is also possible to derive aromatic sulfone with various aromatic Grignard reagents. That is, this silicon compound can be utilized not only as an attribute as a polymerization initiator but also as an intermediate useful for various organic syntheses.

式（１−２）におけるＲ^１、Ｒ^２およびＲ^３は、式（１）におけるこれらの記号と同一の意味を有し、Ａ^２は式（２−２）で示される基である。

A preferred example of the silicon compound of the present invention having a halogenated sulfonyl is a compound represented by the formula (1-2).

R ¹ , R ² and R ³ in formula (1-2) have the same meaning as those symbols in formula (1), and A ² is a group represented by formula (2-2).

In the formula (2-2), X ² is halogen, and examples thereof are chlorine, bromine and iodine. As the initiator group for atom transfer radical polymerization, chlorine and bromine are most preferred. Z ³ is alkylene having 2 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or —COO—. The bonding position of —SO ₂ X ² to the benzene ring is ortho, meta, or para with respect to the bonding position of Z ³ . R ⁶ is alkyl having 1 to 3 carbon atoms. A representing the number of R ⁶ is 0, 1, or 2, with 0 being most preferred. The bonding position of R ⁶ is an arbitrary position excluding the bonding positions of Z ³ and —SO ₂ X ² .

式（２−２−４）において、Ｚ^９は単結合、または１〜３個の炭素原子を有するアルキレンである。 Z ² in the formula (2-2) is preferably a group represented by —C ₂ H ₄ —Z ⁹ as in the case of the formula (2-1). That is, a preferred example of the formula (2-2) is the formula (2-2-4).

In the formula (2-2-4), Z ⁹ is a single bond or alkylene having 1 to 3 carbon atoms.

That is, a preferred example of Z ³ is alkylene having 2 to 5 carbon atoms. Examples of such _{alkylene, -C 2 H 4 -, -} C 3 H 6 -, - C 4 H 8 -, and _-C 5 _{H 10} - is. The most preferred example of Z ³ is —C ₂ H ₄ —. However, the selection of the Z ³ is not limited thereto. In the formula (2-2-4), symbols other than Z ⁹ have the same meaning as in the formula (2-2), and the bonding position of the halogenated sulfonyl group to the benzene ring and R ⁶ to Z ⁹ is These are the same as these bonding positions for Z ³ in the formula (2-2).

As a polymerization method using haloalkylphenyl as an initiation group for radical polymerization, an atom transfer radical polymerization method is known. In this method, a metal complex having, as a catalyst, an element of Group 8, 9, 10, or 11 of the periodic table is used as a catalyst. In this atom transfer radical polymerization, it is known that haloalkylphenyl has an excellent polymerization initiating ability. It is also well known that this polymerization is a living polymerization. That is, the silicon compound of the present invention having haloalkylphenyl has excellent polymerization initiation ability in the presence of a transition metal complex, and can continue to maintain living polymerizability. And it is possible to start superposition | polymerization with respect to all radically polymerizable monomers. In particular, it is possible to develop excellent living polymerizability for styrene derivatives.

In addition, since haloalkylphenyl has strong electrophilicity, an amino group, a hydroxyl group, a mercapto group, etc. can be introduce | transduced into the silicon compound of this invention which has haloalkylphenyl using a various nucleophilic reagent. That is, this silicon compound can be utilized as a useful intermediate.

式（１−３）におけるＲ^１、Ｒ^２およびＲ^３は、式（１）におけるこれらの記号と同一の意味を有し、Ａ^３は式（２−３）で示される基である。

A preferred example of the silicon compound of the present invention having haloalkylphenyl is a compound represented by the formula (1-3).

R ¹ , R ² and R ³ in the formula (1-3) have the same meaning as those symbols in the formula (1), and A ³ is a group represented by the formula (2-3).

X ³ in the formula (2-3) is halogen such as chlorine, bromine, and iodine. As the initiation group for atom transfer radical polymerization, chlorine and bromine are more preferred. Z ⁵ is alkylene having 1 to 3 carbon atoms. Examples of Z ⁵ are methylene, 1,2-ethylene, 1,1-ethylene, 1,3-trimethylene, ethylmethylene, 1-methyl-1,2-ethylene and 2-methyl-1,2-ethylene. . A preferred example of Z ⁵ is methylene. Z ⁷ is an alkylene having 2 to 10 carbon atoms. In this alkylene, one —CH ₂ — may be replaced by —O—. The bonding position of Z ⁵ to the benzene ring is meta or para with respect to the bonding position of Z ⁷ . R ⁷ is alkyl having 1 to 3 carbon atoms. Examples of R ⁷ are methyl, ethyl, propyl and isopropyl. Preferred R ⁷ is methyl. A representing the number of R ⁷ is 0, 1, or 2, with 0 being preferred. The bonding position of R ^{7 to} the benzene ring is an arbitrary position other than the bonding positions of Z ⁵ and Z ⁷ .

式（２−３−４）中のＺ^１０は、単結合または１〜８個の炭素原子を有し、１つの−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンである。 Z ⁷ in formula (2-3) is also preferably a group represented by —C ₂ H ₄ —Z ¹⁰ as in the case of formula (2-1). That is, a preferred example of the formula (2-3) is the formula (2-3-4).

Z ¹⁰ in formula (2-3-4) is a single bond or alkylene having 1 to 8 carbon atoms, and one —CH ₂ — may be replaced by —O—.

That is, a preferred example of Z ⁷ in formula (2-1) is alkylene having 2 to 10 carbon atoms, and one —CH ₂ — may be replaced by —O—. Examples of such ^{Z 7} _{are, -C 2 H 4 -, -} C 3 H 6 -, - OC 2 H 4 -, - OC 3 H 6 -, - CH 2 OC 2 H 4 -, - CH 2 OC _{3 H 6 -, - C 2} H 4 OC 2 H 4 -, and _{-C 2 H 4 OC 3 H 6} - it is. However, the selection range of Z ⁷ is not limited to these. In the formula (2-3-4), symbols other than Z ¹⁰ have the same meaning as the symbols in the formula (2-3), and the bonding position of Z ⁵ and R ⁷ to the benzene ring with respect to Z ¹⁰ is These bond positions are the same as those for Z ⁷ in (2-3).

As a photopolymerization method using a dithiocarbamate group as a polymerization initiating group, a photoinitiator-transfer agent-terminator polymerization method is known. In this photoiniferter polymerization, it is well known that a dithiocarbamate group is radically dissociated by light and has excellent polymerization initiating ability and sensitizing ability. It is also well known that this photopolymerization is a living polymerization. Therefore, as long as the silicon compound of the present invention having a dithiocarbamate group is irradiated with light, it can continue to maintain the polymerization initiating ability and has the ability to initiate photopolymerization with respect to any radically polymerizable monomer. . In particular, it is possible to develop excellent living polymerizability for (meth) acrylic acid derivatives. And since the dithiocarbamate group has pharmacological activity such as radiation resistance, herbicidal effect, complex forming ability, hydrophilicity, etc. in addition to its properties as a photopolymerization initiating group, it is also possible to utilize these properties. is there.

式（１−４）におけるＲ^１、Ｒ^２およびＲ^３は、式（１）におけるこれらの記号と同一の意味を有し、Ａ^４は式（２−４）で示される基である。

A preferred example of the silicon compound of the present invention having a dithiocarbamate group is a compound represented by the formula (1-4).

R ¹ , R ² and R ³ in formula (1-4) have the same meanings as those symbols in formula (1), and A ⁴ is a group represented by formula (2-4).

Z ⁵ , Z ⁷ , R ⁷ and a in the formula (2-4) have the same meaning as those symbols in the formula (2-3), and the bonding position of Z ⁵ and R ⁷ to the benzene ring Is the same as that in the formula (2-3). R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms. Examples of R ⁸ or R ⁹ other than hydrogen are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, 2-methylbutyl, hexyl, 2-methylpentyl, heptyl, 2-methylhexyl, octyl, 2-methylheptyl 2-ethylhexyl, decyl, phenyl, cyclopentyl, and cyclohexyl. Both R ⁸ and R ⁹ can be one of these groups, one can be one of these groups and the other can be hydrogen.

R ⁸ and R ⁹ may combine with each other to form a ring with N. Examples of the dithiocarbamate group in such a case are N-cyclotrimethylenedithiocarbamate group, N-cyclotetramethylenedithiocarbamate group, N-cyclopentamethylenedithiocarbamate group, N-cyclohexamethylenedithiocarbamate group, N- A cycloheptamethylenedithiocarbamate group, an N-cyclooctamethylenedithiocarbamate group, and the like. Preferred dithiocarbamate groups are N, N-dimethyldithiocarbamate group, N, N-diethyldithiocarbamate group, N-methyldithiocarbamate group and N-ethyldithiocarbamate group. An N, N-diethyldithiocarbamate group is most preferred.

式（２−４−３）において、Ｚ^１０は式（２−３−４）におけるＺ^１０と同一の意味を有し、Ｚ^１０以外の記号は式（２−４）における記号と同一の意味を有し、そしてベンゼン環へのＺ^５およびＲ^７のＺ^１０に対する結合位置は、式（２−４）におけるＺ^７に対するこれらの結合位置と同一である。 Z ⁷ in formula (2-4) is also preferably a group represented by —C ₂ H ₄ —Z ¹⁰ as in the case of formula (2-1). That is, a preferred example of the formula (2-4) is the formula (2-4-3).

In the formula ^{(2-4-3), Z 10} have the meanings identical to ^{Z 10} in the formula ^(2-3-4), the symbols other than ^{Z 10} are the same meanings as those of the codes in Formula (2-4) And the bonding positions of Z ⁵ and R ⁷ to Z ¹⁰ on the benzene ring are the same as these bonding positions to Z ⁷ in formula (2-4).

Next, Table 1 shows some specific examples of the compound (1-1), the compound (1-2), the compound (1-3), and the compound (1-4) among the silicon compounds of the present invention. It shows in Table 2-Table 4 using a symbol. In these examples, in the following formula (1-1-1), formula (1-2-1), formula (1-3-1), and formula (1-4-1), R ¹ is phenyl. , Z ¹ is —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₅ H ₁₀ — or —C ₂ H ₄ —O—C ₃ H ₆ —, Z ⁴ is a single bond, —CH ₂ —, —C ₂ H ₄ — or —C ₃ H ₆ —, Z ⁶ is a single bond, —CH ₂ —, —C ₂ H ₄ — or one —CH ₂ — in these alkylenes is —COO. It is an example in the case of a group replaced with-. These examples are preferable examples of the silicon compound of the present invention.

なお、化合物（１−１）、化合物（１−２）、化合物（１−３）、および化合物（１−４）は、表２〜表５に記載された例によって制限されない。

In addition, a compound (1-1), a compound (1-2), a compound (1-3), and a compound (1-4) are not restrict | limited by the example described in Table 2-Table 5.

式（１−１）におけるＲ^１、Ｒ^２およびＲ^３は、式（１）におけるこれらの記号と同一の意味を有し、Ａ^１は式（２−１）で示される基である。

式（２‐１）において、Ｚ^１は２〜２０個の炭素原子を有するアルキレンまたは３〜８個の炭素原子を有するアルケニレンであり、そしてこれらのアルキレンおよびアルケニレンにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、Ｒ^４は水素、１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリール、または７〜２０個の炭素原子を有するアリールアルキルであり、Ｒ^５は１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリールまたは７〜２０個の炭素原子を有するアリールアルキルであり、Ｘ^１はハロゲンである。 Next, the manufacturing method of a compound (1-1) among the silicon compounds of this invention is demonstrated.

R ¹ , R ² and R ³ in formula (1-1) have the same meaning as those symbols in formula (1), and A ¹ is a group represented by formula (2-1).

In formula (2-1), Z ¹ is alkylene having 2 to 20 carbon atoms or alkenylene having 3 to 8 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is — R ⁴ is hydrogen, alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, or arylalkyl having 7-20 carbon atoms , R ⁵ is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms or arylalkyl having 7 to 20 carbon atoms, and X ¹ is halogen.

式（３−１）において、Ｒ^１は式（１）中のＲ^１と同一の意味を有し、Ｍは１価のアルカリ金属原子である。アルカリ金属の好ましい例はナトリウムおよびカリウムである。最も好ましい例はナトリウムである。 A preferred raw material used in the present invention is the compound (3-1).

In the formula (3-1), ^{R 1} has the same meaning as ^{R 1} in formula (1), M is a monovalent alkali metal atom. Preferred examples of alkali metals are sodium and potassium. The most preferred example is sodium.

The compound (3-1) can be obtained by hydrolyzing and condensing a silane compound having a trifunctional hydrolyzable group in the presence of an organic solvent, water and an alkali metal hydroxide. In this method, the compound (3-1) can be produced in a short time and in a high yield (see, for example, WO03 / 024870 pamphlet). In producing the compound (3-1), by using at least two silane compounds having a trifunctional hydrolyzable group, eight R ^{1 s} in the formula (3-1) are at least two different groups. The constituted compound (3-1) can be obtained. Since compound (3-1) exhibits high reactivity, its derivatives can be synthesized easily and with high yield by using this compound as a raw material. For example, a Si—H functional silsesquioxane derivative can be produced by reacting the compound (3-1) with a Si—H functional diorganochlorosilane.

これらの式におけるＲ^１、Ｒ^２およびＲ^３は、式（１）におけるこれらの記号と同一の意味を有する。 The Si—H functional diorganochlorosilane is represented by the formula (4). A preferred example of compound (4) is dimethylchlorosilane. Compound (5) is obtained by reacting compound (3-1) with compound (4).

R ¹ , R ² and R ³ in these formulas have the same meaning as those symbols in formula (1).

In order to synthesize compound (5) by reacting compound (3-1) with compound (4), a method utilizing nucleophilic substitution can be employed. This method is described, for example, in J. Am. Chem. Soc., 112 (1990), 1931-. The conditions for selecting the solvent used in this nucleophilic substitution reaction are that it does not react with the compound (3-1) and the compound (4) and that it is sufficiently dehydrated. Examples of the solvent are tetrahydrofuran, toluene, dimethylformamide and the like. The most preferred solvent is well dehydrated tetrahydrofuran. The preferable usage-amount of a compound (4) is 3-15 times in the equivalent ratio with respect to a compound (3-1). In this reaction, triethylamine may be used as a catalytic role for promptly proceeding the reaction. When using triethylamine, it is preferable that it is 3-15 times in the equivalent ratio with respect to a compound (3-2).

The reaction temperature is not particularly limited as long as the side reaction is not accompanied and the quantitative nucleophilic substitution reaction proceeds. However, the charging of the raw material may be performed under a low temperature condition, for example, in an ice bath. The subsequent reaction may be performed under room temperature conditions or under heating conditions. Specifically, the reaction temperature is in the range of 0 to 150 ° C, more preferably in the range of 0 to 50 ° C. The reaction time is not particularly limited as long as it is sufficient for the quantitative nucleophilic substitution reaction to proceed. Usually, the target silicon compound can be obtained in 1 to 15 hours.

Furthermore, since the compound (3-1) has -ONa as a reactive group, hydrogen chloride is not generated even when chlorosilanes are used in the synthesis reaction of the derivative. Therefore, the reaction operation can be facilitated and the reaction can be completed completely.

式（３−２）におけるＲ^１は式（１）におけるＲ^１と同一の意味を有する。このような化合物は、酸と化合物（３−１）を反応させることにより、容易に得られる。この時の酸との反応においては、必要に応じて有機溶剤を使用することが出来る。化合物（３−１）と有機溶剤を混合し、この混合物に酸を滴下することにより反応を進行させる方法を用いることが出来る。 Another preferred raw material used in the present invention is compound (3-2).

^{R 1} in the formula (3-2) has the same meaning as ^{R 1} in Formula (1). Such a compound can be easily obtained by reacting an acid with the compound (3-1). In the reaction with the acid at this time, an organic solvent can be used as necessary. A method can be used in which the compound (3-1) and an organic solvent are mixed and the reaction is allowed to proceed by dropping an acid into the mixture.

The organic solvent used in this reaction is not particularly limited as long as it does not inhibit the progress of the reaction. For example, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, and halogenated hydrocarbons such as methylene chloride and carbon tetrachloride. Acetates such as methyl acetate, ethyl acetate and butyl acetate, preferably tetrahydrofuran and ethyl acetate.

A desirable ratio of compound (3-1) when mixed with a solvent is 0.05 to 50% by weight based on the weight of the solvent. If it is 50% by weight or less, the concentration of by-product salt can be lowered, which is advantageous for allowing the reaction to proceed. Moreover, if it is 0.05 weight% or more, volume efficiency is good and it is preferable on cost. And a more desirable ratio is 1 to 10 weight%.

The acid used in this reaction is a proton donor (Bronsted acid), and there is no particular limitation as long as it is a compound that can react with compound (3-1) to obtain compound (3-2). For example, cyanic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid, nitric acid, nitrous acid, sulfuric acid, sulfuric acid, carbonic acid, hydrochloric acid, bromic acid, phosphoric acid, boric acid, formic acid, acetic acid, propionic acid, butyric acid, stearic acid, oxalic acid , Malonic acid, succinic acid, adipic acid, acrylic acid, methacrylic acid, oleic acid, maleic acid, chloroformic acid, chloroacetic acid, trifluoroacetic acid, cyclohexanecarboxylic acid, pivalic acid, benzoic acid, toluic acid, naphthoic acid, phthalic acid , Cinnamic acid, nicotinic acid, thiophenecarboxylic acid, S-thioacetic acid, dithioacetic acid, S-thiobenzoic acid, dithiobenzoic acid, thiocarbonic acid, trithiocarbonic acid, xanthogenic acid, methanesulfonic acid, benzenesulfonic acid, p-toluene Examples of sulfonic acid, phenylphosphonic acid, and diphenylphosphinic acid are preferable. Ku is an organic acid, more preferably a carboxylic acid, and most preferably is acetic acid.

When these acids are used in an amount of 4 times mol or more based on the compound (3-1), the reaction can be completed. When the use ratio is within this range, there is little possibility of causing an undesirable side reaction, and the amount of the neutralizing agent used in the post-treatment step can be small and efficient. Furthermore, it is preferable that this use ratio is 4 times mol or more and 10 times mol or less with respect to a compound, More preferably, it is 4 times mol or more and 5 times mol or less.

The reaction temperature may be room temperature, and may be heated as necessary to promote the reaction. Or you may cool as needed in order to control the heat_generation | fever by reaction or an unfavorable reaction.

The reaction time is 0.5 to 8 hours. However, since the reaction time is generally affected by the raw material reactivity, the raw material concentration, the reaction temperature, the shape of the apparatus (stirring efficiency), the shape of the product or by-product, etc. It is not meant to limit the invention.

The compound (3-2) can be synthesized with the compound (5) by reacting with the compound (4) using nucleophilic substitution as in the case of the compound (3-1). The preferable usage-amount of a compound (4) is 3-15 times in the equivalent ratio with respect to a compound (3-2), when making it react with all the Si-OH (silanol) groups of a compound (3-2). In this reaction, hydrogen chloride is generated by the reaction of hydrogen of silanol and chlorine of chlorosilane, and therefore it is necessary to remove this hydrogen chloride from the reaction system. The method for removing hydrogen chloride is not limited, but it is most preferable to use triethylamine. The preferable usage-amount of a triethylamine is 3-15 times in the equivalent ratio with respect to a compound (3-2). A preferable solvent used in the reaction is the same as in the reaction using the compound (3-1). A preferable reaction temperature is a temperature at which a side reaction does not occur simultaneously and a quantitative nucleophilic substitution reaction can proceed. However, when charging the raw materials, it is most preferable to carry out under low temperature conditions, for example, in an ice bath, and thereafter at room temperature. The reaction time is not particularly limited as long as it is sufficient for the quantitative nucleophilic substitution reaction to proceed. Usually, the target silicon compound can be obtained in 10 to 15 hours.

式（６）におけるＺ^２は、単結合、または１〜１８個の炭素原子を有するアルキレン、または２〜６個の炭素原子を有するアルケニレンであり、そしてこれらのアルキレンおよびアルケニレンにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよい。 When synthesizing the silicon compound of the present invention, it is preferable to use a hydrosilylation reaction method using the compound (5). That is, the reaction between the compound (5) and the compound (6) in the presence of a transition metal catalyst.

Z ² in formula (6) is a single bond, or alkylene having 1 to 18 carbon atoms, or alkenylene having 2 to 6 carbon atoms, and any —CH ₂ in these alkylene and alkenylene. -May be replaced by -O-.

Examples of the transition metal catalyst used are platinum, rhodium, iridium, ruthenium, palladium, molybdenum, iron, cobalt, nickel, manganese and the like. Of these, platinum catalysts are more preferred. These catalysts can be used as a homogeneous catalyst dissolved in a solvent or a solid catalyst supported on carbon or silica. It may be used in the form of coexisting phosphine, amine, potassium acetate and the like. A preferable amount of the transition metal catalyst is 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol as a transition metal catalyst atom with respect to 1 mol of the Si—H group in the compound (5).

式（７）におけるＲ^１、Ｒ^２およびＲ^３は式（１）におけるそれぞれの記号と同一の意味を有し、Ｚ^２は式（６）におけるＺ^２と同一の意味を有する。 It is preferable that the usage-amount of a compound (6) is 1-5 times by the equivalent ratio with respect to Si-H group in a compound (5). Since the hydrosilylation reaction proceeds almost quantitatively, there is little point in increasing this equivalent ratio. However, since the effect of shortening the reaction time can be expected, the only adverse effect of using a large amount of the compound (6) is only cost efficiency. On the other hand, in order to leave a part of the Si—H group unreacted, the equivalent ratio need only be smaller than 1. In this way, the compound represented by the formula (7) is obtained.

^R 1, ^{R 2} and ^{R 3} in the formula (7) have the same meanings as each of the symbols in the formula (1), ^{Z 2} has the same meaning as ^{Z 2} in Formula (6).

The preferable reaction temperature in the hydrosilylation reaction is not higher than the boiling point of the solvent used. The compound (6) is a compound having a polymerizable unsaturated bond. In order to prevent this compound from spontaneously polymerizing during the hydrosilylation reaction, the preferred reaction temperature is 20-80 ° C. For the purpose of suppressing this polymerization reaction, a polymerization inhibitor such as a phenol derivative, a phenothiazine derivative or an N-nitrosophenylamine salt derivative may be used. The most preferred polymerization inhibitor is 4-tert-butylpyrocatechol. The preferred amount of use is 1 to 100,000 ppm based on the total weight of the reaction solution. A more preferable range of the amount used is 100 to 20,000 ppm.

The organic solvent used in the hydrosilylation reaction is not particularly limited as long as it can easily dissolve the raw material without reacting with it. Preferred examples of organic solvents are aliphatic hydrocarbons (eg hexane and heptane), aromatic hydrocarbons (eg toluene and xylene), and cyclic ethers (eg tetrahydrofuran and dioxane). Considering the solubility of the compound (5), toluene is most preferable. And in order to control the activity of the catalyst, alcohols such as 2-propanol may be added.

これらの式におけるＺ^２は式（６）のＺ^２と同一の意味を有し、Ｚ^２、Ｒ^１、Ｒ^２およびＲ^３は式（７）におけるこれらの記号と同一の意味を有し、ＴＭＳはトリメチルシリル基を示す。 Compound (7) can also be produced by the following method. First, in the presence of a platinum-divinyltetramethyldisiloxane complex, a compound (7- T) is manufactured. Subsequently, the compound (7) having a hydroxyl group is derived by alcoholysis using a large excess of methanol at room temperature or under slightly warmed conditions (40 ° C.).

^{Z 2} in these formulas have the same meanings as ^{Z 2} in Formula ^(6), Z ^2, R 1, ^{R 2} and ^{R 3} have the same meanings as those of these codes in Formula (7), TMS represents a trimethylsilyl group.

式（８）におけるＲ^４、Ｒ^５およびＸ^１は式（２−１）におけるこれらの記号と同一の意味を有し、Ｘはハロゲンである。このハロゲンの例は塩素、臭素およびヨウ素であり、塩素および臭素が好ましい。Ｘ^１とＸは同一であっても異なっていてもよい。 Then, compound (1-1) is obtained by reacting compound (7) with compound (8) in which halogen is bonded to the α-position carbon.

R ⁴ , R ⁵ and X ¹ in the formula (8) have the same meaning as those symbols in the formula (2-1), and X is a halogen. Examples of this halogen are chlorine, bromine and iodine, with chlorine and bromine being preferred. X ¹ and X may be the same or different.

The hydrogen halide produced as a by-product in this reaction induces a side reaction such as dehydration or addition to a double bond site. Therefore, the reaction is carried out in the presence of an organic base in order to remove this. Examples of organic bases are pyridine, dimethylaniline, triethylamine and tetramethylurea. Other organic bases may be used as long as side reactions can be suppressed and the reaction can proceed rapidly. The most preferred example of the organic base is triethylamine. Although this reaction is a nucleophilic substitution reaction that proceeds quantitatively, the amount of compound (8) used is preferably 1 to 10 times in terms of an equivalent ratio to compound (7). By increasing the amount of compound (8) used, all compounds (7) can be reacted, and the reaction time can be shortened.

This reaction is usually carried out in an inert gas atmosphere such as argon gas or nitrogen gas, using a dry organic solvent inert to the raw material. Examples of organic solvents are cyclic ethers (THF, dioxane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (methylene chloride, chloroform, etc.) and carbon tetrachloride. A preferred example of the organic solvent is methylene chloride. There is no particular limitation on the reaction temperature. However, since this reaction proceeds violently with heat generation, it is usually better to carry out under low temperature conditions. The preferred reaction temperature is 100 ° C. or less, and the most preferred reaction temperature is 35 ° C. or less. Actually, the reaction may be performed under irregular reaction temperature control. For example, in the initial stage, the reaction may be carried out while cooling the reaction system using a dry ice-methanol bath or an ice bath, and then the temperature may be raised to near room temperature to continue the reaction. There is no particular limitation on the reaction time. Usually, the target silicon compound can be obtained in 1 to 10 hours.

式（２‐１‐２）におけるＺ^２は、式（６）におけるＺ^２と同一の意味を有し、Ｘ^１、Ｒ^４およびＲ^５は、式（２−１）におけるこれらの記号と同一の意味を有する。 Compound (1-1) can also be produced by a method in which the reaction step of compound (6) and compound (8) is performed first. First, the compound (6) and the compound (8) are reacted to synthesize a compound represented by the formula (2-1-2).

Z ² in formula (2-1-2) has the same meaning as Z ² in formula (6), and X ¹ , R ⁴ and R ⁵ are the same as those symbols in formula (2-1). Has the meaning of

式（２‐１‐３）におけるＺ^２は、式（６）におけるＺ^２と同一の意味を有し、Ｒ^２およびＲ^３は、式（１−１）と同一の意味を有し、Ｘ^１、Ｒ^４およびＲ^５は、式（２−１）におけるこれらの記号と同一の意味を有する。 Subsequently, the compound (2-1-2) and the compound (4) are subjected to a hydrosilylation reaction to synthesize a compound represented by the formula (2-1-3), and then the compound (3-1) or the compound (3-2). ) To synthesize a compound (1-1). A method for synthesizing the compound (2-1-3) is described in, for example, Macromol. Rapid Commun., 23 (2002), 612-.

Z ² in formula (2-1-3) has the same meaning as Z ² in formula (6), R ² and R ³ have the same meaning as in formula (1-1), and X 2 ¹ , R ⁴ and R ⁵ have the same meaning as these symbols in formula (2-1).

The reaction between compound (6) and compound (8) can be carried out in the same manner as the reaction between compound (7) and compound (8). The hydrosilylation reaction between the compound (2-1-2) and the compound (4) can be carried out in the same manner as the reaction between the compound (6) and the compound (5). The reaction between compound (2-1-3) and compound (3-1) or compound (3-2) is the same as the reaction between compound (4) and compound (3-1) or compound (3-2). Can be implemented.

In the following description, unreacted raw material compounds and solvents may be collectively referred to as “impurities”. When a distillation method is applied to remove impurities, the target compound may be decomposed by being kept under high temperature conditions for a long time. Therefore, in order to remove impurities efficiently without impairing the purity of the compound (1-1), it is preferable to purify by reprecipitation operation. This purification method is performed as follows. First, the reaction solution is dissolved in a solvent that dissolves both the compound (1-1) and impurities. A preferred concentration of the compound (1-1) at this time is roughly 1 to 15% by weight. Next, a solvent that does not dissolve the compound (1-1) but dissolves impurities, a so-called precipitant is added to this solution to precipitate only the compound (1-1). A preferred amount of the precipitating agent is 20 to 50 times based on the weight of the solvent used to dissolve both the compound (1-1) and the impurities. This use amount range is also a rough standard, and may not necessarily be within these ranges together with the concentration range of the compound (1-1).

A preferred solvent for dissolving the compound (1-1) is a solvent having a large dissolving power and a relatively low boiling point. A preferred precipitant is a solvent that is compatible with a solvent for dissolving the compound (1-1), does not dissolve the compound (1-1) at all, dissolves only impurities, and has a relatively low boiling point. Examples of preferred precipitating agents are lower alcohols. A particularly preferred precipitating agent is methanol. And in order to raise a refinement | purification further, what is necessary is just to increase the repetition frequency of reprecipitation operation.

In order to further purify the compound (1-1) after removing the polymerizable unreacted product, it is preferable to apply a column chromatography method. A preferred adsorbent used in this case is silica gel or the like. Preferred developing solvents are hexane, cyclohexane, toluene, chloroform, ethyl acetate, acetone and the like. A more preferred developing solvent is a mixed solvent of ethyl acetate and hexane. The mixing ratio of the solvent is not particularly limited, but may be adjusted so that the transfer rate (Rf value) of the target product with respect to the developing solvent is in the range of 0.1 to 0.7.

式（１−２）におけるＲ^１、Ｒ^２およびＲ^３は、式（１）におけるこれらの記号と同一の意味を有し、Ａ^２は式（２−２）で示される基である。

式（２−２）において、Ｚ^３は２〜１０個の炭素原子を有するアルキレンであり、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、または−ＣＯＯ−で置き換えられてもよく、Ｒ^６は１〜３個の炭素原子を有するアルキルであり、ａは０〜２の整数であり、Ｘ^２はハロゲンであり、ベンゼン環への−ＳＯ_２Ｘ^２−の結合位置は、Ｚ^３の結合位置に対して、オルト位、メタ位またはパラ位であり、Ｒ^６の結合位置は、Ｚ^３および−ＳＯ_２Ｘ^２−のそれぞれの結合位置を除く任意の位置である。 Next, the manufacturing method of a compound (1-2) is demonstrated among the silicon compounds of this invention.

R ¹ , R ² and R ³ in formula (1-2) have the same meaning as those symbols in formula (1), and A ² is a group represented by formula (2-2).

In the formula (2-2), Z ³ is alkylene having 2 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or —COO—, and R 3 ⁶ is an alkyl having 1 to 3 carbon atoms, a is an integer of 0 to 2, X ² is a halogen, and the bonding position of —SO ₂ X ² — to the benzene ring is Z ³ . The position is ortho, meta or para with respect to the bonding position, and the bonding position of R ⁶ is an arbitrary position excluding the bonding positions of Z ³ and —SO ₂ X ² —.

これらの式において、Ｚ^４は単結合または１〜８個の炭素原子を有するアルキレンであり、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、または−ＣＯＯ−で置き換えられてもよく、Ｒ^６、Ｘ^２およびａは、式（２−２）におけるこれらの記号と同一の意味を有し、ベンゼン環への−ＳＯ_２Ｘ^２−の結合位置は、ハロゲン化Ｚ^４の結合位置に対して、オルト位、メタ位またはパラ位であり、Ｒ^６の結合位置は、Ｚ^４および−ＳＯ_２Ｘ^２−のそれぞれの結合位置を除く任意の位置であり、Ｒ^２およびＲ^３は式（１−２）におけるこれらの記号と同一の意味を有する。 First, a compound represented by the formula (2-2-3) is synthesized by a hydrosilylation reaction between the compound represented by the formula (4) and the compound represented by the formula (2-2-2).

In these formulas, Z ⁴ is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or —COO— ⁶ , X ² and a have the same meaning as these symbols in formula (2-2), and the bonding position of —SO ₂ X ² — to the benzene ring is relative to the bonding position of halogenated Z ^4. In the ortho-position, meta-position or para-position, the bonding position of R ⁶ is any position except the bonding positions of Z ⁴ and —SO ₂ X ² —, and R ² and R ³ are represented by the formula ( It has the same meaning as these symbols in 1-2).

Next, the compound (2-2-3) is reacted with the compound (3-1) or the compound (3-2) to produce a silicon compound represented by the formula (1-2).

The hydrosilylation reaction between the compound represented by formula (4) and the compound represented by formula (2-2-2) can be carried out in the same manner as the reaction between compound (5) and compound (6). The reaction between compound (2-2-3) and compound (3-1) or compound (3-2) is the same as the reaction between compound (4) and compound (3-1) or compound (3-2). Can be implemented.

For purification of the compound (1-2) in the reaction mixture, the above-described purification method by reprecipitation operation and / or column chromatography can be used.

これらの式におけるＲ^１、Ｒ^２およびＲ^３は、式（１）におけるこれらの記号と同一の意味を有し、Ａ^３は式（２−３）で示される基であり、Ａ^４は式（２−４）で示される基である。

式（２−３）において、Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり、Ｚ^７は炭素原子の数が２〜１０であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり、Ｒ^７は１〜３個の炭素原子を有するアルキルであり、ａは０〜２の整数であり、Ｘ^３はハロゲンであり、ベンゼン環へのＺ^５の結合位置はＺ^７の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^７のそれぞれの結合位置を除く任意の位置である。

式（２‐４）において、Ｒ^８およびＲ^９は独立して水素、１〜１２個の炭素原子を有するアルキル、５〜１０個の炭素原子を有するシクロアルキルまたは６〜１０個の炭素原子を有するアリールであり、そしてＲ^８およびＲ^９は互いに結合してＮと共に環を形成してもよく、Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり、Ｚ^７は炭素原子の数が２〜１０であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり、Ｒ^７は１〜３個の炭素原子を有するアルキルであり、ａは０〜２の整数であり、ベンゼン環へのＺ^５の結合位置はＺ^７の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^７のそれぞれの結合位置を除く任意の位置である。 Next, the manufacturing method of a compound (1-3) and a compound (1-4) among the silicon compounds of this invention is demonstrated.

R ¹ , R ² and R ³ in these formulas have the same meaning as those symbols in formula (1), A ³ is a group represented by formula (2-3), and A ⁴ is a formula It is a group represented by (2-4).

In the formula (2-3), Z ⁵ is an alkylene having 1 to 3 carbon atoms, in which any —CH ₂ — may be replaced by —O—, and Z ⁷ has the number of carbon atoms. 2 to 10 in which any —CH ₂ — may be replaced by —O—, —COO— or —OCO—, R ⁷ is alkyl having 1 to 3 carbon atoms, a is an integer of 0 to 2, X ³ is a halogen, the bonding position of Z ⁵ on the benzene ring is a meta or para position with respect to the binding position of Z ^7, the bonding position of R ⁷ is Z It is an arbitrary position excluding the bonding positions of ⁵ and Z ⁷ .

In formula (2-4), R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, or 6 to 10 carbon atoms. And R ⁸ and R ⁹ may combine with each other to form a ring with N, and Z ⁵ has 1 to 3 carbon atoms, and any —CH ₂ — may be —O—. Z ⁷ is alkylene having 2 to 10 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—, —COO— or —OCO—. R ⁷ is alkyl having 1 to 3 carbon atoms, a is an integer of 0 to 2, and the bonding position of Z ⁵ to the benzene ring is meta or para to the bonding position of Z ^7. The bonding position of R ⁷ is that of Z ⁵ and Z ⁷ It is an arbitrary position excluding each coupling position.

式（２−３−２）において、Ｚ^６は単結合、または炭素原子の数が１〜８であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり、Ｚ^５、Ｒ^７、Ｘ^３およびａは、式（２−３）におけるこれらの記号と同一の意味を有し、ベンゼン環へのＺ^５の結合位置はＺ^６の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^６のそれぞれの結合位置を除く任意の位置である。 A preferred production method of the compound (1-3) is the compound (5) obtained by the reaction of the compound (3-1) or the compound (3-2) with the compound (4), and the formula (2-3-2). It is a hydrosilylation reaction with the compound shown by these.

In Formula (2-3-2), Z ⁶ is a single bond or 1 to 8 carbon atoms, and any —CH ₂ — is replaced by —O—, —COO— or —OCO—. Z ⁵ , R ⁷ , X ³ and a have the same meaning as those symbols in formula (2-3), and the bonding position of Z ⁵ to the benzene ring is the bonding of Z ⁶ It is a meta position or a para position with respect to the position, and the bonding position of R ⁷ is an arbitrary position excluding the bonding positions of Z ⁵ and Z ⁶ .

The hydrosilylation reaction between the compound (5) and the compound (2-3-2) can be carried out in the same manner as the reaction between the compound (5) and the compound (6).

For purification of the compound (1-3) in the reaction mixture, the above-described purification method by reprecipitation operation and / or column chromatography can be used.

式（９）におけるＲ^８およびＲ^９は、式（２−４）におけるこれらの記号と同一の意味を有し、Ｍ^１は周期律表第１族または第２族の金属元素であり、そしてｐはＭ^１の原子価と同じ値である。Ｍ^１の例は、Ｌｉ、Ｎａ、Ｋ、Ｃｕ、Ｍｇ、Ｃａ、Ｚｎ等である。Ｍ^１の好ましい例はＮａおよびＫである。 It is possible to obtain a silicon compound represented by the formula (1-4) by reacting the compound (1-3) obtained in the hydrosilylation reaction step with a metal salt of dithiocarbamate represented by the formula (9). it can.

R ⁸ and R ⁹ in formula (9) have the same meaning as these symbols in formula (2-4), M ¹ is a metal element of group 1 or group 2 of the periodic table, and p is the same value as the valence of M ¹ . Examples of M ¹ are Li, Na, K, Cu, Mg, Ca, Zn, and the like. Preferred examples of M ¹ are Na and K.

The reaction between the compound (1-3) and the compound (9) is a quantitative nucleophilic substitution reaction, and no side reaction occurs. However, the preferable usage-amount of dithiocarbamate is 1-5 times in the equivalent ratio with respect to the halogen content in a compound (1-3). By using a large amount of this salt, the reaction time can be shortened. The reaction is usually carried out in a dry organic solvent inert to the raw material in an inert gas atmosphere such as nitrogen gas. Examples of organic solvents are lower alcohols (eg methanol), cyclic ethers (eg tetrahydrofuran and dioxane), and aromatic hydrocarbons (eg toluene and xylene). Preferred examples of the organic solvent are tetrahydrofuran and methanol. A preferable reaction temperature is 120 ° C. or less in consideration of a possibility that dithiocarbamate is thermally decomposed. A more preferred temperature is 100 ° C. or lower. Although there is no restriction | limiting in particular in reaction time, Usually, the target silicon compound can be obtained in 1 to 10 hours. If necessary, a phase transfer catalyst such as benzyltrimethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium bromide, trioctylammonium chloride, dioctylmethylammonium chloride, triethylamine or dimethylaniline can be used in the reaction.

For purification of the compound (1-4) in the reaction mixture, the above-described purification method by reprecipitation operation and / or column chromatography method can be used. The reaction between the dithiocarbamate and the compound (1-3) and the purification of the compound (1-4) must be carried out in a draft equipped with a fluorescent lamp and an ultraviolet cut film with ultraviolet rays cut. And since compound (1-4) has dithiocarbamate which is a photosensitizing group, it is preserve | saved in a cool and dark place in the light-shielding container which enclosed inert gas, such as nitrogen and argon, in non-aqueous environment. There must be.

式（２−４−２）において、Ｚ^６は単結合、または炭素原子の数が１〜８であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり、その他の記号は、式（２−４）における記号と同一の意味を有し、ベンゼン環へのＺ^５の結合位置はＺ^６の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^６のそれぞれの結合位置を除く任意の位置である。 Compound (1-4) can also be produced by a method in which the reaction step of a metal salt of dithiocarbamate and an alkyl halide group is first carried out. This production method is a method in which a compound (2-3-2) and a compound (9) are first reacted to obtain a compound represented by the formula (2-4-2).

In the formula (2-4-2), Z ⁶ is a single bond, or the number of carbon atoms is 1 to 8, and arbitrary —CH ₂ — is replaced by —O—, —COO— or —OCO—. The other symbols have the same meaning as the symbols in formula (2-4), and the bonding position of Z ⁵ to the benzene ring is meta or para to the bonding position of Z ^6. And the bonding position of R ⁷ is an arbitrary position excluding the bonding positions of Z ⁵ and Z ⁶ .

This reaction itself is basically the same as the reaction between the compound (1-3) and the compound (9), and can be carried out in the same manner as in this reaction. However, the same precautions as in the reaction of the compound (5) and the compound (2-3-2) in the above production method are necessary in terms of handling a compound having a polymerizable group. That is, the reaction temperature needs to be considerably low and about 20 to 80 ° C., and the use of a polymerization inhibitor is also necessary. In addition to the reaction and purification steps, the ultraviolet rays should be blocked as much as possible during product storage. And a compound (1-4) can be obtained by the hydrosilylation reaction of the said compound (5) and a compound (2-4-2). This hydrosilylation reaction can be carried out in the same manner as in the reaction of the compound (5) and the compound (2-3-2).

式（２−３−３）において、Ｒ^２およびＲ^３は式（４）におけるこれらの記号と同一の意味を有し、他の記号は式（２−３−２）におけるこれらの記号と同一の意味を有する。ベンゼン環へのＺ^５およびＲ^７の結合位置は、式（２−３−２）におけるこれらの記号の結合位置と同一である。 Compound (1-3) can also be produced by a production method using the reaction using compound (3-1) or compound (3-2) as the final reaction step. First, in the presence of a transition metal catalyst, the compound (4) and the compound (2-3-2) are subjected to a hydrosilylation reaction to produce the compound (2-3-3).

In the formula (2-3-3), R ² and R ³ have the same meaning as those symbols in the formula (4), and other symbols are the same as those symbols in the formula (2-3-3). Has the meaning. The bonding positions of Z ⁵ and R ⁷ to the benzene ring are the same as the bonding positions of these symbols in formula (2-3-2).

Then, the compound (2-3-3) is reacted with the compound (3-1) or the compound (3-2) to produce the compound (1-3). The hydrosilylation reaction between compound (4) and compound (2-3-2) can be carried out in the same manner as the hydrosilylation reaction between compound (5) and compound (2-3-2). The reaction between compound (2-3-3) and compound (3-1) or compound (3-2) is the same as the reaction between compound (4) and compound (3-1) or compound (3-2). Can be implemented.

Next, an addition polymerizable monomer capable of initiating polymerization using the compound (1) will be described. This addition polymerizable monomer is a monomer having at least one addition polymerizable double bond. One example of a monomer having one addition polymerizable double bond is a (meth) acrylic acid derivative. Specific examples are (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) Acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 2- (meth) acryloyloxyethyl isocyanate, (meth) acrylate 2-aminoethyl, 2- (2-bromopropanoyloxy) ethyl (meth) acrylate 2- (2-bromoisobutyryloxy) ethyl (meth) acrylate, 1- (meth) acryloxy-2-phenyl-2- (2,2,6,6-tetramethyl-1-piperidinyloxy) Ethane, (1- (4-((4- (meta Acryloxy) ethoxyethyl) phenylethoxy) piperidine, .gamma. (methacryloyloxypropyl) trimethoxysilane, 3- (3,5,7,9,11,13,15- hepta ethylpentamethylene cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15- hepta isobutyl - pentacyclo [9 .5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15- hepta isooctyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7 9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^{3, 9.} 1 ^5,15 . 1 ^7,13 ] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^{3,9 .1,5,15.1,7,13} ] ^{octasiloxane-} 1-yl) propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptaethylpentacyclo [9.5]. .1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11,13, 15 hepta isobutyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3, 5,7 9,11,13,15- hepta isooctyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate , 3 - [(3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane -1- yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11,13,15- heptaphenyl penta cyclo ^[9.5.1.1 3,9 ^{.1 5,15. 1713} ]] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) ) Acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) Acrylate, trifluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2- Perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, and 2- (meth) acryloyloxyethyl phosphorylcholine.

Another example of a monomer having one addition polymerizable double bond is a styrenic monomer. Specific examples thereof include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, m-chloromethylstyrene, o-aminostyrene, p-styrene chlorosulfonic acid, styrenesulfonic acid and salts thereof. , Vinylphenylmethyldithiocarbamate, 2- (2-bromopropanoyloxy) styrene, 2- (2-bromoisobutyryloxy) styrene, 1- (2-((4-vinylphenyl) methoxy) -1-phenyl Ethoxy) -2,2,6,6-tetramethylpiperidine, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13] octasiloxane, 3- (3,5,7,9,11,13,15- hepta ethylpentamethylene cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13} ] octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11,13,15- hepta isobutyl penta cyclo ^[9.5.1.1 3,9 ^{.1 5,15 .1 7,13]} octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11,13,15- hepta isooctyl penta cyclo ^[9.5.1.1 3,9 .1 ^{5 ,} 15.1 ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] oct-siloxane -1 Yl) ethyl styrene, 3- (3,5,7,9,11,13,15- heptaphenyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane 1-yl) ethyl styrene, 3 - ((3,5,7,9,11,13,15- hepta ethylpentamethylene cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7, 13]} octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- hepta isobutyl penta cyclo ^[9.5.1.1 3, 9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- hepta isooctyl penta cyclo [9.5. 1.1 ^3,9 .1 ^5,15 1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^{3, 9} .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, and 3 - ((3,5,7,9,11,13,15- heptaphenyl penta cyclo [9 .5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene.

Other examples of monomers having one addition polymerizable double bond include fluorine-containing vinyl monomers (perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc.), silicon-containing vinyl monomers (vinyl). Trimethoxysilane, vinyltriethoxysilane, etc.), maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, maleimide monomers (maleimide, methyl) Maleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc.), monomers having nitrile groups (acrylonitrile, meta Rilonitrile), monomers having an amide group (acrylamide, methacrylamide, etc.), vinyl ester monomers (vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc.), olefins ( Ethylene, propylene, etc.), conjugated diene monomers (butadiene, isoprene, etc.), vinyl halides (vinyl chloride, etc.), vinylidene halides (vinylidene chloride, etc.), allyl halides (eg, allyl chloride), allyl alcohol, vinyl Pyrrolidone, vinyl pyridine, N-vinyl carbazole, methyl vinyl ketone, and vinyl isocyanate. Further, a macromonomer having one polymerizable double bond per molecule and a main chain of which is a macromer of styrene, (meth) acrylic acid ester, diorganosiloxane or alkylene glycol is also exemplified.

Examples of monomers having two addition polymerizable double bonds are divinylbenzene and di (meth) acrylate monomers. Examples of di (meth) acrylate monomers include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalate ester neopentyl glycol di ( Meth) acrylate, trimethylolpropane di (meth) acrylate, bis [(meth) acryloyloxyethoxy] bisphenol A, bis [(meth) acryloyloxyethoxy] tetrabromobispheno A, bis [(meth) acryloxypolyethoxy] bisphenol A, 1,3-bis (hydroxyethyl) 5,5-dimethylhydantoin, 3-methylpentanediol di (meth) acrylate, hydroxypivalate ester neopentyl glycol The derivatives di (meth) acrylate and bis [(meth) acryloyloxypropyl] tetramethyldisiloxane. Furthermore, a macromonomer having two polymerizable double bonds in the molecule and a main chain of which is a macromer of styrene, (meth) acrylic acid ester, diorganosiloxane or alkylene glycol is also exemplified.

Examples of monomers having three or more addition polymerizable double bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta ( (Meth) acrylate, tris (2-hydroxyethylisocyanate) tri (meth) acrylate, tris (diethylene glycol) trimaleate tri (meth) acrylate, 3,7,14-tris [((((meth) acryloyloxypropyl) dimethylsiloxy)] -1,3,5,7,9,11,14- hepta ethyl tricyclo ^{[7.3.3.1 5 and 11]} hept siloxane, 3,7,14- tris [(((meth) acryloyloxy propyl ) Dimethylsiloxy)]-1 3,5,7,9,11,14- hepta isobutyl tricyclo ^{[7.3.3.1 5 and 11]} hept siloxane, 3,7,14- tris [(((meth) acryloyloxy propyl) dimethylsiloxy )] - 1,3,5,7,9,11,14- hept isooctyl tricyclo ^{[7.3.3.1 5 and 11]} hept siloxane, 3,7,14- tris [(((meth) acryloyloxypropyl) dimethylsiloxy)] - 1,3,5,7,9,11,14- hept cyclopentanol tilt Li cyclo ^{[7.3.3.1 5 and 11]} hept siloxane, 3,7,14- tris [ (((meth) acryloyloxy propyl) dimethylsiloxy)] - 1,3,5,7,9,11,14- heptaphenyl tricyclo ^{[7.3.3.1 5 and 11]} hept siloxane, Kutakisu (3- (meth) acryloyloxy propyl dimethylsiloxy) octasilsesquioxane, and octakis (3- (meth) acryloyloxy propyl) it is octasilsesquioxane. Furthermore, the macromonomer which has three or more polymerizable double bonds in a molecule | numerator and whose principal chain is a macromer of styrene, (meth) acrylic acid ester, diorganosiloxane, or alkylene glycol is also mentioned.

The above monomers may be used alone or a plurality thereof may be copolymerized. The copolymerization may be random copolymerization or block copolymerization. Preferred monomers used in the present invention are (meth) acrylic acid derivatives and styrene derivatives. A more preferred monomer is a (meth) acrylic acid derivative. A plurality of (meth) acrylic acid derivatives may be copolymerized, or a plurality of styrene derivatives may be copolymerized. At least one (meth) acrylic acid derivative and at least one styrene derivative may be copolymerized.

Next, a method of subjecting an addition polymerizable monomer to atom transfer radical polymerization using the compound (1-1), the compound (1-2), or the compound (1-3) as an initiator and a transition metal complex as a catalyst Will be described. The atom transfer radical polymerization method in the present invention is one of the living radical polymerization methods. Examples of documents describing living radical polymerization methods are J. Am. Chem. Soc., 117 (1995), 5614-, Macromolecules, 28 (1995), 7901-, and Science, 272 (1996), 866. -That's it.

Preferable examples of the transition metal complex used as the polymerization catalyst are metal complexes having a group metal of Group 7, Group 8, Group 9, Group 10 or Group 11 of the periodic table as a central metal. Further preferred catalysts are zero-valent copper complexes, monovalent copper complexes, divalent ruthenium complexes, divalent iron complexes and divalent nickel complexes. Of these, a copper complex is preferable. Examples of monovalent copper compounds are cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. When a copper compound is used, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, pyridylmethanimine (N- (n-propyl) -2-pyridylmethane, Imine), polyamines (tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc.), or polycyclic alkaloids such as L-(-)-sparteine are added as ligands. . A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Examples of other suitable catalysts include divalent iron bistriphenylphosphine complexes (FeCl ₂ (PPh ₃ ) ₂ ), divalent nickel bistriphenylphosphine complexes (NiCl ₂ (PPh ₃ ) ₂ ), and 2 This is a bistributylphosphine complex of nickel (NiBr ₂ (PBu ₃ ) ₂ ).

A solvent may be used for the polymerization reaction. Examples of solvents used include hydrocarbons (eg, benzene, toluene, etc.), ethers (eg, diethyl ether, THF, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbons (eg, methylene chloride, chloroform, chlorobenzene, etc.) ), Ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol (eg, methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, etc.), nitrile (eg, acetonitrile, propionitrile, Benzonitrile, etc.), esters (eg, ethyl acetate, butyl acetate, etc.), carbonate solvents (eg, ethylene carbonate, propylene carbonate, etc.), amide solvents (eg, N, N-dimethylformamide, N, N-di) Tylacetamide, etc.), hydrochlorofluorocarbon solvents (eg, HCFC-141b, HCFC-225, etc.), hydrofluorocarbon solvents (eg, HFCs, etc.), perfluorocarbon solvents (eg, perfluoropentane, perfluorohexane, etc.) An alicyclic hydrofluorocarbon solvent (eg, fluorocyclopentane, fluorocyclobutane, etc.), an oxygen-containing fluorine solvent (eg, fluoroether, fluoropolyether, fluoroketone, fluoroalcohol, etc.), and water. The compounds in parentheses listed here are preferred examples of the respective solvents. These may be used alone or in combination of two or more. Polymerization can also be carried out in an emulsion system or a system using supercritical fluid CO ₂ as a medium. In addition, the solvent which can be used is not restrict | limited to these examples.

Atom transfer radical polymerization can be performed under reduced pressure, normal pressure, or increased pressure, depending on the type of addition polymerizable monomer and the type of solvent. The polymerization catalyst or generated radical may be deactivated when it comes into contact with oxygen. In such a case, it is important to perform the polymerization in an inert gas atmosphere such as nitrogen or argon because the polymerization rate decreases or a good living polymer cannot be obtained. In this reaction, it is necessary to previously remove dissolved oxygen in the polymerization system under reduced pressure. And it is also possible to transfer to a superposition | polymerization process under reduced pressure as it is after the removal process of dissolved oxygen. A conventional method can be adopted for the atom transfer radical polymerization, and it is not particularly limited by the polymerization method. For example, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a bulk-suspension polymerization method, or the like can be employed. And polymerization temperature is the range of 0-200 degreeC, and preferable polymerization temperature is the range of room temperature-150 degreeC.

式（１−１−２）において、すべてのＲ^１１は炭素原子の数が１〜８であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ_２−が−Ｏ−、−ＣＨ＝ＣＨ−、シクロアルキレンまたはシクロアルケニレンで置き換えられてもよいアルキル、任意の水素がハロゲン、メチルまたはメトキシで置き換えられてもよいフェニル、非置換のナフチル、および任意の水素がフッ素、１〜４個の炭素原子を有するアルキル、ビニルまたはメトキシで置き換えられてもよいフェニル基と炭素原子の数が１〜８であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレン基とで構成されるフェニルアルキルから選択される同一の基であり；フェニルまたはフェニルアルキルのフェニル基が複数の置換基を有するときは、それらの置換基は同一の基であってもよいし異なる基であってもよく；Ｒ^２およびＲ^３は１〜８個の炭素原子を有するアルキル、フェニルおよびシクロへキシルから独立して選択される基である。そして、Ａ^１は式（２−１）で示される基である。

式（２−１）において、Ｚ^１は２〜２０個の炭素原子を有するアルキレンまたは３〜８個の炭素原子を有するアルケニレンであり、そしてこれらのアルキレンおよびアルケニレンにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；Ｒ^４は水素、１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリール、または７〜２０個の炭素原子を有するアリールアルキルであり；Ｒ^５は１〜２０個の炭素原子を有するアルキル、６〜２０個の炭素原子を有するアリールまたは７〜２０個の炭素原子を有するアリールアルキルであり；そして、Ｘ^１はハロゲンである。 When the compound (1-1-2) is used as an initiator, the polymer obtained by the above method is represented by the formula (P-1). In the following description, the polymer represented by the formula (P-1) is represented by the polymer (P-1).

In formula (1-1-2), all R ¹¹ have 1 to 8 carbon atoms, any hydrogen may be replaced with fluorine, and any —CH ₂ — is —O—, -CH = CH-, alkyl optionally substituted with cycloalkylene or cycloalkenylene, phenyl optionally substituted with halogen, methyl or methoxy, unsubstituted naphthyl, and optionally hydrogen substituted with fluorine, 1- An alkyl group having 4 carbon atoms, a phenyl group which may be replaced by vinyl or methoxy, and an alkylene group having 1 to 8 carbon atoms and in which any —CH ₂ — may be replaced by —O— And when the phenyl group of phenyl or phenylalkyl has a plurality of substituents, it is Selected R ² and R ³ are independently from hexyl alkyl, the phenyl and cycloalkyl having from 1 to 8 carbon atoms; the substituents identical to the may be a group may be different groups It is a group. A ¹ is a group represented by the formula (2-1).

In formula (2-1), Z ¹ is alkylene having 2 to 20 carbon atoms or alkenylene having 3 to 8 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is — May be replaced by O-; R ⁴ is hydrogen, alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, or arylalkyl having 7-20 carbon atoms R ⁵ is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms or arylalkyl having 7 to 20 carbon atoms; and X ¹ is halogen.

式（Ｐ−１）におけるＲ^１１、Ｒ^２およびＲ^３は、式（１−１−２）におけるこれらの記号と同一の意味を有し、Ｂ^１は式（２−１−Ｐ）で示される基である。

式（２‐１‐Ｐ）において、Ｐ^１は付加重合性単量体の重合によって得られる構成単位の連鎖である。そして、その他の記号は式（２−１）における記号と同一の意味を有する。 In introducing A ¹ into the silsesquioxane derivative as a polymerization initiating group, a typical method for obtaining a derivative that is not hydrolyzed is a method in which a Grignard reagent is reacted with Si-halogen and a method in which Si-H is reacted. This is a method of reacting a compound having an aliphatic unsaturated bond. The latter is usually referred to as a hydrosilylation reaction method. In the present invention, the hydrosilylation reaction method is easier to apply in terms of the availability of raw materials, but is not limited thereto.

R ¹¹ , R ² and R ³ in formula (P-1) have the same meanings as those symbols in formula (1-1-2), and B ¹ is represented by formula (2-1-P). Group.

In the formula (2-1-P), P ¹ is a chain of structural units obtained by polymerization of an addition polymerizable monomer. The other symbols have the same meaning as the symbols in formula (2-1).

式（１‐２‐２）におけるＲ^１１、Ｒ^２およびＲ^３は、式（１−１−２）におけるこれらの記号と同一の意味を有し、Ａ^２は式（２−２）で示される基である。そしてＢ^２は式（２−２−Ｐ）で示される基である。

式（２−２）において、Ｚ^３は２〜１０個の炭素原子を有するアルキレンであり、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、または−ＣＯＯ−で置き換えられてもよく；Ｒ^６は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；Ｘ^２はハロゲンであり；ベンゼン環への−ＳＯ_２Ｘ^２の結合位置は、Ｚ^３の結合位置に対して、オルト位、メタ位またはパラ位であり、Ｒ^６の結合位置は、Ｚ^３および−ＳＯ_２Ｘ^２のそれぞれの結合位置を除く任意の位置である。Ａ^２を重合開始基としてシルセスキオキサン誘導体に導入する場合も、化合物（１−１−２）を得る場合と同様に、Ｓｉ−ハロゲンに対してグリニヤー試薬を反応させる方法とＳｉ−Ｈに対して脂肪族不飽和結合を有する化合物を反応させる方法を用いることができる。

式（Ｐ−２）におけるＲ^１１、Ｒ^２およびＲ^３は、式（１−２−２）におけるこれらの記号と同一の意味を有し、Ｂ^２は式（２−２−Ｐ）で示される基である。

式（２‐２‐Ｐ）において、Ｐ^２は付加重合性単量体の重合によって得られる構成単位の連鎖であり、この他の記号は式（２−２）におけるこれらの記号と同一の意味を有し、ベンゼン環への−ＳＯ_２Ｘ^２−およびＲ^６の結合位置は、式（２‐２）におけるそれ俺の結合位置と同一である。 When the compound (1-2-2) is used as an initiator, the polymer obtained by the above method is represented by the formula (P-2). In the following description, the polymer represented by the formula (P-2) is represented by a polymer (P-2).

R ¹¹ , R ² and R ³ in formula (1-2-2) have the same meaning as those symbols in formula (1-1-2), and A ² is represented by formula (2-2). Group. B ² is a group represented by the formula (2-2P).

In Formula (2-2), Z ³ is alkylene having 2 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or —COO—; R ⁶ is alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; X ² is halogen; the bonding position of —SO ₂ X ² to the benzene ring is the bonding of Z ³ The position is ortho, meta, or para with respect to the position, and the bonding position of R ⁶ is an arbitrary position excluding the bonding positions of Z ³ and —SO ₂ X ² . When A ² is introduced as a polymerization initiating group into a silsesquioxane derivative, as in the case of obtaining the compound (1-1-2), Si-H is reacted with a Grignard reagent and Si-H On the other hand, a method of reacting a compound having an aliphatic unsaturated bond can be used.

R ¹¹ , R ² and R ³ in formula (P-2) have the same meaning as those symbols in formula (1-2-2), and B ² is represented by formula (2-2P). Group.

In the formula (2-2-P), P ² is a chain of structural units obtained by polymerization of the addition polymerizable monomer, and other symbols have the same meaning as those symbols in the formula (2-2). And the bonding position of —SO ₂ X ² — and R ⁶ to the benzene ring is the same as that of the bond position in Formula (2-2).

式（１‐３‐２）におけるＲ^１１、Ｒ^２およびＲ^３は、式（１−１−２）におけるこれらの記号と同一の意味を有し、Ａ^３は式（２−３）で示される基である。

式（２−３）において、Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｚ^７は炭素原子の数が２〜１０であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり；Ｒ^７は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；Ｘ^３はハロゲンであり；そして、ベンゼン環へのＺ^５の結合位置はＺ^７の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^７のそれぞれの結合位置を除く任意の位置である。Ａ^３を重合開始基としてシルセスキオキサン誘導体に導入する場合も、化合物（１−１−２）を得る場合と同様に、Ｓｉ−ハロゲンに対してグリニヤー試薬を反応させる方法とＳｉ−Ｈに対して脂肪族不飽和結合を有する化合物を反応させる方法を用いることができる。

式（Ｐ−３）におけるＲ^１１、Ｒ^２およびＲ^３は、式（１−３−２）におけるこれらの記号と同一の意味を有し、Ｂ^３は式（２−３−Ｐ）で示される基である。

式（２‐３‐Ｐ）において、Ｐ^３は付加重合性単量体の重合によって得られる構成単位の連鎖であり、この他の記号は式（２−３）におけるこれらの記号と同一の意味を有し、ベンゼン環へのＺ^５およびＲ^７の結合位置は、式（２−３）におけるそれぞれの結合位置と同一である。 When the compound (1-3-2) is used as an initiator, the polymer obtained by the above method is represented by the formula (P-3). In the following description, the polymer represented by the formula (P-3) is represented by a polymer (P-3).

R ¹¹ , R ² and R ³ in formula (1-3-2) have the same meaning as those symbols in formula (1-1-2), and A ³ is represented by formula (2-3). Group.

In Formula (2-3), Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁷ is carbon number 2 to 10 wherein any —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁷ is an alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; X ³ is halogen; and the bonding position of Z ⁵ to the benzene ring is the meta position or the para position with respect to the bonding position of Z ⁷ , and the bonding position of R ⁷ Is an arbitrary position excluding the bonding positions of Z ⁵ and Z ⁷ . May be introduced into the silsesquioxane derivative A ³ as a polymerization initiator group, as in the case of obtaining a compound (1-1-2), the method and Si-H reacting Grignard reagents for Si- halogen On the other hand, a method of reacting a compound having an aliphatic unsaturated bond can be used.

R ¹¹ , R ² and R ³ in the formula (P-3) have the same meaning as those symbols in the formula (1-3-2), and B ³ is represented by the formula (2-3-P). Group.

In the formula (2-3-P), P ³ is a chain of structural units obtained by polymerization of the addition polymerizable monomer, and other symbols have the same meaning as those symbols in the formula (2-3). And the bonding positions of Z ⁵ and R ⁷ to the benzene ring are the same as the respective bonding positions in the formula (2-3).

The structure of the polymer (P-1) can be controlled by appropriately selecting the monomer to be used. For example, when the monomer is homopolymerized, silsesquioxane to which the homopolymer is bonded is obtained. When a plurality of monomers are simultaneously added and polymerized, silsesquioxane having a random copolymer bonded thereto is obtained. If a method of sequentially adding the monomers, for example, a method of completing the polymerization by adding the second monomer after the polymerization of the first monomer is completed, the block copolymer is obtained. Bound silsesquioxane can be obtained. By repeating this stepwise polymerization using a plurality of monomers, a silsesquioxane having a multiblock copolymer bonded thereto can be obtained. And it can also be set as the crosslinked polymer which has a three-dimensional network structure by coexisting a polyfunctional monomer as needed.

When polymerizing ordinary addition polymerizable monomers, a silsesquioxane bonded with a hyperbranched polymer is obtained by using a compound having a polymerizable functional group and also a function as an initiator. Can do. Examples of such compounds are 2- (2-bromopropanoyloxy) ethyl (meth) acrylate, 2- (2-bromoisobutyryloxy) ethyl (meth) acrylate, 2- (2-bromopropanoyloxy ) Styrene, and 2- (2-bromoisobutyryloxy) styrene. By using a silicon compound having a (meth) acryl group or a styryl group in combination, a structural unit containing a silicon atom can be introduced into the structure of the polymer. Examples of this silicon compound are trialkoxysilane, polydimethylsiloxane and silsesquioxane. After copolymerization of an addition-polymerizable monomer having an initiating group that does not participate in atom transfer radical polymerization, the resulting polymer is used as an initiator for addition in another polymerization mode (for example, nitroxyl polymerization or photo-iniferter polymerization). A polymerizable monomer can be polymerized to form a graft copolymer. Examples of addition polymerizable monomers having initiating groups not involved in atom transfer radical polymerization are 1- (2- (4-vinylphenylmethoxy) -1-phenylethoxy) -2,2,6,6-tetramethyl Piperidine, 1- (meth) acryloyloxy-2-phenyl-2- (2,2,6,6-tetramethyl-1-piperidinyloxy) ethane, (1- (4- (4- (meth) acryloyl) Oxyethoxyethyl) phenylethoxy) piperidine, and vinylphenylmethyldithiocarbamate.

A monomer having a glycidyl group (eg, glycidyl (meth) acrylate), a monomer having an oxetanyl group (eg, 3-ethyl-3- (meth) acryloyloxymethyloxetane), or a monomer having a dioxolane ( Example: After copolymerization with 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane), the resulting polymer is used as a thermal or photolatent cationic polymerization initiator. If an aliphatic sulfonium salt, an aromatic sulfonium salt or an aromatic iodonium salt is added, a crosslinked polymer having a three-dimensional network structure can be obtained by cationic polymerization. Examples of aliphatic sulfonium salts that are thermal latent cationic polymerization initiators are 3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimonate and 2-butenyltetramethylenesulfonium hexafluoroantimonate These are sold by Asahi Denka Kogyo Co., Ltd. Aromatic sulfonium salts, which are heat-latent or photo-latent cationic polymerization initiators, are commercially available from Sanshin Chemical Industry Co., Ltd. and Asahi Denka Kogyo Co., Ltd. Diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate is also an example of an aromatic sulfonium salt. An example of an aromatic iodonium salt is (4-pentadecyloxyphenyl) phenyl iodonium hexafluoroantimonate. When performing photolatent cationic polymerization, you may use together a photosensitizer, for example, Adeka optomer SP-100 (made by Asahi Denka Kogyo Co., Ltd.). Further, when obtaining a crosslinked polymer having a three-dimensional network structure by cationic polymerization, a monofunctional or polyfunctional glycidyl crosslinking agent, or a monofunctional or polyfunctional oxetane crosslinking agent may be present together.

Next, the purification method of a polymer (P-1) is demonstrated. This polymer is isolated and purified by efficiently removing unreacted addition polymerizable monomers. Although there are various methods, a purification method by reprecipitation operation is preferable. This purification method is performed as follows. First, a solvent that does not dissolve the polymer (P-1) but dissolves the unreacted monomer in the polymerization reaction solution containing the polymer (P-1) and the unreacted monomer, a so-called precipitant. Is added to this solution to precipitate only the polymer (P-1). A preferred amount of the precipitating agent is 20 to 50 times based on the weight of the polymerization reaction solution.

A preferred precipitant is a solvent that is compatible with the solvent used in the polymerization, does not dissolve the polymer (P-1) at all, dissolves only the unreacted monomer, and has a relatively low boiling point. Examples of preferred precipitating agents are lower alcohols and aliphatic hydrocarbons. Particularly preferred precipitating agents are methanol and hexane. And in order to raise the removal efficiency of an unreacted monomer further, what is necessary is just to increase the repetition frequency of reprecipitation operation. By this method, only the polymer (P-1) can be precipitated in a poor solvent, and the unreacted monomer and the polymer can be easily separated by a filtration operation.

In the polymer (P-1) isolated by the above method, the transition metal complex that is a polymerization catalyst remains, which may cause problems such as coloring of the polymer, influence on physical properties and environmental safety. . Therefore, it is necessary to remove this catalyst residue at the end of the polymerization reaction. The catalyst residue can be removed by an adsorption treatment using activated carbon or the like. Examples of adsorbents other than activated carbon are ion exchange resins (acidic, basic or chelate type), and inorganic adsorbents. The inorganic adsorbent has a solid acid, a solid base, or a neutral character. Since this is a particle having a porous structure, it has a very high adsorption capacity. One of the characteristics of inorganic adsorbents is that they can be used in a wide temperature range from low temperature to high temperature.

Examples of inorganic adsorbents are silicon dioxide, magnesium oxide, silica / alumina, aluminum silicate, activated alumina, clay clay such as acid clay, activated clay, zeolite (zeolite) adsorbent, dawsonite compounds , And hydrotalcite compounds. There are natural and synthetic zeolites, but any of them may be used. There are various types of silicon dioxide such as crystalline, amorphous, amorphous, glassy, synthetic and natural products, but in the present invention, powdered silicon dioxide can be used regardless of the type. . Examples of natural aluminum silicate are pumice, fly ash, kaolin, bentonite, activated clay, diatomaceous earth and the like. Synthetic aluminum silicate has a large specific surface area and a high adsorption capacity. The hydrotalcite compound is a hydrated carbonate of aluminum / magnesium hydroxide.

The acidic adsorbent and the basic adsorbent are preferably used in combination with activated carbon. Examples of the acidic adsorbent are acidic clay, activated clay, aluminum silicate and the like. Examples of basic adsorbents are activated alumina, the aforementioned zeolite adsorbents, hydrotalcite compounds and the like. These adsorbents may be used alone or in admixture of two or more. And the polymer (P-1) manufactured by atom transfer radical polymerization can be refine | purified by making it contact with activated alumina. As the activated alumina, a commercial product from Aldrich or the like can be used. When performing an adsorption treatment using activated alumina in combination with other adsorbents, the adsorbents can be mixed and brought into contact with each other, but they may be brought into contact with each other in separate steps. When contacting with the adsorbent, the reaction solution may be used as it is, or the reaction solution may be diluted with a solvent. The diluting solvent may be selected from common solvents provided that it is not a poor solvent for the polymer. There is no particular limitation on the temperature of the adsorbent treatment. Generally, the treatment may be performed at 0 ° C to 200 ° C. A preferred temperature range is from room temperature to 180 ° C. And the usage-amount of adsorption agent is the range of 0.1-500 weight% based on the weight of a polymer (P-1). In view of economy and operation, a preferable range is 0.5 to 10% by weight.

For the solid-liquid contact between the adsorbent and the polymer solution, a batch method in which stirring and mixing and solid-liquid separation are performed by a batch operation can be used. In addition to this, a fixed bed method in which a container is filled with an adsorbent and the polymer solution is passed, a moving bed method in which the liquid is passed through the moving bed of the adsorbent, a fluidized bed method in which the adsorbent is fluidized with liquid and adsorbed, etc. The continuous method can also be used. Furthermore, if necessary, operations for improving the dispersion efficiency such as shaking of the container or use of ultrasonic waves can be combined with the mixing and dispersing operation by stirring. After the polymer solution is brought into contact with the adsorbent, the adsorbent is removed by a method such as filtration, centrifugation, and sedimentation separation, and a water washing treatment is performed as necessary to obtain a purified polymer solution. The treatment with the adsorbent may be performed on the polymer (P-1) which is the final product, but may be performed on the intermediate product for producing the polymer. For example, in each polymerization stage of the block copolymer obtained by atom transfer radical polymerization, it is possible to isolate this polymer and perform an adsorption treatment. The polymer (P-1) that has been treated with the adsorbent may be separated by precipitation in a poor solvent or by distilling off volatile components such as a solvent under reduced pressure.

Further, the catalyst residue can be removed by using a water-insoluble solvent and a complexing agent aqueous solution, or by performing a purification treatment using a water-insoluble solvent and a complexing agent aqueous solution further containing an electrolyte component. That is, after the polymer (P-1) is dissolved in a water-insoluble solvent, a complexing agent aqueous solution or a complexing agent aqueous solution further containing an electrolyte component is added to the polymer (P-1) solution, followed by stirring and mixing. Then, by converting the transition metal component into a complex with the complexing agent and extracting it into the aqueous layer, the concentration of the catalyst component remaining in the polymer (P-1) can be significantly reduced.

Moreover, you may refine | purify a polymerization reaction liquid as object. When the viscosity of the polymerization reaction solution is high, a purification treatment may be performed after adding a water-insoluble solvent to obtain an appropriate solution viscosity. That is, after the polymerization reaction is completed, the polymerization reaction solution containing the polymer (P-1) is diluted with a predetermined amount of a non-aqueous solvent, and then a complexing agent aqueous solution or a complexing agent aqueous solution further containing an electrolyte component is added to this solution. A water-insoluble solvent containing the aqueous solution and the polymer (P-1) by physical operation such as centrifugal separation or stationary separation. To separate. By such a purification treatment, the concentration of the catalyst component remaining in the polymer (P-1) can be significantly reduced.

The operation procedure of this purification process does not necessarily have to be as described above. For example, after adding a complexing agent or a complexing agent and an electrolyte component to a polymer (P-1) or a polymerization reaction solution containing a polymer (P-1), a water-insoluble solvent is added, and water is further added. Good. Regardless of the operation procedure, the purification process is finally the same extraction process as the operation procedure described first, and the same effect can be obtained.

Here, a solution obtained by dissolving the polymer (P-1) with a water-insoluble solvent, a polymerization reaction solution or a solution obtained by diluting the polymerization reaction solution with a water-insoluble solvent may be referred to as a polymer (P-1) solution. . The mixing / contact of the polymer (P-1) solution with the complexing agent aqueous solution or the complexing agent aqueous solution further containing an electrolyte component is preferably stirred in a batch-type tank-type treatment tank provided with a stirrer. A shaking-type tank-type treatment tank may be used. The polymer concentration in the polymer (P-1) solution is a uniform solution and is a viscosity that allows stirring and mixing with the complexing agent aqueous solution, but is preferably 40% by weight or less. . When the polymer concentration in the polymer (P-1) solution is increased, precipitation and thickening of the polymer may become a problem, but in that case, the polymer can be heated to about 70 to 100 ° C. What is necessary is just to process under heating using the processing tank provided with heating apparatuses, such as a steam coil or a steam jacket. If the polymer concentration in the polymer (P-1) solution is low and it is a homogeneous solution at room temperature, stirring and contact can be performed at room temperature.

For oil-water separation between the polymer (P-1) solution and the complexing agent aqueous solution or the complexing agent aqueous solution further containing an electrolyte component, centrifugal separation or static separation utilizing the difference in specific gravity, or the difference in electrical properties is utilized. Electrostatic oil purification or the like can be used. In the present invention, since two-phase oil-water separation is required, the use of a two-phase separation type decanter is most preferable, but other centrifuges can naturally be used. In addition, when using an inorganic adsorbent in combination, since solids such as sludge are included, a three-phase separation type decanter will be used in that case. Is possible. And the polymer processed by the said process can be isolated by making it precipitate in a poor solvent, or distilling off volatile components, such as a solvent, under reduced pressure.

The number of mixing / contact and oil / water separation steps of the polymer (P-1) solution and the complexing agent aqueous solution or the complexing agent aqueous solution further containing the electrolyte component is determined by the concentration of the catalyst component remaining in the polymer (P-1). There is no particular limitation as long as it can be significantly reduced. That is, when the mixing / contacting and oil / water separation step is one step, the transition metal component in the polymer (P-1) is analyzed for each step to reduce the content to the target content. It is good also as the frequency | count of a process.

About the addition ratio of the complexing agent with respect to the transition metal component contained in a polymer (P-1), it is preferable that the molar ratio of the complexing agent with respect to a transition metal component is generally 1-1000 equivalent. Since the transition metal content in the polymer (P-1) can be predicted in advance when the polymerization reaction solution is charged, the transition metal content included in the polymer (P-1) to be treated is The amount of the complexing agent may be determined. The concentration of the complexing agent in the complexing agent aqueous solution is preferably in the range of 0.001 to 20% by weight.

Furthermore, in the complexing agent aqueous solution containing the electrolyte component, the main purpose is to improve the oil-water separation efficiency by increasing the specific gravity of the aqueous solution. It is not limited. In general, it can be used in a saturated or half-saturated state.

Such a process may be performed on the polymer (P-1) which is the final product, but may be performed on an intermediate product for producing the polymer. For example, in each polymerization stage of the block copolymer obtained by atom transfer radical polymerization, it is possible to isolate the polymer and perform such treatment.

Examples of water-insoluble solvents used in this purification step are anisole, benzene, carbon tetrachloride, chlorobenzene, chloroform, 1-chloronaphthalene, dibenzylnaphthalene, o-dichlorobenzene, m-dichlorobenzene, 1,1-dichloroethane. 1,2-dichloroethane, dichloromethane, diisopropyl ether, N, N-dimethylaniline, diphenyl ether, ethyl acetate, mesitylene, methyl acetate, isoamyl acetate, cyclohexanone, cyclopentanone, nitrobenzene, nitromethane, tetrachloroethylene, tetralin, toluene, trichloroethylene, And xylene. More preferred examples are chloroform, ethyl acetate and toluene.

The aqueous complexing agent solution used is an aqueous solution of at least one compound selected from aliphatic carboxylic acids, aromatic carboxylic acids, ammonia, amines, aminocarboxylic acids, amino acids, phosphoric acids, phosphonic acids, and inorganic sulfur compounds. . Among these compounds, compounds other than inorganic sulfur compounds may be in the form of salts as required, for example, alkali metal salts such as sodium, potassium and lithium, alkaline earth metal salts such as calcium and barium, iron (III) and vanadium. Such as heavy metal salts such as hydrochlorides, ammonium salts, amine salts, partially neutralized salts having a metal or basic substance equivalent to or less than the carboxyl group, or a mixture of these salts.

Examples of aliphatic carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, adipic acid, fumaric acid, citraconic acid , Itaconic acid, tricarbazic acid, propane-1,1,2,3-tetracarboxylic acid, butane-1-glycolic acid, lactic acid, β-hydroxypropionic acid, malic acid, tartaric acid, citric acid, alloisocitric acid, gluconic acid Pyruvic acid, oxalic acid, diglycolic acid and thiodiglycolic acid. Examples of aromatic carboxylic acids are benzoic acid, phthalic acid, isophthalic acid, mandelic acid, salicylic acid, 5-sulfosalicylic acid, α-carboxy-o-anisic acid, and o- (carboxymethylthio) benzoic acid.

Examples of amines are diethylamine, methylamine, ethylamine, propylamine, triethylamine, morpholine, piperidine, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, Nn-propylethylenediamine, N-isopropylethylenediamine, N- (2 -Hydroxyethyl) ethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, N, N'-di-n-propylethylenediamine, N, N-di (2-hydroxyethyl) ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-diaminopropane, meso-2,3-diaminobutane, rac-2,3 Diaminobutane, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, triethylenediamine, diethylenetriamine, 3,3'-diaminodipropylamine, triethylenetetraamine, 2-hydroxyethylamine, 2-methoxyethylamine, 2,2'- Dihydroxydiethyleneamine and polyamidoamine.

Examples of aminocarboxylic acids are iminodiacetic acid, iminodipropionic acid, N-methyliminodiacetic acid, N- (3,3′-dimethylbutyl) iminodiacetic acid, phenyliminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropion Acid, hydroxypropyliminodiacetic acid, 2-hydroxycyclohexyliminodiacetic acid, methoxyethyliminodiacetic acid, 2-hydroxybenzyliminodiacetic acid, N- (o-carboxyphenyl) iminodiacetic acid, N- (m-carboxyphenyl) iminodi Acetic acid, N- (p-carboxyphenyl) iminodiacetic acid, N- (carbamoylmethyl) iminodiacetic acid, cyanomethyliminodiacetic acid, aminoethyliminodiacetic acid, 2-ethoxycarbonylaminoethyliminodiacetic acid, phosphonomethyliminodiacetic acid , Phosphono Tiliminodiacetic acid, sulfoethyliminodiacetic acid, o-sulfophenyliminodiacetic acid, m-sulfophenyliminodiacetic acid, nitrilotriacetic acid, carboxyethyliminodiacetic acid, carboxymethyliminodipropionic acid, nitrilotripropionic acid, N, N′- Ethylenediamine, ethylenediamine-N, N′-dipropionic acid, N, N′-di (hydroxyethyl) ethylenediaminediacetic acid, Nn-butylethylenediaminetriacetic acid, N-cyclohexylethylenediaminetriacetic acid, N′-hydroxyethyl-N , N, N′-triacetic acid, benzylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid-zinc, ethylenediaminetetraacetic acid-2sodium, ethylenediaminetetraacetic acid-calcium, ethyl Diaminetetraacetic acid-magnesium, ethylenediaminetetraacetic acid-2 potassium, ethylenediamine-N, N′-diacetic acid N, N′-dipropionic acid, ethylenediamine-N, N′-di (2-propionic acid), ethylenediamine-N, N'-disuccinic acid, ethylenediamine-N, N'-diglutaric acid, ethylenediaminetetrapropionic acid, 1,2-propylenediaminetetraacetic acid, trimethylenediaminetetraacetic acid, tetramethylenediaminetetraacetic acid, pentamethylenediaminetetraacetic acid, hexamethylene Diaminetetraacetic acid, octamethylenediaminetetraacetic acid, 1,2-cyclopentanediaminetetraacetic acid, trans-cyclohexane-1,2-diaminetetraacetic acid, cyclohexane-1,4-diaminetetraacetic acid, 1,3,5-to Liaminocyclohexaacetic acid, o-phenylenediaminetetraacetic acid, 2-hydroxytrimethylenediaminetetraacetic acid, ethyl etherdiaminetetraacetic acid, hydantoic acid, (S, S) -ethylenediamine disuccinic acid, (S, S) -ethylenediaminedi Glutaric acid, (S) -aspartic acid-N, N-diacetic acid, (S, S) -iminodisuccinic acid, (S) -glutamic acid-N, N-diacetic acid, (S) -α-alanine-N, N -Diacetic acid and taurine-N, N-diacetic acid.

Examples of amino acids are glycine, sarcoxin, glycine methyl ester, valine, alanine, β-alanine, norleucine, leucine, isoleucine, phenylalanine, tyrosine, cysteine, methionine, serine, threonine, asparagine, glutamine, lysine, ε-polylysine, histidine Arginine, glutamic acid, polyglutamic acid, aspartic acid, 1,2-diaminopropionic acid, proline, tryptophan, and N-ethylglycine.

Examples of phosphoric acids are hexametaphosphoric acid, tetrametaphosphoric acid and condensed phosphoric acid. Examples of phosphonic acids are ethylidene diphosphonic acid, diethylenetriaminepenta (methylenephosphonic acid), methyldiphosphonic acid, nitrilotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), and 1,2-propylenediaminetetra (methylene Phosphonic acid).

Examples of inorganic sulfur compounds include thiosulfate (eg, sodium thiosulfate), polythionate (eg, SO ₃ — (S) _n —SO ₃ (n = 1 to 4)), dithionite (eg, : Sodium dithionate), sulfites (eg sodium sulfite), and dithionates (eg sodium dithionate).

There is no selection condition for the water to be used other than considering prevention of contamination of the polymer. Water through a filter of 50 μm or less is preferable, and pure water treated with an ion exchange resin is more preferable.

Examples of electrolyte components are sodium chloride, ammonium chloride, sodium acetate, sodium phosphate, sodium citrate, sodium tartrate, sodium benzoate, sodium sorbate, sodium phthalate, and sodium metabisulfite, which are Potassium salt may be used. Among the compounds used in the above complexing agent aqueous solution, those that can be used as electrolyte components are included. When using an electrolyte component, at least one of these is added to the aqueous complexing agent solution.

In order to remove the residual catalyst, an adsorption treatment using activated carbon or the like may be used in combination with the above method. When solid-liquid contact of an ion exchange resin or an inorganic adsorbent and a polymer solution is used in combination, a batch-type method in which stirring and mixing and solid-liquid separation are performed by a batch operation can be used. In addition to this, a fixed bed method in which a container is filled with an adsorbent and the polymer solution is passed, a moving bed method in which the liquid is passed through the moving bed of the adsorbent, a fluidized bed method in which the adsorbent is fluidized with liquid and adsorbed, etc. The continuous method can also be used. Furthermore, if necessary, operations for improving the dispersion efficiency such as shaking of the container or use of ultrasonic waves can be combined with the mixing and dispersing operation by stirring. After the polymer solution is brought into contact with the adsorbent, the adsorbent is removed by a method such as filtration, centrifugation, and sedimentation separation, and a washing treatment is performed as necessary to further increase the degree of purification.

A method for analyzing the molecular weight and molecular weight distribution of the polymer (P-1) will be described. Usually, the molecular weight of the addition polymer can be measured by gel permeation chromatography (GPC) using a calibration curve using a linear polymer such as polystyrene or poly (methyl methacrylate) as a standard sample. However, the polymer (P-1) belongs to a vinyl monomer polymer starting from silsesquioxane, that is, a branched polymer compound. Therefore, with the structure of the polymer (P-1), in determining the molecular weight, it is necessary to use a calibration curve with a linear polymer such as polystyrene or poly (methyl methacrylate) as a standard sample. It is considered that there is a problem in terms of accuracy. However, since the terminal portion of the polymer (P-1) is silsesquioxane, it can be easily decomposed under acidic conditions or basic conditions. That is, by separating the addition polymer from the silsesquioxane and then measuring the molecular weight, the accuracy of the molecular weight analysis of the polymer portion can be further improved. When decomposing the polymer (P-1) under acidic conditions, it is preferable to use hydrofluoric acid. When decomposing the polymer (P-1) under basic conditions, it is preferable to use potassium hydroxide. The polymer (P-1) can be decomposed in either a homogeneous system or a heterogeneous system. For example, the silsesquioxane part of the polymer (P-1) can be separated by a homogeneous mixed system of an organic solvent (THF, acetonitrile, etc.) and hydrofluoric acid capable of dissolving the polymer (P-1). . Even in a heterogeneous mixed system of toluene and hydrofluoric acid, the silsesquioxane moiety can be decomposed. In this case, a phase transfer catalyst is preferably used in combination. Examples of the phase transfer catalyst are benzyltrimethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium bromide, trioctylammonium chloride, dioctylmethylammonium chloride, triethylamine, dimethylaniline and the like. When potassium hydroxide is used, it can be decomposed in a mixed solvent of THF, ethanol and water.

When the addition polymer separated by these methods is measured by GPC, the molecular weight of the addition polymer portion in the polymer (P-1), that is, the molecular weight of the so-called graft chain can be determined. By using a universal calibration curve obtained from the viscosity and GPC data, it is possible to determine the molecular weight of the polymer (P-1) itself. The absolute molecular weight of the polymer (P-1) can also be determined by a terminal group determination method, a membrane osmotic pressure method, an ultracentrifugation method, a light scattering method, or the like.

The preferred molecular weight of the graft chain of the polymer (P-1) is in the range of 500 to 1,000,000 in terms of number average molecular weight in terms of poly (methyl methacrylate). A more preferable range is 1000 to 100,000. However, the upper limit and the lower limit of this range do not have any special meaning. The molecular weight distribution is preferably in the range of 1.01 to 2.0 in terms of dispersity (Mw / Mn).

The molecular weight of the graft chain can be adjusted by the ratio between the vinyl monomer and the α-haloester group which is an initiating group. That is, the theoretical molecular weight of the graft chain of the polymer (P-1) is predicted from the vinyl monomer / α-haloester group molar ratio and the monomer consumption rate using the following calculation formula: Can do.

Mn = (Consumption rate of monomer (mol%) / 100) × MW _M × (Molar ratio of vinyl monomer to α-haloester group) + MW _I

In this calculation formula, Mn is the theoretical number average molecular weight, MW _M is the molecular weight of the vinyl monomer, and MW _I is the molecular weight of the α-haloester group. In order to obtain a polymer having the above number average molecular weight range, the molar ratio of vinyl monomer / α-haloester group is about 2/1 to about 40000/1, preferably about 10 / It can be selected from a range of 1 to about 5000/1. The number average molecular weight can also be adjusted by changing the polymerization time.

From the vinyl monomer / compound (1-1-2) molar ratio and the monomer consumption rate, the theoretical molecular weight of the polymer (P-1) itself can be predicted using the following formula: it can.

Mn = (consumption rate of monomer (mol%) / 100) × MW _M × (molar ratio of vinyl monomer to compound (1-1-2)) + MW _I

In this calculation formula, Mn is the theoretical number average molecular weight, MW _M is the molecular weight of the vinyl monomer, and MW _I is the molecular weight of the compound (1-1-2).

Any method of GPC, ¹ H-NMR, and gas chromatography can be employed as a method for determining the monomer consumption rate (hereinafter sometimes referred to as “conversion rate”).

The explanation regarding the polymer (P-1) is also applied to the polymer (P-2) and the polymer (P-3).

Next, a method for photopolymerizing a vinyl monomer using the compound (1-4) as an initiator, that is, a so-called photo-iniferter polymerization method will be described. In this photoiniferter polymerization, it is well known that a dithiocarbamate group is radically dissociated by light and has excellent polymerization initiating ability and sensitizing ability. It is well known that the photopolymerization in this case is radical polymerization and is also living polymerization. Such information is disclosed in, for example, Polymer Bulletin, 11 (1984), 135-, Macromolecules, 19 (1986), 287-. Therefore, as long as the silicon compound of the present invention having a dithiocarbamate group is irradiated with light, it can continue to maintain the polymerization initiating ability and has the ability to initiate photopolymerization with respect to any radically polymerizable monomer. .

It is well known that the dithiocarbamate group has the functions of a polymerization initiator, a chain transfer agent and a polymerization terminator during photopolymerization, and the reaction mechanism has already been clarified. The compound (1-4) of the present invention having a dithiocarbamate group is dissociated into a radical on the alkylphenyl group bonded to the silicon compound and a dithiocarbamate radical by light irradiation. The radical on the alkylphenyl group is involved in the initiation reaction, and the dithiocarbamate radical is involved in the termination reaction. When the light irradiation is stopped or the monomer is consumed, the dithiocarbamate radical is added to the growth terminal as a terminator and forms a dithiocarbamate group again. Therefore, the polymer thus produced can also be used as a polymer photoinitiator having photopolymerization initiating ability. The silicon compound having a dithiocarbamate group of the present invention is decomposed by irradiating with an ultraviolet ray having a wavelength of 250 to 500 nm having an energy necessary for radical dissociation of the dithiocarbamate group, more preferably an ultraviolet ray having a wavelength of 300 to 400 nm. The polymerization of the vinyl monomer coexisting therewith can be initiated.

The embodiment of the polymerization reaction can be appropriately adopted from bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk-suspension polymerization, or the like. As a solvent in the case of producing by solution polymerization, a solvent having a small chain transfer constant and capable of dissolving a vinyl monomer and a polymer thereof is preferable. Examples of such preferred solvents are benzene, toluene, xylene, ethylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, methyl cellosolve, ethyl cellosolve, dimethylformamide, isopropyl alcohol, butanol, hexane, heptane and the like. A solvent having no characteristic absorption in the ultraviolet region of 250 to 500 nm is rather preferable. The polymerization temperature is in the range of 0 to 200 ° C, preferably in the range of room temperature to 150 ° C, but is not particularly limited.

Photoiniferter polymerization can be performed under reduced pressure, normal pressure, or increased pressure, depending on the type of vinyl monomer and the type of solvent. Usually, it is important to carry out under an inert gas atmosphere such as nitrogen or argon, for example, under the flow of an inert gas. Since it is necessary to remove the dissolved oxygen in the polymerization system under reduced pressure in advance, it is possible to proceed to the polymerization step under reduced pressure as it is after the dissolved oxygen removing step.

式（１−４−２）において、Ｒ^１１、Ｒ^２およびＲ^３は、式（１−１−２）におけるこれらの記号と同一の意味を有し、Ａ^４は式（２−４）で示される基である。

式（２−４）において、Ｒ^８およびＲ^９は独立して水素、１〜１２個の炭素原子を有するアルキル、５〜１０個の炭素原子を有するシクロアルキルまたは６〜１０個の炭素原子を有するアリールであり、そしてＲ^８およびＲ^９は互いに結合してＮと共に環を形成してもよく；Ｚ^５は炭素原子の数が１〜３であって任意の−ＣＨ_２−が−Ｏ−で置き換えられてもよいアルキレンであり；Ｚ^７は炭素原子の数が２〜１０であって任意の−ＣＨ_２−が−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよいアルキレンであり；Ｒ^７は１〜３個の炭素原子を有するアルキルであり；ａは０〜２の整数であり；そして、ベンゼン環へのＺ^５の結合位置はＺ^７の結合位置に対してメタ位またはパラ位であり、Ｒ^７の結合位置はＺ^５およびＺ^７のそれぞれの結合位置を除く任意の位置である。Ａ^４を重合開始基としてシルセスキオキサン誘導体に導入する場合も、化合物（１−１−２）を得る場合と同様に、Ｓｉ−ハロゲンに対してグリニヤー試薬を反応させる方法とＳｉ−Ｈに対して脂肪族不飽和結合を有する化合物を反応させる方法を用いることができる。 When the compound (1-4-2) is used as an initiator, the polymer obtained by the above method is represented by the formula (P-4). In the following description, the polymer represented by the formula (P-4) is represented by a polymer (P-4).

In the formula (1-4-2), R ¹¹ , R ² and R ³ have the same meaning as those symbols in the formula (1-1-2), and A ⁴ represents the formula (2-4). It is the group shown.

In formula (2-4), R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, or 6 to 10 carbon atoms. And R ⁸ and R ⁹ may combine with each other to form a ring with N; Z ⁵ has 1 to 3 carbon atoms and any —CH ₂ — may be —O—. Z ⁷ is alkylene having 2 to 10 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—, —COO— or —OCO—. R ⁷ is alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; and the bonding position of Z ⁵ to the benzene ring is meta-position to the bonding position of Z ⁷ or a para-position, binding position of ^{R 7} is ^{Z 5} and ⁷ is any position excluding the respective bonding positions. May be introduced into the silsesquioxane derivative A ⁴ as a polymerization initiator group, as in the case of obtaining a compound (1-1-2), the method in the Si-H reacting the Grignard reagent with respect to Si- halogen On the other hand, a method of reacting a compound having an aliphatic unsaturated bond can be used.

式（Ｐ−４）におけるＲ^１１、Ｒ^２およびＲ^３は、式（１−４−２）におけるこれらの記号と同一の意味を有し、Ｂ^４は式（２−４−Ｐ）で示される基である。

式（２‐４‐Ｐ）において、Ｐ^４はビニル系単量体の重合体からなる基であり、この他の記号は式（２−４）における記号と同様の意味を有し、そしてベンゼン環へのＺ^５およびＲ^７の結合位置は式（２−４）におけるこれらの結合位置と同一である。

R ¹¹ , R ² and R ³ in formula (P-4) have the same meaning as those symbols in formula (1-4-2), and B ⁴ is represented by formula (2-4-P). Group.

In the formula (2-4-P), P ⁴ is a group composed of a polymer of a vinyl monomer, and other symbols have the same meaning as the symbols in the formula (2-4), and benzene The bonding positions of Z ⁵ and R ⁷ to the ring are the same as these bonding positions in the formula (2-4).

The structure of the polymer (P-4) can be controlled in the same manner as in the case of obtaining the polymer (P-1) by the atom transfer radical polymerization method. By using an initiator monomer such as N, N-diethyldithiocarbamoylmethylstyrene or N-ethyldithiocarbamoylmethylstyrene in combination with a usual vinyl monomer polymerization, Oxan can be obtained. After copolymerization with a vinyl monomer having an initiating group that does not participate in photo-iniferter polymerization, the obtained polymer is used as an initiator, and further, in other polymerization modes (for example, atom transfer radical polymerization method) A graft copolymer can also be formed by polymerizing the monomer. Examples of vinyl monomers having an initiating group that does not participate in photoiniferter polymerization are 1- (2-((4-ethenylphenyl) methoxy) -1-phenylethoxy) -2,2,6,6- Tetramethylpiperidine, 1- (meth) acryloxy-2-phenyl-2- (2,2,6,6-tetramethyl-1-piperidinyloxy) ethane, (1- (4-((4- (meta ) Acryloxy) ethoxyethyl) phenylethoxy) piperidine, 2- (2-bromopropanoyloxy) ethyl (meth) acrylate, 2- (2-bromoisobutyryloxy) ethyl (meth) acrylate, p-chloromethylstyrene, 2- (2-bromopropanoyloxy) styrene, 2- (2-bromoisobutyryloxy) styrene and the like.

In addition, a polymer (P-4) can be inactivated with respect to an ultraviolet-ray by processing the dithiocarbamate group of the terminal after completion | finish of photoiniferter polymerization. Examples of the inactivation method include a method of treating the polymer (P-4) with an acidic solution or a basic solution, a method of treating the polymer (P-4) at a high temperature of 250 ° C. or higher for several minutes, and high-energy electromagnetic radiation having a wavelength of 220 nm or less. There are a method of irradiating, a method of photopolymerization after adding a monomer having an ultraviolet absorbing group, and a method of simply adding an ultraviolet absorber. The terminal dithiocarbamate group is substituted by adding a reagent having a large chain transfer constant (thiol derivative, thiuram, zanddates, nitroxides, etc.) while irradiating the obtained polymer (P-4) with ultraviolet rays. Is also possible.

A method for isolating and purifying the polymer (P-4) will be described. This compound is isolated and purified by efficiently removing unreacted vinyl monomers. Although there are various methods, the purification method by the reprecipitation operation is preferable. By this method, only the polymer (P-4) can be precipitated in a poor solvent, and the unreacted monomer and the polymer can be easily separated by a filtration operation. The polymer may be isolated by distilling off volatile components such as solvents and unreacted monomers under reduced pressure. A preferred solvent for dissolving the polymer (P-4) is a solvent having a large dissolving power and a relatively low boiling point. A preferred precipitant is compatible with the solvent of the polymer (P-4), does not dissolve the polymer (P-4) at all, dissolves only impurities or unreacted monomers, and has a relatively low boiling point. It is. Examples of preferred precipitants are lower alcohols and aliphatic hydrocarbons. A particularly preferred precipitating agent is methanol or hexane. And in order to raise a refinement | purification further, what is necessary is just to increase the repetition frequency of reprecipitation operation.

The molecular weight and molecular weight distribution of the polymer (P-4) can be analyzed in the same manner as in the method described for the polymer (P-1). The number average molecular weight of a polymer of vinyl monomers bonded to silsesquioxane, so-called graft chain, is in the range of 500 to 1,000,000. A more preferable range is 1000 to 100,000. However, the upper limit and the lower limit of this range do not have any special meaning. The molecular weight distribution of the graft chain is preferably in the range of 1.01 to 3.0 in terms of dispersion. It is also possible to determine the molecular weight of the polymer (P-4) by using a universal calibration curve obtained from the viscosity and GPC data. The absolute molecular weight of the polymer (P-4) can also be determined by a terminal group determination method, a membrane osmotic pressure method, an ultracentrifugation method, a light scattering method, or the like. The molecular weight of the graft chain in the polymer (P-4) can be adjusted in the same manner as in the case of the polymer (P-1).

The present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

The meanings of symbols used in the examples are as follows.
Ph: Phenyl TMS: Trimethylsilyl Mn: Number average molecular weight Mw: Weight average molecular weight EDTA · 2Na: Disodium ethylenediaminetetraacetate dihydrate

The molecular weight data in the examples are all polystyrene-converted values obtained by GPC (gel permeation chromatography). The measurement conditions for GPC are shown below.
Apparatus: JASCO GULLIVER 1500 (intelligent differential refractometer RI-1530) manufactured by JASCO Corporation
Solvent: Tetrahydrofuran (THF)
Flow rate: 1 ml / min
Column temperature: 40 ° C
Columns used: The following columns from Tosoh Corporation (used in series)
TSKguardcolumn HXL-L (GUARDCOLUMN)
TSKgel G1000HxL (exclusion limit molecular weight (polystyrene): 1,000)
TSkgel G2000HxL (exclusion limit molecular weight (polystyrene): 10,000)
Standard sample for calibration curve: Polymer Laboratories, Polymer Standards (PL), Polystyrene

In Examples 6 to 19, Shodex KF-G (GUARDCOLUMN) manufactured by Showa Denko KK and two Shodex KF-804L (exclusion limit molecular weight (polystyrene): 400,000) are connected in series, and a calibration curve is used. As a standard sample, Shodex STANDARD M-75 (polymethyl methacrylate) manufactured by Showa Denko Co., Ltd. was used. Other conditions are the same as above.

Example 1
<Compound (3-1-1): Synthesis of phenylsilsesquioxane derivative bonded with sodium>
In a reaction vessel having an internal volume of 50 liters equipped with a reflux condenser, a thermometer, and a stirring device, phenyltrimethoxysilane (6.54 kg), 2-propanol (26.3 liters), pure water (0.66 kg), and Sodium hydroxide (0.88 kg) was charged and sealed with dry nitrogen. The mixture was heated with stirring and reacted at reflux for 5 hours. After completion of the reaction, the heater was removed from the reaction vessel, and this vessel was left at room temperature for 15 hours to cool the reaction mixture. The supernatant was removed from the reaction mixture thus obtained by decantation. The white solid remaining in the reaction vessel was washed once with 2-propanol (9.87 kg). This was transferred to a stainless steel vat lined with a polytetrafluoroethylene sheet and dried for 24 hours at an internal temperature of 80 ° C. and a pressure of 6.7 × 10 ⁻⁴ MPa using a vacuum dryer. A white powdery compound (A-1) was obtained.

Example 2
<Introduction of trimethylsilyl group into compound (A-1)>
Compound (A-1) (1.2 g), tetrahydrofuran (10 g), and triethylamine (1.6 g) were charged into a 50 ml four-necked flask equipped with a reflux condenser and sealed with dry nitrogen. Under stirring with a magnetic stirrer, trimethylchlorosilane (2.2 g) was added dropwise over about 1 minute while maintaining the solution temperature at 15 to 20 ° C. After completion of the dropwise addition, stirring was continued at 15 ° C. for 3.5 hours. After completion of the reaction, the reaction product was washed with pure water and vacuum dried to obtain a white solid (1.2 g). This is designated as Compound (AT).

The compound (AT) was subjected to structural analysis by gel permeation chromatography (GPC), ¹ H-NMR, and ²⁹ Si-NMR. From the GPC chart, it was confirmed that the white solid showed monodispersity, the number average molecular weight in terms of polystyrene was 970, and the weight average molecular weight was 990. ^{From the 1} H-NMR chart, it was confirmed that the phenyl group and the trimethylsilyl group were present at an integration ratio of 2: 1. ^{From the 29} Si-NMR chart, there are two peaks having a phenyl group and derived from the T structure at −76.12 ppm and −78.95 ppm at an integration ratio of 1: 1, and a peak derived from the trimethylsilyl group is 10. It was confirmed that there was one in 62 ppm (both based on tetramethylsilane). These results support that the compound (AT) has a structure represented by the formula (3-T). Therefore, the compound (A-1) is a compound having a structure represented by the formula (3-1-1). The T structure is a term indicating a partial structure in which three oxygen atoms are bonded to one silicon atom, that is, —Si (O—) ₃ .

Example 3
<Compound (5-1): Synthesis of organosilicon compound having hydrosilyl group>
A compound (3-1-1) (69 g) obtained by using the stirring bar, the method of Example 1 in a four-necked flask having an internal volume of 1000 ml equipped with a dropping funnel, a thermometer, and a reflux condenser. Toluene (540 g) was charged and sealed with dry nitrogen. While stirring with a magnetic stirrer, dimethylchlorosilane (9.1 g) was added dropwise from the dropping funnel in about 35 minutes. At this time, the dropping rate was adjusted so that the solution temperature was 25 ° C to 35 ° C. After completion of the dropwise addition, the mixture was heated with stirring, and stirring was continued for 3 hours in a reflux state to complete the reaction. After completion of the reaction, the solution was allowed to cool down to 50 ° C. or lower. Next, 160 g of pure water was slowly dropped from the dropping funnel. After completion of dropping, the mixture was stirred for about 10 minutes to hydrolyze unreacted dimethylchlorosilane, and sodium chloride was dissolved. The reaction mixture thus obtained was transferred to a separatory funnel and separated into an organic layer and an aqueous layer. The obtained organic layer was washed with saturated brine, and then washed with water until neutrality. The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure using a rotary evaporator to obtain 71 g of a white solid. This white solid was washed with normal heptane (350 ml) and dried under reduced pressure to obtain 50 g of a white powdery solid.

The structure of the obtained white powdery solid was analyzed by gel permeation chromatography (GPC), ¹ H-NMR, ²⁹ Si-NMR and IR analysis. From the GPC chart, it was confirmed that the white solid was monodisperse, the number average molecular weight in terms of polystyrene was 900, and the weight average molecular weight was 910. ^{From the 1} H-NMR chart, it was confirmed that the integration ratio based on the phenyl group, hydrosilyl group, and methyl group was 40: 4: 24. ^{From the 29} Si-NMR chart, a peak suggesting a dimethylsilyl group was confirmed at −3.28 ppm (based on tetramethylsilane). Furthermore, from the IR spectrum measured by the KBr tablet method, absorption based on the stretching vibration of Si—H was confirmed at 2142 cm ⁻¹ . These results suggest that the compound obtained by the reaction of the compound (3-1-1) and dimethylchlorosilane has a structure represented by the formula (5-1).

Example 4
<Synthesis of silicon compound having hydroxyethoxypropyl group>
In a 50 ml four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer and a stirrer, compound (5-1) (5.2 g) obtained by using the method of Example 3 and ethylene glycol mono Allyl ether (6.6 g) and toluene (5.2 g) were charged and sealed with dry nitrogen. While stirring with a magnetic stirrer, the reaction solution was heated to a temperature of 42 ° C. After adding a platinum-divinyltetramethyldisiloxane complex / xylene solution (platinum content: 3.0 wt%, 33 μl) using a microsyringe, the reaction solution temperature was heated to 60 ° C. and stirring was continued for 2 hours. . And as a result of sampling the reaction liquid and performing IR analysis, it was confirmed that absorption of 2138 cm ⁻¹ suggesting Si—H group disappeared. The reaction mixture was then concentrated under reduced pressure, and the residue was diluted to 20% by weight with ethyl acetate (28 g). And powdered activated carbon (0.4g) was added and stirring was continued for 1.5 hours. The activated carbon was removed by filtration and then concentrated under reduced pressure to obtain 6.6 g of a viscous and transparent liquid.

The obtained viscous liquid was subjected to IR analysis by a liquid film method, and as a result, absorption due to O—H stretching vibration of a hydroxyl group was confirmed at 3450 cm ⁻¹ . As a result of ²⁹ Si-NMR analysis, a peak of 11.42 ppm corresponding to (3- (2-hydroxyethyloxy) propyl) dimethylsilyl group was confirmed. As a result of GPC analysis, the number average molecular weight was 1180 and the weight average molecular weight was 1230 in terms of polystyrene. The above data suggested that the viscous liquid was a compound having a chemical structure represented by formula (7-1).

Example 5
<Synthesis of silicon compound having 2-bromo-2-methylpropanoyloxyethoxypropyl group>
In an argon flask having an internal volume of 100 ml under an argon atmosphere, the compound (7-1) (1.0 g) obtained in Example 4, triethylamine (0.35 g) dried with molecular sieves (4A) and dry methylene chloride were used. (10 ml) was charged. The compound (7-1) was dissolved using a magnetic stirrer while stirring at room temperature, and then the solution was cooled using a dry ice-methanol bath, and the liquid temperature was kept at -78 ° C. Next, 2-bromo-2-methylpropanoyl bromide (0.81 g, 6.0 equivalents relative to compound (7-1)) was quickly added to this solution, and the mixture was stirred at -78 ° C for 1 hour. The mixture was further stirred at room temperature for 2 hours. After completion of the reaction, triethylamine-bromide was removed by filtration. Methylene chloride (50 ml) was added to the resulting reaction solution, and then washed once with water (100 ml), washed twice with an aqueous sodium bicarbonate solution (1%, 100 ml), and washed twice with water (100 ml). Were sequentially performed, and then dried over anhydrous magnesium sulfate (5 g). Then, this solution was concentrated at room temperature using a rotary evaporator to make the liquid volume about 5 ml. Methanol (50 ml) was added to the concentrated liquid (5 ml) to separate the viscous liquid component. Then, after leaving still in a -35 degreeC freezer and fully making the phase separation of a viscous liquid component, this component was acquired by decantation. This viscous liquid was purified by column chromatography and dried under reduced pressure at 40 ° C. for 6 hours to obtain a transparent viscous liquid (0.86 g, yield: 63.7%).

The GPC purity of this transparent viscous liquid was 98.3%. From the results of ¹ H-NMR, ¹³ C-NMR and ²⁹ Si-NMR shown below, it was found that this compound had a structure represented by the formula (1-1-3).
¹ H NMR (400 MHz, CDCl ₃ , TMS standard: δ = 0.0 ppm): 7.55-7.10 (m, 40H, Ph-Si), 4.17 (t, 8H,-[CH ₂ ] -O- (C = O) -), 3.39 (t, 8H , - [CH 2] -OC 2 H 4 -), 2.98 (t, 8H, -C 3 H 6 -O- [CH 2] -), 1.89 (s, 24H, - C (Br) [(CH ₃ ) ₂ ]), 1.29 (tt, 8H, -CH _2- [CH ₂ ] -CH _2- ), 0.42 (t, 8H, Si- [CH ₂ ]-), 0.27 ( s, 24H, -OSi [(CH ₃ ) ₂ ]-).
_{^{13 C NMR (100MHz, CDCl 3}} , TMS standard: δ = 0.0 ppm): 171.8 (C = O), 134.5~127.7 (Ph-Si), 73.9 (- [CH 2] -OC 2 H 4 -), 67.9 (-C ₃ H ₆ -O- [CH ₂ ]-), 65.1 (-[CH ₂ ] -O- (C = O)-), 55.8 (-[C] (Br) (CH ₃ ) ₂ ), 30.8 (-C (Br) [(CH ₃ ) ₂ ]), 23.1 (-CH _2- [CH ₂ ] -CH _2- ), 14.0 (Si- [CH ₂ ]-), -0.30 (-OSi [( CH ₃ ) ₂ ]-).
²⁹ Si NMR (79 MHz, CDCl ₃ , TMS standard: δ = 0.0 ppm): 11.31 (-O [Si] (CH ₃ ) ₂ CH _2- ), -76.10, -78.85 (Ph-SiO _1.5 ).

Example 6
<Preparation of polymerization solution>
In a draft cut with ultraviolet rays, cuprous bromide was introduced into an ampoule made of heat-resistant glass, and the compound (1-1-3) / methyl methacrylate / L-(-)-obtained in Example 5 was further obtained. Sparteine / anisole solution was added and cooled quickly with liquid nitrogen. Thereafter, freeze vacuum deaeration (pressure: 1.0 Pa) was performed three times in a vacuum apparatus equipped with an oil rotary pump, and the ampule was quickly sealed using a hand burner while maintaining the vacuum state. At this time, the ratio of the compound (1-1-3), methyl methacrylate, cuprous bromide and L-(−)-spartein in this polymerization solution was 1: 1200: 4 in this order. : 8, and the amount of anisole used was such that the concentration of methyl methacrylate was 50% by weight.

<Polymerization>
The sealed heat-resistant glass ampoule was set in a constant temperature shaking bath and polymerized to obtain a brown and viscous solution of the polymer (a). At this time, the polymerization temperature was 70 ° C., and the polymerization time was 0.5 hours. The monomer conversion rate in this polymerization reaction system was determined by measuring the ¹ H-NMR measurement after diluting the polymer (a) solution with deuterated chloroform, and determining the relationship between the proton ratios of the substituents in each of the monomer and the polymer. I asked for it. The obtained polymer (a) was recovered by reprecipitation purification with hexane to prepare an ethyl acetate solution (5% by weight) of this polymer (a), and 300 ml together with an aqueous EDTA · 2Na solution (2% by weight, 100 ml). -The copper complex was removed by adsorption by flushing with a separatory funnel. Further, this solution was added dropwise to hexane to reprecipitate the polymer, which was dried under reduced pressure (80 ° C., 6 hours). Table 6-1 shows the results of analysis of the monomer conversion rate in this polymerization reaction system, the theoretical number average molecular weight of the polymer (a) derived from the monomer conversion rate, the number average molecular weight actually measured by GPC measurement, and the molecular weight distribution. It was street.

<Theoretical molecular weight analysis of graft chain>
The theoretical molecular weight of the graft chain was calculated by the following formula, assuming that the ester bond that is the initiation terminal of the polymerization was cleaved by hydrolysis by hydrofluoric acid treatment, and all the termination terminals of the polymerization were Br Was as shown in Table 6-2.

<Calculation formula>
Theory of graft chain Mn = (monomer consumption rate (mol%) / 100) × MW _M × (molar ratio of vinyl monomer to α-bromoester group) + MW _I

<Parameters used for calculation>
MW _M = 100 (methyl methacrylate)
Molar ratio of vinyl monomer to α-bromoester group = 300
MW _I = 167.01 (BrC (CH ₃ ) ₂ CO ₂ H)

<Measurement of molecular weight of graft chain>
A mixed solution of hydrofluoric acid (0.17 ml) and acetonitrile (0.83 ml) was prepared. The polymer (a) (10 mg) was dissolved in this mixed solution in a polypropylene microtube (1.5 ml) into which a stirrer was introduced, and the mixture was stirred in an incubator equipped with a magnetic stirrer at 40 ° C. for 24 hours. Subsequently, the polymer was recovered by drying at 80 ° C. for 3 hours in a vacuum dryer. The results of GPC measurement of this polymer were as shown in Table 6-2.

Examples 7-12
Except having changed polymerization time as shown in Table 6-1, it superposed | polymerized like Example 6 and obtained the brown and viscous solution of each of a polymer (b)-a polymer (g). . Each polymer was purified in the same manner as in Example 6, and the monomer conversion, theoretical number average molecular weight, number average molecular weight and molecular weight distribution were determined. The results are shown in Table 6-1. The theoretical number average molecular weight calculation of the graft chain, the hydrofluoric acid treatment of the polymer, and the number average molecular weight and molecular weight distribution analysis of the graft chain by GPC measurement were performed in the same manner as in Example 6, and the results are shown in Table 6 It was shown in 2.

Example 13
<Preparation of polymerization solution>
In a draft cut with ultraviolet rays, cuprous bromide was introduced into an ampoule made of heat-resistant glass, and a compound (1-1-3) / methyl methacrylate / L-(-)-sparteine / anisole solution was added. Cooled quickly using liquid nitrogen. Thereafter, freeze vacuum deaeration (pressure: 1.0 Pa) was performed three times in a vacuum apparatus equipped with an oil rotary pump, and the ampule was quickly sealed using a hand burner while maintaining the vacuum state. At this time, the ratio of the compound (1-1-3), methyl methacrylate, cuprous bromide and L-(−)-spartein in this polymerization solution was 1: 600: 4 in this order of molar ratio. : 8, and the amount of anisole used was such that the concentration of methyl methacrylate was 50% by weight.

<Polymerization>
The sealed heat-resistant glass ampoule was set in a constant temperature shaking bath and polymerized to obtain a brown and viscous solution of the polymer (2a). At this time, the polymerization temperature was 70 ° C., and the polymerization time was 0.25 hours. The monomer conversion rate in this polymerization reaction system is the relationship between the proton ratio of the substituents in each of the monomer and the polymer by performing ¹ H-NMR measurement after diluting the polymer (2a) solution with deuterated chloroform. I asked for it. The obtained polymer was recovered by reprecipitation purification with hexane to prepare an ethyl acetate solution (5 wt%) of this polymer (2a), and 300 ml-separated with an EDTA · 2Na aqueous solution (2 wt%, 100 ml). The copper complex was adsorbed and removed by flushing with a funnel. Further, this solution was added dropwise to hexane to reprecipitate the polymer (2a), which was dried under reduced pressure (80 ° C., 6 hours). Table 7-1 shows the results of analysis of the monomer conversion rate in this polymerization reaction system and the theoretical number average molecular weight of the polymer (2a) derived from the monomer conversion rate, the number average molecular weight actually measured by GPC measurement, and the molecular weight distribution. It was street.

<Theoretical molecular weight analysis of graft chain>
The theoretical molecular weight of the graft chain is calculated by the following formula, assuming that the ester bond that is the initiation terminal of polymerization is cleaved by hydrolysis by hydrofluoric acid treatment, and all the termination terminals of polymerization are Br. Was as shown in Table 7-2.

<Calculation formula>
Theory of graft chain Mn = (monomer consumption rate (mol%) / 100) × MW _M × (molar ratio of vinyl monomer to α-bromoester group) + MW _I
<Parameters used for calculation>
MW _M = 100 (methyl methacrylate)
Molar ratio of vinyl monomer to α-bromoester group = 150
MW _I = 167.01 (BrC (CH ₃ ) ₂ CO ₂ H)

<Measurement of molecular weight of graft chain>
A mixed solution of hydrofluoric acid (0.17 ml) and acetonitrile (0.83 ml) was prepared. The polymer (2a) (10 mg) was dissolved in this mixed solution in a polypropylene microtube (1.5 ml) into which a stirrer was introduced, and stirred in an incubator equipped with a magnetic stirrer at 40 ° C. for 24 hours. Subsequently, the polymer was recovered by drying at 80 ° C. for 3 hours in a vacuum dryer. The results of GPC measurement of the recovered polymer were as shown in Table 7-2.

Examples 14-19
Except having changed superposition | polymerization time as shown in Table 7-1, it superposed | polymerized like Example 13 and obtained the brown and viscous solution of each of a polymer (2b)-a polymer (2g). . Each polymer was purified in the same manner as in Example 13, and the monomer conversion, theoretical number average molecular weight, number average molecular weight, and molecular weight distribution were determined. The results are shown in Table 7-1. The number average molecular weight calculation of the graft chain, the hydrofluoric acid treatment of the polymer, and the number average molecular weight and molecular weight distribution analysis of the graft chain by GPC measurement were performed in the same manner as in Example 13, and the results are shown in Table 7- It was shown in 2.

Example 20
<Compound (3-2-1): Synthesis of phenylsilsesquioxane having silanol using compound (3-1-1) as a raw material>
The compound (3-1-1) (6 g) obtained in Example 1 and tetrahydrofuran (50 ml) and tetrahydrofuran (50 ml) were charged into a reaction vessel having an internal volume of 100 ml equipped with a dropping funnel and a thermometer, and sealed with dry nitrogen. While stirring, glacial acetic acid (2.4 g) was added dropwise over about 10 seconds while maintaining the solution temperature at 22-27 ° C. After completion of the dropping, stirring was continued at room temperature for 1 hour, and then ion exchanged water (20 g) was added dropwise. Stirring was continued for 10 minutes after the completion of dropping, and then the mixture was transferred to a separatory funnel to separate an organic layer and an aqueous layer. The organic layer thus obtained was washed once with saturated aqueous sodium hydrogen carbonate, and then washed repeatedly with ion-exchanged water to make it neutral. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 5.3 g of a white powdery solid.

When the white powdery solid thus obtained was subjected to IR analysis, absorption based on the stretching of Si—OH was confirmed at 3300 cm ⁻¹ . As a result of measuring ²⁹ Si-NMR, a signal derived from a structure represented by PhSi (OH) O _2/2 at −69.32 ppm and a signal represented by PhSiO _3/2 at −79.45 ppm were obtained. Each signal was confirmed. As a result of measuring ¹ H-NMR, signals other than the phenyl group were not confirmed. As a result of measuring the average molecular weight by GPC, the number average molecular weight was 760 and the weight average molecular weight was 780 in terms of polystyrene. The above data suggests that the obtained white powdery solid has the structure of the formula (3-2-1).

Example 21
<Compound (5-1): Synthesis of organosilicon compound having hydrosilyl group>
By performing the same operation as in Example 3, except that the compound (3-2-1) obtained in Example 20 was used instead of the compound (3-1-1) obtained in Example 1. Compound (5-1) can be synthesized.

Example 22
<Synthesis of silicon compound having hydroxypropyl group>
By the same operation as in Example 4 except that allyl alcohol (4.0 equivalents or more with respect to the compound (5)) is used instead of ethylene glycol monoallyl ether, it is represented by the formula (7-2). Compounds can be synthesized.

Example 23
<Synthesis of silicon compound having 2-bromo-2-methylpropanoyloxypropyl group>
By performing the same operation as in Example 5, except that the compound (7-1) obtained in Example 22 was used instead of the compound (7-1) obtained in Example 4, the formula (1) was obtained. -1-4) can be synthesized.

この式におけるＣＭＳは、下記の式のいずれかで示される基である。

Example 24
<Synthesis of silicon compound having chloromethylphenylethyl group>
By performing the same operation as in Example 4 except that chloromethylstyrene (4.0 equivalents or more with respect to the compound (5)) is used instead of ethylene glycol monoallyl ether, the formula (1-3-3) is obtained. ) Can be synthesized.

CMS in this formula is a group represented by any of the following formulas.

この式におけるＢＤＣは、下記の式のいずれかで示される基である。

Example 25
<Synthesis of a silicon compound having a dithiocarbamoyl group>
Using the compound (1-3-3) obtained in Example 24 as a raw material, tetrahydrofuran, sodium N, N-diethyldithiocarbamate trihydrate (1.0 equivalent or more with respect to the chloromethylphenylethyl group) ) Can be synthesized to synthesize a silicon compound having a dithiocarbamoyl group represented by formula (1-4-3).

BDC in this formula is a group represented by any of the following formulas.

Example 26
<Synthesis of 2-bromo-2-methylpropanoyloxypropyldimethylchlorosilane>
Using allyl alcohol as a raw material, 2-bromo-2-methylpropanoyl bromide (1.0 equivalents or more with respect to hydroxyl groups) is reacted in methylene chloride in the presence of triethylamine (1.0 equivalents or more with respect to hydroxyl groups). To synthesize a compound represented by the formula (10). Further, the compound (10) and dimethylchlorosilane (1.0 equivalent or more with respect to the allyl group) are used as a transition metal catalyst atom with respect to a platinum-divinyltetramethyldisiloxane complex / xylene solution (one mole of Si-H group). 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol) is used as a catalyst to synthesize 2-bromo-2-methylpropanoyloxypropyldimethylchlorosilane represented by the formula (11-1). Can do.

Example 27
<Synthesis of silicon compound having 2-bromo-2-methylpropanoyloxypropyl group>
Example, except that 2-bromo-2-methylpropanoyloxypropyldimethylchlorosilane obtained in Example 26 (4.0 equivalents or more relative to compound (3-1-1)) was used instead of dimethylchlorosilane. By performing the same operation as 3, the silicon compound represented by the formula (1-1-4) can be synthesized.

Example 28
<Synthesis of silicon compound having 2-bromo-2-methylpropanoyloxypropyl group>
A silicon compound represented by the formula (1-1-4) is obtained by performing the same operation as in Example 27 except that the compound (3-2-1) is used instead of the compound (3-1-1). Can be synthesized.

Example 29
<Synthesis of 2-bromo-2-methylpropanoyloxyethoxypropyldimethylchlorosilane>
2-Bromo-2-methylpropanoyloxyethoxypropyldimethylchlorosilane represented by the formula (11-2) is obtained by performing the same operation as in Example 26 except that ethylene glycol monoallyl ether is used instead of allyl alcohol. Can be synthesized.

Example 30
<Synthesis of silicon compound having 2-bromo-2-methylpropanoyloxyethoxypropyl group>
Instead of 2-bromo-2-methylpropanoyloxypropyldimethylchlorosilane obtained in Example 26, 2-bromo-2-methylpropanoyloxyethoxypropyldimethylchlorosilane obtained in Example 29 (compound (3-1) A silicon compound represented by the formula (1-1-3) can be synthesized by performing the same operation as in Example 27 except that 4.0 equivalent or more) is used with respect to 1).

Example 31
<Synthesis of silicon compound having 2-bromo-2-methylpropanoyloxyethoxypropyl group>
A silicon compound represented by the formula (1-1-3) is obtained by performing the same operation as in Example 30, except that the compound (3-2-1) is used instead of the compound (3-1-1). Can be synthesized.

この式におけるＣＭＳは、下記のいずれかで示される基である。

Example 32
<Synthesis of chloromethylphenylethyldimethylchlorosilane>
A chloromethylphenylethyldimethylchlorosilane represented by the formula (11-3) can be synthesized by performing the same operation as in Example 26 except that chloromethylstyrene is used instead of allyl alcohol.

CMS in this formula is a group represented by any of the following.

この式におけるＣＭＳは、式（１１−３）におけるＣＭＳと同一である。 Example 33
<Synthesis of silicon compound having chloromethylphenylethyl group>
Instead of 2-bromo-2-methylpropanoyloxypropyldimethylchlorosilane obtained in Example 26, chloromethylphenylethyldimethylchlorosilane obtained in Example 32 (4.0 relative to compound (3-1-1)) was obtained. The silicon compound represented by the formula (1-3-3) can be synthesized by performing the same operation as in Example 27 except that the equivalent or more) is used.

CMS in this formula is the same as CMS in formula (11-3).

Example 34
<Synthesis of silicon compound having chloromethylphenylethyl group>
A silicon compound represented by the formula (1-3-3) is obtained by performing the same operation as in Example 33 except that the compound (3-2-1) is used instead of the compound (3-1-1). Can be synthesized.

この式におけるＴｓＣｌは、下記のいずれかで示される基である。

Example 35
<Synthesis of chlorosulfonylethyldimethylchlorosilane>
A chlorosulfonyldimethylchlorosilane represented by the formula (11-4) can be synthesized by performing the same operation as in Example 26 except that chlorosulfonylstyrene is used instead of allyl alcohol.

TsCl in this formula is a group represented by any of the following.

この式におけるＴｓＣｌは、式（１１−４）におけるＴｓＣｌと同一である。 Example 36
<Synthesis of silicon compound having chlorosulfonylethyl group>
Instead of 2-bromo-2-methylpropanoyloxypropyldimethylchlorosilane obtained in Example 26, 4.0 equivalents of chlorosulfonylethyldimethylchlorosilane obtained in Example 35 (compound (3-1-1)) The silicon compound represented by the formula (1-2-3) can be synthesized by performing the same operation as in Example 27, except that

TsCl in this formula is the same as TsCl in formula (11-4).

Example 37
<Synthesis of silicon compound having chlorosulfonylethyl group>
A silicon compound represented by the formula (1-2-3) is obtained by conducting the same operation as in Example 36 except that the compound (3-2-1) is used instead of the compound (3-1-1). Can be synthesized.

Claims (54)

Silicon compound represented by formula (1):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; and A is a group capable of initiating polymerization on a monomer. . Each R ¹ is hydrogen, the number of carbon atoms is 1-45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene Or optionally substituted with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — may be —O -, -CH = CH- or a group independently selected from an arylalkyl composed of an alkylene group optionally substituted by cycloalkylene; R ² and R ³ represent from 1 to 8 carbon atoms A group independently selected from alkyl, phenyl and cyclohexyl having A; and A has the ability to initiate living radical polymerization on monomers The silicon compound according to claim 1, which is a group. Each R ¹ is hydrogen, the number of carbon atoms is 1-45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene Or optionally substituted with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — may be —O -, -CH = CH- or a group independently selected from an arylalkyl composed of an alkylene group optionally substituted by cycloalkylene; R ² and R ³ represent from 1 to 8 carbon atoms And A is a group independently selected from alkyl, phenyl and cyclohexyl; and A is a formula (2-1), formula (2-2), formula (2-3) and formula The silicon compound according to claim 1, which is a group represented by any one of (2-4):

Where Z ¹ is alkylene having 2 to 20 carbon atoms or alkenylene having 3 to 8 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is replaced by —O—. R ⁴ is hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; R ⁵ is 1 Alkyl having -20 carbon atoms, aryl having 6-20 carbon atoms or arylalkyl having 7-20 carbon atoms; and X ¹ is halogen;

Here, Z ³ is an alkylene having 2 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or —COO—; R ⁶ is 1 to 3 A is an integer of 0 to 2; X ² is a halogen; the bonding position of —SO ₂ X ² to the benzene ring is relative to the bonding position of Z ³ ; In the ortho-position, meta-position or para-position, and the bonding position of R ⁶ is an arbitrary position excluding the bonding positions of Z ³ and —SO ₂ X ² ;

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁷ is 2 to 10 carbon atoms. Any alkylene —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁷ is alkyl having 1 to 3 carbon atoms; X ³ is a halogen; and the bonding position of Z ⁵ to the benzene ring is the meta position or the para position with respect to the bonding position of Z ⁷ , and the bonding position of R ⁷ is Z ⁵ and Z Any position except for each of the ⁷ binding positions;

Where R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms; R ⁸ and R ⁹ may be bonded to each other to form a ring with N; Z ⁵ may have 1 to 3 carbon atoms and any —CH ₂ — may be replaced by —O—. Z ⁷ is alkylene having 2 to 10 carbon atoms in which any —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁷ is Alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; and the bonding position of Z ⁵ to the benzene ring is meta or para with respect to the bonding position of Z ⁷ , R ⁷ is bonded to each of Z ⁵ and Z ⁷ It is an arbitrary position excluding the coupling position. Each R ¹ has 1-30 hydrogen and carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene The silicon compound according to claim 3, which is a group independently selected from alkyl. Each R ¹ has from 2 to 20 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene and from 1 to 20 the number of carbon atoms, arbitrary hydrogen may be replaced by fluorine, and at least one -CH 2 _- is a group which is independently selected from alkyl is replaced by cycloalkenylene, wherein Item 4. The silicon compound according to Item 3. Each R ¹ is a group independently selected from phenyl and unsubstituted naphthyl, optionally substituted with any hydrogen or alkyl having 1 to 10 carbon atoms; In alkyl, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, —CH═CH—, cycloalkylene, or phenylene; The silicon compound according to claim 3, wherein the substituent may be the same group or different groups. Each R ¹ is optionally substituted with any hydrogen or halogen or an alkyl having 1 to 12 carbon atoms and a phenyl group and the number of carbon atoms is 1 to 12, and any hydrogen is replaced with fluorine And any —CH ₂ — is a group independently selected from phenylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted with cycloalkylene; In the alkyl as a substituent of the group, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O—, —CH═CH—, cycloalkylene, or phenylene. And when the phenyl group has a plurality of substituents, the substituents may be the same group or different groups. Of the silicon compound. Each R ¹ has from ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl optionally substituted with cycloalkenylene, phenyl optionally substituted with hydrogen, halogen or methyl or methoxy, unsubstituted naphthyl and optionally hydrogen with fluorine, alkyl having 1 to 4 carbon atoms, vinyl Or a phenyl group which may be replaced by methoxy and an alkylene group having 1 to 8 carbon atoms and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene A group independently selected from phenylalkyl composed of: and the phenyl group of phenyl or phenylalkyl is a plurality of substituted When having, those substituents may be different groups may be the same group, a silicon compound according to claim 3. All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl optionally substituted with cycloalkenylene, phenyl optionally substituted with hydrogen, halogen or methyl or methoxy, unsubstituted naphthyl and optionally hydrogen with fluorine, alkyl having 1 to 4 carbon atoms, vinyl Or a phenyl group which may be replaced by methoxy and an alkylene group having 1 to 8 carbon atoms and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene And the same group selected from phenylalkyl, and the phenyl group of phenyl or phenylalkyl has a plurality of substituents. When, those substituents may be different groups may be the same group, a silicon compound according to claim 3. 4. The silicon compound according to claim 3, wherein all R < ¹ > is phenyl. 4. The silicon compound of claim 3, wherein all R < ¹ > is phenyl and R < ² > and R < ³ > are methyl. All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl optionally substituted with cycloalkenylene, phenyl optionally substituted with hydrogen, halogen or methyl or methoxy, unsubstituted naphthyl and optionally hydrogen with fluorine, alkyl having 1 to 4 carbon atoms, vinyl Or a phenyl group which may be replaced by methoxy and an alkylene group having 1 to 8 carbon atoms and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from the group consisting of phenylalkyl; and the phenyl group of phenyl or phenylalkyl having a plurality of substituents Is to those substituents may be the same group may be different groups; and, a group A is represented by the formula (2-1), the silicon compound according to claim 3.

Where Z ¹ is alkylene having 2 to 20 carbon atoms or alkenylene having 3 to 8 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is replaced by —O—. R ⁴ is hydrogen, alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, or arylalkyl having 7-20 carbon atoms; R ⁵ is 1 Alkyl having -20 carbon atoms, aryl having 6-20 carbon atoms or arylalkyl having 7-20 carbon atoms; and X ¹ is halogen. All R ¹ are phenyl; A is a group represented by the formula (2-1); and Z ¹ in the formula (2-1) has 2 to 10 carbon atoms, The silicon compound according to claim 3, wherein CH ₂ — is alkylene which may be replaced by —O—. All R ¹ is phenyl; R ² and R ³ are methyl; A is a group represented by formula (2-1); and in formula (2-1), Z ¹ is —C _{2 H 4 -, - C 3 H} 6 - or _{-C 2 H 4 -O-C 3} H 6 - and is a ^{R 4} and ^{R 5} are methyl, and ^{X 1} is bromine, according to claim 3 The silicon compound. All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl optionally substituted with cycloalkenylene, phenyl optionally substituted with hydrogen, halogen or methyl or methoxy, unsubstituted naphthyl and optionally hydrogen with fluorine, alkyl having 1 to 4 carbon atoms, vinyl Or a phenyl group which may be replaced by methoxy and an alkylene group having 1 to 8 carbon atoms and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from the group consisting of phenylalkyl; and the phenyl group of phenyl or phenylalkyl having a plurality of substituents Is to those substituents may be the same group may be different groups; and, a group A is represented by the formula (2-2), the silicon compound according to claim 3.

Here, Z ³ is an alkylene having 2 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or —COO—; R ⁶ is 1 to 3 A is an integer of 0 to 2; X ² is a halogen; the bonding position of —SO ₂ X ² to the benzene ring is relative to the bonding position of Z ³ ; In the ortho-position, meta-position or para-position, the bond position of R ⁶ is an arbitrary position excluding the bond positions of Z ³ and —SO ₂ X ² . All R ¹ are phenyl; A is a group represented by formula (2-2); Z ³ in formula (2-2) is —C ₂ H ₄ —Z ⁹ ; and Z ⁹ is The silicon compound according to claim 3, wherein the silicon compound has a single bond or an alkylene group having 1 to 8 carbon atoms, and any —CH ₂ — may be replaced by —O— or —COO—. All R ¹ is phenyl; R ² and R ³ are methyl; A is a group represented by formula (2-2); and in formula (2-2), Z ³ is —C ₂ The silicon compound according to claim 3, which is H ₄ —, X ² is chlorine or bromine, and a is 0. All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl optionally substituted with cycloalkenylene, phenyl optionally substituted with hydrogen, halogen or methyl or methoxy, unsubstituted naphthyl and optionally hydrogen with fluorine, alkyl having 1 to 4 carbon atoms, vinyl Or a phenyl group which may be replaced by methoxy and an alkylene group having 1 to 8 carbon atoms and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from the group consisting of phenylalkyl; and the phenyl group of phenyl or phenylalkyl having a plurality of substituents Is to those substituents may be the same group may be different groups; and, a group A is represented by the formula (2-3), the silicon compound according to claim 3.

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁷ is 2 to 10 carbon atoms. Any alkylene —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁷ is an alkyl having 1 to 3 carbon atoms; X ³ is a halogen; and the bonding position of Z ⁵ to the benzene ring is the meta position or the para position with respect to the bonding position of Z ⁷ , and the bonding position of R ⁷ is Z ⁵ and Z ^{7 is} an arbitrary position excluding each coupling position. All R ¹ are phenyl; A is a group represented by formula (2-3); Z ⁷ in formula (2-3) is —C ₂ H ₄ —Z ¹⁰ ; and Z ¹⁰ is The silicon according to claim 3, wherein the silicon is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — may be replaced by —O—, —COO— or —OCO—. Compound. All R ¹ is phenyl; R ² and R ³ are methyl; A is a group represented by formula (2-3); and in formula (2-3), Z ⁵ is —CH ₂ - a, ^{Z 7} is _-C 2 _{H 4} - a and, ^{X 3} is chlorine or bromine, and a is 0, the silicon compound according to claim 3. All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl optionally substituted with cycloalkenylene, phenyl optionally substituted with hydrogen, halogen or methyl or methoxy, unsubstituted naphthyl and optionally hydrogen with fluorine, alkyl having 1 to 4 carbon atoms, vinyl Or a phenyl group which may be replaced by methoxy and an alkylene group having 1 to 8 carbon atoms and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from the group consisting of phenylalkyl; and the phenyl group of phenyl or phenylalkyl having a plurality of substituents Is to those substituents may be the same group may be different groups; and, a group A is represented by the formula (2-4), the silicon compound according to claim 3.

Where R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms; R ⁸ and R ⁹ may be bonded to each other to form a ring with N; Z ⁵ may have 1 to 3 carbon atoms and any —CH ₂ — may be replaced by —O—. Z ⁷ is alkylene having 2 to 10 carbon atoms in which any —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁷ is Alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; and the bonding position of Z ⁵ to the benzene ring is meta or para with respect to the bonding position of Z ⁷ ; R ⁷ is bonded to each of Z ⁵ and Z ⁷ . It is an arbitrary position excluding the coupling position. All R ¹ is phenyl; A is a group represented by formula (2-4); and in formula (2-4), Z ⁷ is —C ₂ H ₄ —Z ¹⁰ , and Z ¹⁰ 4. The silicon according to claim 3, wherein is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — may be replaced by —O—, —COO— or —OCO—. Compound. All R ¹ is phenyl; R ² and R ³ are methyl; A is a group of formula (2-4); and in formula (2-4), R ⁸ and R ⁹ are ethyl, ^{Z 5} is -CH ₂ - a, ^{Z 7} is _-C 2 _{H 4} - a and, and a is 0, the silicon compound according to claim 3. A method for producing a silicon compound represented by the formula (1-1), wherein the compound represented by the formula (5) is obtained by the step (a), and further the step (c) is carried out after the step (b). :

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; and A ¹ is a group of formula (2-1-1):

Here, Z ² is a single bond, or alkylene having 1 to 18 carbon atoms, or alkenylene having 2 to 6 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is — May be replaced by O-; R ⁴ is hydrogen, alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, or arylalkyl having 7-20 carbon atoms R ⁵ is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms or arylalkyl having 7 to 20 carbon atoms; and X ¹ is halogen;
<Process (a)>
A step of obtaining a compound represented by the formula (5) by reacting the compound represented by the formula (3-1) with the compound represented by the formula (4):

Here, in these formulas, R ¹ , R ² and R ³ have the same meaning as these symbols in formula (1-1); M is a monovalent alkali metal atom;
<Step (b)>
A step of reacting a compound represented by the formula (5) with a compound represented by the formula (6) in the presence of a transition metal catalyst to obtain a silicon compound represented by the formula (7):

Here, ^{Z 2} in these formulas have the same meanings as ^{Z 2} in Formula ^{(2-1-1), R 1, R} 2 and ^{R 3} in the formula (7) in Formula (1-1) Has the same meaning as these symbols;
<Step (c)>
A step of reacting a compound represented by the formula (7) with a compound represented by the formula (8) to obtain a silicon compound represented by the formula (1-1):

Here, R ⁴ , R ⁵ and X ¹ have the same meaning as these symbols in formula (2-1-1); X is halogen. All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl, optionally substituted with cycloalkenylene, phenyl, optionally substituted with halogen, methyl or methoxy, unsubstituted naphthyl, and optionally hydrogen, fluorine, alkyl having 1 to 4 carbon atoms, An alkylene group having 1 to 8 carbon atoms and a phenyl group which may be replaced by vinyl or methoxy, and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene And the same group selected from the group consisting of phenylalkyl; and the phenyl group of phenyl or phenylalkyl has a plurality of substituents Come, those substituents same may be a group to be a different group; R ² and R ³ are alkyl, independently from cyclohexyl phenyl and cycloalkyl having 1-8 carbon atoms The production method according to claim 24, which is a group selected in the above. The process according to claim 24, wherein all R ¹ are phenyl; R ² and R ³ are methyl. A method for producing a silicon compound represented by the formula (1-1), wherein the compound represented by the formula (5) is obtained by the step (d), and further the step (c) is carried out after the step (b). :

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; and A ¹ is a group of formula (2-1-1):

Here, Z ² is a single bond, or alkylene having 1 to 18 carbon atoms, or alkenylene having 2 to 6 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is — May be replaced by O-; R ⁴ is hydrogen, alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, or arylalkyl having 7-20 carbon atoms R ⁵ is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms or arylalkyl having 7 to 20 carbon atoms; and X ¹ is halogen;
<Step (d)>
A step of obtaining a compound represented by the formula (5) by reacting a compound represented by the formula (3-2) with a compound represented by the formula (4):

Here, R ¹ , R ² and R ³ in these formulas have the same meaning as those symbols in formula (1-1).
<Step (b)>
A step of reacting a compound represented by the formula (5) with a compound represented by the formula (6) in the presence of a transition metal catalyst to obtain a silicon compound represented by the formula (7):

Here, ^{Z 2} in these formulas have the same meanings as ^{Z 2} in Formula ^{(2-1-1), R 1, R} 2 and ^{R 3} in the formula (7) in Formula (1-1) Has the same meaning as these symbols;
<Step (c)>
A step of reacting a compound represented by the formula (7) with a compound represented by the formula (8) to obtain a silicon compound represented by the formula (1-1):

Here, R ⁴ , R ⁵ and X ¹ have the same meaning as these symbols in formula (2-1-1); X is a halogen. All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl, optionally substituted with cycloalkenylene, phenyl, optionally substituted with halogen, methyl or methoxy, unsubstituted naphthyl, and optionally hydrogen, fluorine, alkyl having 1 to 4 carbon atoms, An alkylene group having 1 to 8 carbon atoms and a phenyl group which may be replaced by vinyl or methoxy, and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene And the same group selected from the group consisting of phenylalkyl; and the phenyl group of phenyl or phenylalkyl has a plurality of substituents Come, those substituents same may be a group to be a different group; R ² and R ³ are alkyl, independently from cyclohexyl phenyl and cycloalkyl having 1-8 carbon atoms The production method according to claim 27, which is a group selected in the above. 28. The method of claim 27, wherein all R ¹ is phenyl; R ² and R ³ are methyl. The method for producing a silicon compound represented by the formula (1-3), wherein the step (f) is performed after the step (e):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; and A ³ is a group of formula (2-3-1):

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁶ is a single bond or 1 carbon atom. a 8 arbitrary -CH ₂ - -O -, - COO- or -OCO- in be replaced may be alkylene; ^{R 7} is alkyl having 1-3 carbon atoms; a Is an integer from 0 to 2; X ³ is a halogen; and the bonding position of Z ⁵ to the benzene ring is meta or para to the bonding position of Z ⁶ , and the bonding position of R ⁷ is Any position except for the respective bonding positions of Z ⁵ and Z ⁶ ;
<Process (e)>
A step of reacting a compound represented by the formula (4) with a compound represented by the formula (3-1) or a compound represented by the formula (3-2) to obtain a silicon compound represented by the formula (5):

Wherein R ¹ , R ² and R ³ in these formulas have the same meaning as these symbols in formula (1-3); M is a monovalent alkali metal atom;
<Step (f)>
A step of reacting a compound represented by the formula (5) with a compound represented by the formula (2-3-2) to obtain a silicon compound represented by the formula (1-3):

Here, Z ⁵ , Z ⁶ , R ⁷ , a and X ³ have the same meaning as these symbols in formula (2-3-1); the bonding position of Z ⁵ and R ⁷ to the benzene ring is These bond positions are the same as those in formula (2-3-1). All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl, optionally substituted with cycloalkenylene, phenyl, optionally substituted with halogen, methyl or methoxy, unsubstituted naphthyl, and optionally hydrogen, fluorine, alkyl having 1 to 4 carbon atoms, An alkylene group having 1 to 8 carbon atoms and a phenyl group which may be replaced by vinyl or methoxy, and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene And the same group selected from the group consisting of phenylalkyl; and the phenyl group of phenyl or phenylalkyl has a plurality of substituents Come, those substituents same may be a group to be a different group; R ² and R ³ are alkyl, independently from cyclohexyl phenyl and cycloalkyl having 1-8 carbon atoms The production method according to claim 30, which is a group selected by The process according to claim 30, wherein all R ¹ is phenyl; R ² and R ³ are methyl. A method for producing a silicon compound represented by formula (1-4), comprising reacting a silicon compound represented by formula (1-3) with a compound represented by formula (9):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having carbon atoms; A ⁴ is a group of formula (2-4-1):

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms and any —CH ₂ — may be replaced by —O—; Z ⁶ is a single bond or 1 carbon atom. a 8 arbitrary -CH ₂ - -O -, - COO-, or replaced by -OCO- be alkylene be; ^{R 8} and ^{R 9} are independently hydrogen, 1 to 12 carbons Alkyl having atoms, cycloalkyl having 5 to 10 carbon atoms, or aryl having 6 to 10 carbon atoms, and R ⁸ and R ⁹ may be bonded together to form a ring with N R ⁷ is alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; and the bond position of Z ⁵ to the benzene ring is meta-position to the bond position of Z ⁶ or In the para position, the bonding position of R ⁷ is Z ⁵ and Z Any position except for each of the ⁶ binding positions;

Here, R ¹ , R ² and R ³ have the same meaning as these symbols in formula (1-4); A ³ is a group represented by formula (2-3-1);

Where Z ⁵ , Z ⁶ , R ⁷ and a have the same meaning as these symbols in formula (2-4-1); X ³ is halogen; Z ⁵ and R ⁷ to the benzene ring Are the same as those in formula (2-4-1);

Where R ⁸ and R ⁹ have the same meaning as these symbols in formula (2-4-1); M ¹ is a metal element of Group 1 or Group 2 of the Periodic Table; p is the same value as the valence of M ¹ . All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl, optionally substituted with cycloalkenylene, phenyl, optionally substituted with halogen, methyl or methoxy, unsubstituted naphthyl, and optionally hydrogen, fluorine, alkyl having 1 to 4 carbon atoms, An alkylene group having 1 to 8 carbon atoms and a phenyl group which may be replaced by vinyl or methoxy, and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene And the same group selected from the group consisting of phenylalkyl; and the phenyl group of phenyl or phenylalkyl has a plurality of substituents Come, those substituents same may be a group to be a different group; R ² and R ³ are alkyl, independently from cyclohexyl phenyl and cycloalkyl having 1-8 carbon atoms The production method according to claim 33, which is a group selected in the above. All of ^{R 1} are phenyl; ^{R 2} and ^{R 3} are methyl, A process according to claim 33. The method for producing a silicon compound represented by the formula (1-1), wherein the step (h) is performed after the step (g):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; A ¹ is a group of formula (2-1-1):

Here, Z ² is a single bond, or alkylene having 1 to 18 carbon atoms, or alkenylene having 2 to 6 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is — May be replaced by O-; R ⁴ is hydrogen, alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, or arylalkyl having 7-20 carbon atoms R ⁵ is alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms or arylalkyl having 7 to 20 carbon atoms; and X ¹ is halogen;
<Process (g)>
A step of obtaining a compound represented by the formula (2-1-3) by reacting a compound represented by the formula (4) with a compound represented by the formula (2-1-2) in the presence of a transition metal catalyst. :

Here, R ² and R ³ in these formulas have the same meaning as those symbols in formula (1-1); Z ² , R ⁴ , R ⁵ and X ¹ are the formulas (2-1-1- Have the same meaning as these symbols in 1);
<Step (h)>
By reacting the compound represented by the formula (2-1-3) with the compound represented by the formula (3-1) or the compound represented by the formula (3-2), it is represented by the formula (1-1). Obtaining a silicon compound:

Here, R ¹ in these formulas has the same meaning as R ¹ in formula (1-1); M is a monovalent alkali metal atom. All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl, optionally substituted with cycloalkenylene, phenyl, optionally substituted with halogen, methyl or methoxy, unsubstituted naphthyl, and optionally hydrogen, fluorine, alkyl having 1 to 4 carbon atoms, An alkylene group having 1 to 8 carbon atoms and a phenyl group which may be replaced by vinyl or methoxy, and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene And the same group selected from the group consisting of phenylalkyl; and the phenyl group of phenyl or phenylalkyl has a plurality of substituents Come, those substituents same may be a group to be a different group; R ² and R ³ are alkyl, independently from cyclohexyl phenyl and cycloalkyl having 1-8 carbon atoms The production method according to claim 36, which is a group selected in the above. The process according to claim 36, wherein all R ¹ is phenyl; R ² and R ³ are methyl. The method for producing a silicon compound represented by formula (1-2), wherein step (j) is performed after step (i):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having carbon atoms; and A ² is a group of formula (2-2-1):

Here, Z ⁴ is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or —COO—; R ⁶ is An alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; X ² is a halogen; and the bonding position of —SO ₂ X ² to the benzene ring is the bonding position of Z ^4. On the other hand, in the ortho-position, meta-position or para-position, the bonding position of R ⁶ is an arbitrary position excluding the bonding positions of Z ⁴ and —SO ₂ X ² ;
<Process (i)>
A step of reacting a compound represented by the formula (4) with a compound represented by the formula (2-2-2) in the presence of a transition metal catalyst to obtain a compound represented by the formula (2-2-3):

Here, R ² and R ³ in these formulas have the same meaning as those symbols in formula (1-2); Z ⁴ , R ⁶ , a and X ² are the formulas (2-2-2- Have the same meaning as these symbols in 1); the bonding positions of —SO ₂ X ² and R ⁶ to the benzene ring are the same as these bonding positions in formula (2-2-1);
<Process (j)>
A compound represented by the formula (2-2-3) is reacted with a compound represented by the formula (3-1) or a compound represented by the formula (3-2), thereby being represented by the formula (1-2). Obtaining a silicon compound:

Here, R ¹ in these formulas has the same meaning as R ¹ in formula (1-1); M is a monovalent alkali metal atom. All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl, optionally substituted with cycloalkenylene, phenyl, optionally substituted with halogen, methyl or methoxy, unsubstituted naphthyl, and optionally hydrogen, fluorine, alkyl having 1 to 4 carbon atoms, An alkylene group having 1 to 8 carbon atoms and a phenyl group which may be replaced by vinyl or methoxy, and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene And the same group selected from the group consisting of phenylalkyl; and the phenyl group of phenyl or phenylalkyl has a plurality of substituents Come, those substituents same may be a group to be a different group; R ² and R ³ are alkyl, independently from cyclohexyl phenyl and cycloalkyl having 1-8 carbon atoms 40. The production method according to claim 39, which is a group selected by 40. The method of claim 39, wherein all R ¹ is phenyl; R ² and R ³ are methyl. The method for producing a silicon compound represented by the formula (1-3), wherein the step (l) is carried out after the step (k):

Here, each R ¹ is hydrogen, the number of carbon atoms is ¹ to 45, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH— , Cycloalkylene, or alkyl which may be replaced with cycloalkenylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl groups and any hydrogen may be replaced with fluorine, and any —CH ₂ — Are independently selected from arylalkyl composed of —O—, —CH═CH— or an alkylene group optionally substituted by cycloalkylene; R ² and R ³ are 1-8 A group independently selected from alkyl, phenyl and cyclohexyl having a carbon atom; and A ³ is a group of formula (2-3-1):

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁶ is a single bond or 1 carbon atom. a 8 arbitrary -CH ₂ - -O -, - COO- or -OCO- in be replaced may be alkylene; ^{R 7} is alkyl having 1-3 carbon atoms; a Is an integer from 0 to 2; X ³ is a halogen; and the bonding position of Z ⁵ to the benzene ring is meta or para to the bonding position of Z ⁶ , and the bonding position of R ⁷ is Any position except for the respective bonding positions of Z ⁵ and Z ⁶ ;
<Process (k)>
A step of reacting a compound represented by the formula (4) with a compound represented by the formula (2-3-2) in the presence of a transition metal catalyst to obtain a compound represented by the formula (2-3-3). :

Here, R ² and R ³ in these formulas have the same meaning as these symbols in formula (1-3); Z ⁵ , Z ⁶ , R ⁷ , a, and X ³ are represented by the formula ( Have the same meaning as these symbols in 2-3-1); the bonding positions of Z ⁵ and R ⁷ to the benzene ring are the same as these bonding positions in formula (2-3-1);
<Step (l)>
By reacting the compound represented by the formula (2-3-3) with the compound represented by the formula (3-1) or the compound represented by the formula (3-2), it is represented by the formula (1-3). Obtaining a silicon compound:

Here, R ¹ in these formulas has the same meaning as R ¹ in formula (1-3); M is a monovalent alkali metal atom. All R ¹ have ¹ to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — is —O—, —CH═CH—, cycloalkylene, or Alkyl, optionally substituted with cycloalkenylene, phenyl, optionally substituted with halogen, methyl or methoxy, unsubstituted naphthyl, and optionally hydrogen, fluorine, alkyl having 1 to 4 carbon atoms, An alkylene group having 1 to 8 carbon atoms and a phenyl group which may be replaced by vinyl or methoxy, and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene And the same group selected from the group consisting of phenylalkyl; and the phenyl group of phenyl or phenylalkyl has a plurality of substituents Come, those substituents same may be a group to be a different group; R ² and R ³ are alkyl, independently from cyclohexyl phenyl and cycloalkyl having 1-8 carbon atoms 43. The production method according to claim 42, which is a group selected by 43. The method of claim 42, wherein all R ¹ is phenyl; R ² and R ³ are methyl. A polymer obtained by polymerizing an addition polymerizable monomer using the silicon compound according to claim 1 as an initiator and a transition metal complex as a catalyst. A polymer obtained by polymerizing an addition polymerizable monomer using the silicon compound according to claim 3 as an initiator and a transition metal complex as a catalyst. Polymer represented by formula (P-1):

Here, all R ¹¹ have 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms The number of carbon atoms is 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; the phenyl or phenylalkyl phenyl group is substituted more than once When having, those substituents may be the same group in a may be different groups; R ² and R ³ are alkyl having 1 to 8 carbon atoms, from cyclohexyl phenyl and cycloalkyl An independently selected group; and B ¹ is a group of formula (2-1-P):

Here, Z ¹ is alkylene having 2 to 20 carbon atoms or alkenylene having 3 to 8 carbon atoms, and any —CH ₂ — in these alkylene and alkenylene is replaced by —O—. R ⁴ is hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; R ⁵ is 1 to 20 Alkyl having 6 carbon atoms, aryl having 6-20 carbon atoms or arylalkyl having 7-20 carbon atoms; X ¹ is halogen; and P ¹ is an addition polymerizable monomer It is a chain of structural units obtained by polymerization of the body. Polymer represented by formula (P-2):

Here, all R ¹¹ have 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms The number of carbon atoms is 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; the phenyl or phenylalkyl phenyl group is substituted more than once When having, those substituents may be the same group in a may be different groups; R ² and R ³ are alkyl having 1 to 8 carbon atoms, from cyclohexyl phenyl and cycloalkyl An independently selected group; and B ² is a group of formula (2-2P):

Here, Z ³ is alkylene having 2 to 10 carbon atoms, and arbitrary —CH ₂ — in the alkylene may be replaced by —O— or —COO—; R ⁶ is 1 to 3 A is an integer of 0 to 2; X ² is a halogen; the bonding position of —SO ₂ — to the benzene ring is ortho to the bonding position of Z ^3. , Meta position or para position, and the bond position of R ⁶ is any position except the bond positions of Z ³ and —SO ₂ —; and P ² is obtained by polymerization of an addition polymerizable monomer. It is a chain of structural units obtained. Polymer represented by formula (P-3):

Here, all R ¹¹ have 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms The number of carbon atoms is 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; the phenyl or phenylalkyl phenyl group is substituted more than once When having, those substituents may be the same group in a may be different groups; R ² and R ³ are alkyl having 1 to 8 carbon atoms, from cyclohexyl phenyl and cycloalkyl An independently selected group; and B ³ is a group of formula (2-3-P):

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁷ is 2 to 10 carbon atoms. Any alkylene —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁷ is alkyl having 1 to 3 carbon atoms; X ³ is a halogen; the bonding position of Z ⁵ to the benzene ring is the meta position or the para position with respect to the bonding position of Z ⁷ , and the bonding position of R ^{7 is} the position of Z ⁵ and Z ⁷ P ³ is a chain of structural units obtained by polymerization of addition polymerizable monomers. Polymer represented by formula (P-4):

Here, all R ¹¹ have 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, —CH═CH—, cyclo Alkylene, or alkyl optionally substituted with cycloalkenylene, any hydrogen substituted with halogen, methyl or methoxy phenyl, unsubstituted naphthyl, and any hydrogen substituted with fluorine, 1-4 carbon atoms The number of carbon atoms is 1 to 8 and any —CH ₂ — may be replaced by —O—, —CH═CH— or cycloalkylene The same group selected from phenylalkyls composed of a good alkylene group; the phenyl or phenylalkyl phenyl group is substituted more than once When having, those substituents may be the same group in a may be different groups; R ² and R ³ are alkyl having 1 to 8 carbon atoms, from cyclohexyl phenyl and cycloalkyl Independently selected groups; and B ⁴ is a group of formula (2-4-P):

Here, Z ⁵ is alkylene having 1 to 3 carbon atoms, and arbitrary —CH ₂ — may be replaced by —O—; Z ⁷ is 2 to 10 carbon atoms. Any —CH ₂ — may be replaced by —O—, —COO— or —OCO—; R ⁸ and R ⁹ are independently hydrogen, alkyl having 1 to 12 carbon atoms , aryl having a cycloalkyl or 6-10 carbon atoms having 5 to 10 carbon atoms, and R ⁸ and R ⁹ may be bonded to each other to form a ring with N; R ⁷ is An alkyl having 1 to 3 carbon atoms; a is an integer of 0 to 2; the bonding position of Z ⁵ to the benzene ring is meta or para to the bonding position of Z ⁷ , R ⁷ bond positions are Z ⁵ and Z ⁷ bond positions. And P ⁴ is a chain of structural units obtained by polymerization of an addition polymerizable monomer. 48. The polymer according to claim 47, wherein the addition polymerizable monomer is at least one selected from the group of (meth) acrylic acid derivatives and the group of styrene derivatives. The polymer according to claim 48, wherein the addition polymerizable monomer is at least one selected from the group of (meth) acrylic acid derivatives and the group of styrene derivatives. The polymer according to claim 49, wherein the addition polymerizable monomer is at least one selected from the group of (meth) acrylic acid derivatives and the group of styrene derivatives. 51. The polymer according to claim 50, wherein the addition polymerizable monomer is at least one selected from the group of (meth) acrylic acid derivatives and the group of styrene derivatives.