JP2009269854A - Fluorene skeleton-bearing silicon compound and its polymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new fluorene skeleton-bearing silicon compound having excellent properties including high refractive index, causing no cracking even if a thick film is formed by sol-gel reaction. <P>SOLUTION: The new silicon compound is represented by formula [wherein, ring Z is an aromatic hydrocarbon ring; R<SP>1</SP>is an alkylene group; R<SP>2</SP>is H or methyl; Y is a group -(XR<SP>3</SP>)<SB>p</SB>-SiR<SP>4</SP>R<SP>5</SP>R<SP>6</SP>(wherein, X is a sulfur atom or imino; R<SP>3</SP>is an alkylene group; R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>are each H, hydroxy, halogen atom, alkoxy or hydrocarbon group; p is an integer; wherein, at least one of R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>is H, hydroxy, halogen atom or group -OR<SP>7</SP>); and m, n1 and n2 are each an integer]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel silicon compound having a fluorene skeleton, a method for producing the same, a polymerization composition containing the silicon compound, and a cured product obtained by curing the polymerizable composition.

  In an optical material using an organic material, various properties such as high refractive index, low birefringence, high transmittance, water resistance, and impact resistance are required. For example, it is known that the refractive index depends on the resin used for the material, but as a typical resin having a high refractive index, a polymer having a fluorene skeleton (fluorene polymer), a cycloolefin polymer, a polycarbonate Etc. Among them, a fluorene polymer using a fluorene monomer as a monomer has an excellent refractive index, a low birefringence, and a high transparency, so that it can be said to be an ideal optical material.

  In order to develop such high performance in fluorene polymers, fluorene monomers, which are raw materials for fluorene polymers, have been vigorously developed. For example, a compound having a fluorene skeleton (a 9,9-bisarylfluorene skeleton such as a 9,9-bisphenylfluorene skeleton) is known to have an excellent function in terms of refractive index, heat resistance, and the like. As a method for expressing such excellent functions of the fluorene skeleton in the resin, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene (BCF) In general, bisaminophenylfluorene (BAFL), bisphenoxyethanol fluorene (BPEF) or the like is used as a constituent component of the resin, and a fluorene skeleton is introduced into a part of the skeleton structure of the resin.

  A technique for forming a film using a compound (monomer) having a fluorene skeleton (9,9-bisphenylfluorene skeleton) or a fluorene polymer is also known.

For example, JP-A-2005-314692 (Patent Document 1) discloses an epoxy resin having a fluorene skeleton [for example, diglycidyl ether of 9,9-bis (monohydroxyphenyl) fluorene, 9,9-bis (mono Hydroxyphenyl) Diglycidyl ether of C _2-4 alkylene oxide adduct of fluorenes, etc.], a photopolymerizable resin composition composed of alkoxysilanes and a photoacid generator is applied onto a substrate to form a coating film. A method for producing a cured product (cured film) of the photopolymerizable resin composition by irradiating with light after forming is disclosed. This document also describes that the photopolymerizable composition may further contain a non-silicon alkoxide such as titanium alkoxide.

  JP 2007-91870 A (Patent Document 2) discloses a hydrolytic condensable organosilicon having a polyfunctional (meth) acrylate having a fluorene skeleton and a polymerizable group [for example, (meth) acryloyl group, etc.]. A polymerizable composition composed of a compound and a photoacid generator is applied onto a substrate to form a coating film, and then irradiated with light to produce a cured product (cured film) of the polymerizable resin composition. A method is disclosed. This document also describes that the polymerizable composition may further contain a non-silicon alkoxide such as titanium alkoxide.

  By the methods described in these documents, a cured film having excellent characteristics such as high heat resistance, high refractive index, and high hardness can be obtained. However, when the thickness of the obtained film is increased, cracks are generated, the surface is rough, and the surface smoothness is impaired.

From such a background, a novel fluorene monomer capable of forming a thick film having excellent characteristics such as a high refractive index is demanded.
Japanese Patent Laying-Open No. 2005-314692 (Claims, paragraph numbers [0057] to [0059]) JP 2007-91870 A (claims, paragraph numbers [0083] to [0084])

  Accordingly, an object of the present invention is to provide a silicon compound having a novel fluorene skeleton having excellent properties such as a high refractive index and high transparency, a method for producing the same, and a polymerizable composition containing the silicon compound. .

  Another object of the present invention is to provide a silicon compound having a novel fluorene skeleton that does not generate cracks even when a cured film having a relatively large thickness is formed, a method for producing the same, and a polymerizable composition containing the silicon compound. There is.

  Still another object of the present invention is to provide a cured film having excellent characteristics such as a high refractive index and having excellent surface smoothness without cracks on the surface, even if it is a thick film.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that a 9,9-bisarylfluorene skeleton (such as 9,9-bisphenylfluorene skeleton) and a specific linking group are present on the aryl group of the fluorene skeleton A novel fluorene compound that has a reactive group (such as an alkoxy group) bonded directly to a silicon atom, has excellent properties such as high refractive index and high transparency, and excellent transparency and flexibility This fluorene compound and a hydrolytic condensable organometallic compound can be used to form a thick film, and even if it is a thick film, it has an excellent high refractive index without generating cracks. The present inventors have found that a cured film having excellent characteristics can be obtained.

  That is, the silicon compound having a fluorene skeleton of the present invention has the following formula (1):

{Wherein, ring Z represents an aromatic hydrocarbon ring, R ¹ represents an alkylene group, R ² represents a hydrogen atom or a methyl group, and Y represents a group — (XR ³ ) _p —SiR ⁴ R ⁵ R ^6. [Wherein, X represents a sulfur atom or an imino group, R ³ represents an alkylene group, and R ⁴ , R ⁵ and R ⁶ are the same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, a group —OR ^7. (Wherein R ⁷ represents a hydrocarbon group) or a hydrocarbon group, and p represents an integer of 1 or more. However, at least one of R ⁴ , R ^5, and R ⁶ is a hydrogen atom, a hydroxyl group, a halogen atom, or a group —OR ⁷ . M is an integer of 0 or more, n1 is an integer of 1 or more, and n2 is an integer of 0 or more. }
It is represented by

In the formula (1), the ring Z may be, for example, a benzene ring or a naphthalene ring, the R ¹ may be, for example, a C _2-4 alkylene group, and m is about 1 to 4. R ³ may be a C _2-4 alkylene group. Further, in the formula (1), group -SiR ⁴ R ⁵ R ⁶ is an alkoxysilyl group, for example, _{di-C 1-4} alkyl _{C 1-4} alkoxysilyl _{group, C 1-4} alkyl di _{C 1-4} alkoxysilyl It may be a group or a tri-C _1-4 alkoxysilyl group.

  In the formula (1), X may be a sulfur atom. Such a compound in which X is a sulfur atom has a high refractive index, and is preferable in terms of imparting a high refractive index to the polymerizable composition and its cured product. Such a compound in which X is a sulfur atom is typically represented by the formula (1), wherein X is a sulfur atom, p is 1, n1 is about 1 to 2, and n2 is 1 to 2. It may be about 2.

  In the present invention, the following formula (2)

(In the formula, Z, R ¹ , R ² , m, n1, and n2 are the same as above.)
And a compound represented by the following formula (3)
^{R 4 R 5 R 6 Si- (} R 3 X) p -H (3)
(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , X and p are the same as above.)
And a method for producing the silicon compound by reacting with a compound represented by the formula:

  In this method, a catalyst can be appropriately used according to the compound represented by the formula (3) and the reaction type. For example, in the presence of a base catalyst, the compound represented by the formula (2) and X is a sulfur atom. A compound represented by a certain formula (3) may be reacted. In this reaction system, the compound represented by the formula (3) is added to the compound represented by the formula (2) by a Michael addition type reaction, and the silicon compound is obtained.

  The present invention also includes a polymerizable composition composed of the silicon compound. Such a polymerizable composition includes, for example, the silicon compound and at least one hydrolytic condensable organic non-silicon metal compound selected from a hydrolytic condensable organic titanium compound and a hydrolytic condensable organic zirconium compound. You may comprise. With such a polymerizable composition, a cured product having a high refractive index can be obtained. In the polymerizable composition, in particular, the hydrolytic condensable organic non-silicon metal compound may be composed of at least an oligomer of titanium alkoxides.

  In the polymerizable composition, the ratio of the hydrolytic condensable non-silicon-based organometallic compound may be about 0.3 to 5 parts by weight with respect to 1 part by weight of the silicon compound.

  The polymerizable composition may further contain an acid catalyst composed of a photoacid generator. When the polymerizable composition is composed of such a photoacid generator, it can be cured (hydrolytic condensation) by light irradiation, which is advantageous in terms of handling properties.

  Further, the present invention includes a cured product obtained by curing the polymerizable composition. Such a cured product may be a cured film having a thickness of 300 nm or more. In this invention, even if it is such a thick film, the cured film without a crack can be obtained.

  The silicon compound having a novel fluorene skeleton of the present invention has a 9,9-bis (aryl) fluorene skeleton, and has excellent characteristics such as high refractive index and high transparency. In particular, the silicon compound (or the polymerizable composition thereof) of the present invention does not generate cracks even when it is subjected to hydrolysis condensation and a cured film having a relatively large thickness is formed. Therefore, in the present invention, a thick film having excellent characteristics such as a high refractive index and excellent surface smoothness without cracks on the surface can be obtained.

  The silicon compound having a fluorene skeleton of the present invention is represented by the following formula (1).

{Wherein, ring Z represents an aromatic hydrocarbon ring, R ¹ represents an alkylene group, R ² represents a hydrogen atom or a methyl group, and Y represents a group — (XR ³ ) _p —SiR ⁴ R ⁵ R ^6. [Wherein, X represents a sulfur atom or an imino group, R ³ represents an alkylene group, and R ⁴ , R ⁵ and R ⁶ are the same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, a group —OR ^7. (Wherein R ⁷ represents a hydrocarbon group) or a hydrocarbon group, and p represents an integer of 1 or more. However, at least one of R ⁴ , R ^5, and R ⁶ is a hydrogen atom, a hydroxyl group, a halogen atom, or a group —OR ⁷ . M is an integer of 0 or more, n1 is an integer of 1 or more, and n2 is an integer of 0 or more. }
In the formula (1), the fluorene skeleton may be fluorene or a fluorene having a substituent (specifically, a substituent other than the 9th position of fluorene). Examples of the substituent include a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [eg, alkyl group, aryl group (C _6-10 aryl group such as phenyl group)], etc. And a non-reactive substituent, particularly a halogen atom, a cyano group or an alkyl group (particularly an alkyl group). Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . The number of substituents may be an integer of 0 to 4, preferably 0 to 2, and more preferably 0. When the number of substitutions is plural (two or more), the substituents may be different from each other or the same. Further, the substituents substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the substituent to the benzene ring constituting the fluorene is not particularly limited. In the two benzene rings constituting fluorene, the number of substitutions may be the same or different from each other.

In the formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z include a benzene ring and a condensed polycyclic aromatic hydrocarbon ring (specifically, a condensed polycyclic carbon ring including at least a benzene ring). Hydrogen ring). Examples of the condensed polycyclic aromatic hydrocarbon corresponding to the condensed polycyclic aromatic hydrocarbon ring include condensed bicyclic hydrocarbons (for example, C _8-20 condensed bicyclic hydrocarbons such as indene and naphthalene, preferably C _10-16 condensed bicyclic hydrocarbons) and condensed tricyclic hydrocarbons (for example, anthracene, phenanthrene, etc.) and the like, and the like. Preferable condensed polycyclic aromatic hydrocarbons include naphthalene and anthracene, and naphthalene is particularly preferable. The two rings Z may be the same or different rings, and may usually be the same ring.

  Preferred ring Z includes a benzene ring and a naphthalene ring (particularly a benzene ring).

Ring Z may have a substituent. As the substituent, usually, for example, an alkyl group (for example, a C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group, etc.), a cyclo Alkyl group (C _5-10 cycloalkyl group such as cyclopentyl group and cyclohexyl group), aryl group [for example, phenyl group, alkylphenyl group (methylphenyl group (or tolyl group, 2-methylphenyl group, 3- Methyl phenyl group, etc.), dimethylphenyl group (xylyl group, etc.), C _6-10 aryl group such as naphthyl group, etc.], aralkyl group (C _6-10 aryl-C _1-4 alkyl such as benzyl group, phenethyl group, etc.) Hydrocarbon group such as a group; alkoxy group (methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group) , T-like _{C 1-6} alkoxy group such as butoxy), such as _{C 5-10} cycloalkyl group such as a cycloalkoxy group (hexyloxy group cyclohexylene), _{C 6-10} aryl, such as aryloxy group (phenoxy group Oxy groups), ether groups (substituted hydroxyl groups) such as aralkyloxy groups (for example, C _6-10 aryl-C _1-4 alkyloxy groups such as benzyloxy groups); alkylthio groups (methylthio groups, ethylthio groups, propylthio groups) , N-butylthio group, C _1-6 alkylthio group such as t-butylthio group), cycloalkylthio group (C _5-10 cycloalkylthio group such as cyclohexylthio group), arylthio group (C such as thiophenoxy group) _6-10 arylthio group), aralkylthio group (e.g., benzylthio _{C 6-10} aryl _{-C 1-4} alkylthio group) thioether group, such as (substituted mercapto group) and the like; _{C 1-6} acyl group such as an acyl group (acetyl group); an alkoxycarbonyl group (such as methoxycarbonyl group C _1-4 alkoxy - carbonyl group); a hydroxyl group; a mercapto group; a carboxyl group; hydroxy (poly) alkoxy group [e.g., hydroxyalkoxy group (e.g., hydroxy _{C 2-10} alkoxy groups such as 2-hydroxyethoxy group, Preferably a hydroxy C _2-6 alkoxy group, more preferably a hydroxy C _2-4 alkoxy group), a hydroxy polyalkoxy group (for example, a 2- (2-hydroxyethoxy) ethoxy group, etc.) hydroxydi to tetra C _2-10 alkoxy Groups, preferably hydroxydi to te Tiger C _2-4 an alkoxy group), etc.]; methylol group; a halogen atom (fluorine atom, chlorine atom, an iodine atom, a bromine atom); nitro group; cyano group; amino group; a substituted amino group (such as dialkylamino group) Etc.

Among these, preferable substituents include hydrocarbon groups [for example, alkyl groups (for example, C _1-6 alkyl groups), cycloalkyl groups (for example, C _5-8 cycloalkyl groups), aryl groups (for example, C 1 _6-10 aryl groups), aralkyl groups (for example, C _6-8 aryl-C _1-2 alkyl groups), etc.], non-reactive substituents such as alkoxy groups (C _1-4 alkoxy groups, etc.). In particular, the substituent substituted on the ring Z is a hydrocarbon such as an alkyl group [C _1-4 alkyl group (especially methyl group)] or an aryl group [eg C _6-10 aryl group (especially phenyl group)]. It may be a group.

  In the same ring Z, when the number of substituents is plural (two or more), the substituents may be different from each other or the same. In the two rings Z, the substituents may be the same or different. In addition, the number of substituents substituted on the ring Z is preferably 0 to 8, preferably 0 to 4 (for example, 1 to 3), more preferably 0 to 2, particularly 0 to 1 (for example, 0). May be. In the plurality of rings Z, the number of substituents may be the same or different from each other, and may usually be the same.

Examples of the alkylene group represented by the group R ¹ in the formula (1) include an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group. A C _1-10 alkylene group, preferably a C _2-6 alkylene group, more preferably a C _2-4 alkylene group, particularly a C _2-3 alkylene group. When m is 2 or more, the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group. In the two aromatic hydrocarbon rings, the groups R ¹ may be the same or different, and may usually be the same.

The number (number of added moles) m of the oxyalkylene group (OR ¹ ) can be selected from the range of about 0 to 12 (for example, 1 to 12), for example, 0 to 8, preferably 0 to 4, and more preferably 0. It may be ˜2, especially 1-2. The number of substitutions m may be the same or different for different rings Z.

In the group Y of the formula (1), X is a sulfur atom (—S—) or an imino group (—NH—). In particular, in terms of improving the refractive index, the compound represented by the formula (1) wherein X is a sulfur atom is advantageous. In the group Y, R ³ is an alkylene group. Examples of the alkylene group include the groups exemplified for the group R ¹ , for example, C _2-6 alkylene groups such as ethylene group, trimethylene group (1,3-propanediyl group), tetramethylene group, preferably C _2-4 alkylene. Group, more preferably C _2-3 alkylene group and the like. In the group Y, the repeating number p of the group —XR ³ may be 1 or more, and may be, for example, 1 to 10, preferably 1 to 4, and more preferably 1 to 2. In addition, when group X is a sulfur atom, p is often 1.

In the group Y of the formula (1), R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a hydroxyl group, a halogen atom, a group —OR ⁷ (wherein R ⁷ represents a hydrocarbon group), Or it is a hydrocarbon group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Of these halogen atoms, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

In the group —OR ⁷ , the hydrocarbon group R ⁷ includes, for example, a saturated aliphatic hydrocarbon group [for example, C ₁ such as an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc. _-6 alkyl groups, preferably C _1-4 alkyl groups, more preferably C _1-2 alkyl groups, etc.], unsaturated aliphatic hydrocarbon groups [eg alkenyl groups (eg vinyl groups, allyl groups, etc.) C _2-6 alkenyl group, preferably C _2-4 alkenyl group etc.)], aromatic hydrocarbon group [eg aryl group (eg C _6-10 aryl group such as phenyl group etc.)] and the like. It is done. Of these hydrocarbon groups R ⁷ , an alkyl group is preferable, and a lower alkyl group (for example, a C _1-4 alkyl group such as a methyl group, an ethyl group, or a propyl group, particularly a C _1-2 alkyl group) is particularly preferable. .

In R ⁴ , R ⁵ and R ⁶ , examples of the hydrocarbon group include the same hydrocarbon groups as described above. Of these hydrocarbon groups, an alkyl group, an aryl group, and the like are preferable, and an alkyl group (for example, a C _1-4 alkyl group such as a methyl group) is particularly preferable.

As mentioned above, at least one of R ⁴ , R ⁵ and R ⁶ is a hydrogen atom, a hydroxyl group, a halogen atom, or a group —OR ⁷ . Such a group is important in that it directly bonds to a silicon atom and imparts polymerizability (hydrolytic condensation property) or reactivity to the compound represented by the formula (1). Among these, at least one of R ⁴ , R ⁵ and R ⁶ is a chlorine atom or an alkoxy group (that is, a group in which R ⁷ is an alkyl group, for example, a C _1-4 alkoxy group such as a methoxy group or an ethoxy group). Or an aryloxy group (that is, a group in which R ⁷ is an aryl group, for example, a C _6-10 aryloxy group such as a phenoxy group), particularly an alkoxy group (for example, C _1-4). An alkoxy group, preferably a _C1-2 alkoxy group).

In the formula (1), the representative group —SiR ⁴ R ⁵ R ⁶ includes, for example, a dialkylalkoxysilyl group (for example, a diC _1-4 alkyl-C ₁ such as a dimethylmethoxysilyl group or a dimethylethoxysilyl group). _-4 alkoxysilyl group), diarylalkoxysilyl group (for example, di-C _6-10 aryl-C _1-4 alkoxysilyl group such as diphenylmethoxysilyl group, diphenylethoxysilyl group), alkylarylalkoxysilyl group (for example, methyl One of R ⁴ , R ⁵ and R ⁶ such as C _1-4 alkyl-C _6-10 aryl-C _1-4 alkoxysilyl group such as phenylmethoxysilyl group) is a hydrogen atom, a hydroxyl group, a halogen atom, or a silyl group is a group -OR ^7; alkyldialkoxysilyl group (e.g. Methyl dimethoxy silyl group, C _1-4 alkyl such as methyl diethoxy silyl group, an ethyl dimethoxy silyl group, ethyl diethoxy silyl group - di C _1-4 alkoxysilyl group), an aryl dialkoxysilyl group (e.g., phenyl dimethoxy silyl Two of R ⁴ , R ⁵ and R ⁶ such as a group, a C _6-10 aryl-diC _1-4 alkoxysilyl group such as a phenyldiethoxysilyl group) are a hydrogen atom, a hydroxyl group, a halogen atom, or a group -OR ⁷ silyl group; trialkoxysilyl group (for example, tri-C _1-4 alkoxysilyl group such as trimethoxysilyl group, triethoxysilyl group, trimesilyl group, ethyldiethoxysilyl group), dialkoxyaryloxysilyl group (e.g., di-C such dimethoxyphenoxy silyl group _1- R, such as alkoxy _{-C 6-10} aryloxy silyl group), triaryl oxy silyl group (e.g., tri _{C 6-10} aryloxy silyl group such as tri-phenoxy silyl group), trihalosilyl group (e.g., trichlorosilyl group, etc.) ⁴ , R ⁵ and R ⁶ all include a hydrogen atom, a hydroxyl group, a halogen atom, or a silyl group that is a group —OR ⁷ .

Among these, a silyl group in which one of R ⁴ , R ⁵ and R ⁶ is an alkoxy group, such as a dialkylalkoxysilyl group (for example, a diC _1-4 alkyl-C _1-4 alkoxysilyl group, particularly a dialkyl group). C _1-4 alkyl-C _1-2 alkoxysilyl group), alkyl dialkoxysilyl groups (for example, C _1-4 alkyl-di C _1-4 alkoxysilyl groups, especially C _1-4 alkyl-diC _1-2). An alkoxysilyl group) and a trialkoxysilyl group (for example, a tri-C _1-4 alkoxysilyl group, particularly a tri-C _1-2 alkoxysilyl group) are preferable.

  Moreover, in said Formula (1), n1 should just be 1 or more, for example, 1-8 (for example, 1-6), Preferably it is 1-4, More preferably, it is 1-2, Especially even if it is 1. Good. Moreover, n2 should just be 0 or more, for example, 0-8 (for example, 0-6), Preferably it is 1-4, More preferably, it may be 1-2, especially 1. n1 and n2 may be the same or different. Usually, n1 and n2 may be the same [for example, 1 or more (for example, 1-2)]. Moreover, the sum total of n1 and n2 is 1-15 (for example, 1-12), for example, Preferably 2-10, More preferably, it is 2-8 (for example, 2-6), Especially 2-4 (for example, 2 ).

  The silicon compound of the present invention as described above has a polymerizable (or condensable) silicon-containing group such as an alkoxysilyl group, and the silicon-containing group and the 9,9-bisarylfluorene skeleton are Because it has a structure linked by a specific linking group containing an ethylene group or a propylene group, it is relatively flexible, and even when subjected to hydrolysis treatment, curing shrinkage can be suppressed. Such cure shrinkage seems to be related to the kind of the hydrolytic condensable organometallic compound to be combined in the polymerizable composition as described later.

(Production method)
The silicon compound of the present invention is not particularly limited and is not particularly limited as long as it can be introduced into the 9,9-bisarylfluorene skeleton. Usually, the compound represented by the following formula (2) [in the formula (1), the group Y And a compound corresponding to the skeleton excluding [Image Omitted] and a compound represented by the following formula (3) (a compound corresponding to the group -Y in the formula (1)) can be produced. That is, by adding the compound represented by the following formula (3) to the compound represented by the following formula (2) (particularly, by addition of a Michael addition type reaction), the compound represented by the above formula (1) is represented. A compound can be obtained efficiently. Such a method is simple, and a silicon compound as a raw material is often easily available, and is a method for advantageously producing the silicon compound of the present invention.

(In the formula, Z, R ¹ , R ² , m, n1, and n2 are the same as described above.)
^{R 4 R 5 R 6 Si- (} R 3 X) p -H (3)
(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , X and p are the same as above.)
In the formula (2), Z, R ¹ , R ² , m, n1, and n2 are the same as described above, and the preferred embodiments are also the same as described above.

  Representative compounds represented by the formula (2) include, for example, 9,9-bis ((meth) acryloyloxyaryl) fluorenes, 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl ) Fluorenes are included.

As 9,9-bis ((meth) acryloyloxyaryl) fluorenes, for example, 9,9-bis ((meth) acryloyloxyphenyl) fluorene [for example, 9,9-bis (4- (meth) acryloyloxy) Phenyl) fluorene and the like], 9,9-bis ((meth) acryloyloxy-alkylphenyl) fluorene [eg, 9,9-bis (4- (meth) acryloyloxy-3-methylphenyl) fluorene, 9,9- 9,9-bis ((meth) acryloyloxy-mono or diC _1-4 alkylphenyl) fluorene] such as bis (4- (meth) acryloyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis ((Meth) acryloyloxy-arylphenyl) fluorene [for example, 9,9-bis (4- (meth) 9,9-bis ((meth) acryloyloxy-mono or di-C _6-10 arylphenyl) fluorene] such as acryloyloxy-3-phenylphenyl) fluorene, 9,9-bis (di to tetra (meth) acryloyloxy 9,9-bis ((meth) acryloyloxyphenyl) fluorenes such as phenyl) fluorene [for example, 9,9-bis (3,4-di (meth) acryloyloxyphenyl) fluorene, etc.]; 9,9-bis 9,9-bis ((meth) acryloyloxynaphthyl) fluorenes such as ((meth) acryloyloxynaphthyl) fluorene [eg, 9,9-bis (6- (meth) acryloyloxy-2-naphthyl) fluorene, etc.] Etc. are included.

Further, 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorenes correspond to the 9,9-bis ((meth) acryloyloxyaryl) fluorenes, and in the formula (2), a compound wherein m is 1 or more, for example, 9,9-bis ((meth) acryloyloxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis ((meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (9,9-bis [4- (2- (meth) acryloyloxypropoxy) phenyl] fluorene) (Meth) acryloyloxydi to tetraalkoxyphenyl) fluorene {e.g. 9,9-bis {4- [2- (2- (meth) acryloyloxy) ethoxy] phenyl} fluorene such as 9,9-bis ((meth) acryloyloxy-di _{C 2-4} alkoxyphenyl) fluorene} etc. 9,9-bis (( (Meth) acryloyloxy (poly) alkoxyphenyl) fluorenes; 9,9-bis ((meth) acryloyloxyalkoxynaphthyl) fluorene {eg, 9,9-bis [6- (2- (meth) acryloyloxyethoxy)- 9,9-bis ((meth) acryloyloxy C _2-4 alkoxynaphthyl) fluorene}, 9,9-bis ((meth) acryloyloxydi to tetraalkoxynaphthyl) fluorene {eg, 9-bis (naphthyl) fluorene {eg, 9 , 9-bis {6- [2- (2-hydroxyethoxy) ethoxy] -2 Etc. 9,9-bis ((meth) acryloyloxy-di _{C 2-4} alkoxy-naphthyl) fluorene} etc. 9,9-bis ((meth) acryloyloxy (poly) alkoxy naphthyl) fluorene such as naphthyl} fluorene It is.

In the formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , X and p are the same as described above, and preferred embodiments are also the same as described above.

Representative examples of the compound represented by the formula (3) include, for example, mono to trialkoxysilanes having a mercapto group [for example, mercaptoalkylalkyldialkoxysilane (for example, 3-mercaptopropylmethyldimethoxysilane, 3- Mercapto C _2-4 alkyl C _1-4 alkyl diC _1-4 alkoxysilane) such as mercaptopropylmethyldiethoxysilane, mercaptoalkyltrialkoxysilane (eg 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane) , alkoxysilane having a mercapto group such as 3-mercapto C _2-4 alkyl tri C _1-4 alkoxysilane such as mercaptopropyltriethoxysilane) mercaptoalkyl mono- to tri-alkoxysilanes such as] S; mono- to tri-alkoxysilanes having an amino group {e.g., amino C _2-4 alkyl C ₁ such as aminoalkyl alkyl dialkoxy silanes (e.g., 3-aminopropyl methyl dimethoxy silane, 3-aminopropyl methyl diethoxy silane _-4 alkyl di _{C 1-4} alkoxysilane), aminoalkyl trialkoxy silane (e.g., 2-aminoethyl trimethoxy silane, 3-aminopropyl trimethoxysilane, 3-aminopropyl amino _{C 2-4} alkyl, such as triethoxy silane aminoalkyl mono- or trialkoxysilane such as tri C _1-4 alkoxy silane); (aminoalkyl amino) alkyl - alkyl dialkoxy silanes [e.g., 3- [N-(2-aminoethyl) amino] propyl methyl dimethoxy Shi Emissions, such as such as (amino _{C 2-4 alkylamino) C 1-4} alkyl _{-C 1-4} alkyl di _{C 1-4} alkoxysilane, (aminoalkylamino) alkyl - trialkoxysilane [e.g., 2-[N- N- (amino C _2-4 alkyl) amino C _2-4 alkyltri-C such as (2-aminoethyl) amino] ethyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane _1-4 alkoxysilanes having an amino group such as].

  In the reaction, the proportion of the compound represented by the formula (3) can be appropriately selected according to the number of n1 and n2 in the formula (1), and relative to 1 mol of the compound represented by the formula (2). For example, 1 mol or more (for example, 1 to 20 mol), preferably 1.2 to 15 mol (for example, 1.5 to 10 mol), more preferably 2 to 8 mol (for example, 2.2 to 5). Mol) degree. In particular, when obtaining a compound in which n1 and n2 are 1 in the formula (1), the proportion of the compound represented by the formula (3) is 1 mol of the compound represented by the formula (2). On the other hand, for example, 2 mol or more (for example, 2 to 20 mol), preferably 2.1 to 15 mol (for example, 2.2 to 10 mol), more preferably about 2.3 to 5 mol. Good.

  The reaction may be performed in a solvent. The solvent is not particularly limited as long as it is an inert or non-reactive solvent for the compound represented by the formula (2) and the compound represented by the formula (3). For example, ethers ( For example, dialkyl ethers such as diethyl ether and dipropyl ether, cyclic ethers such as 1,4-dioxane, dioxolane and tetrahydrofuran), ketones (for example, dialkyl ketones such as acetone, methyl ethyl ketone, diisopropyl ketone and isobutyl methyl ketone), Esters (for example, acetates such as methyl acetate, ethyl acetate, and butyl acetate), hydrocarbons (for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene), halogenated hydrocarbon solvents (chlorinated) Methylene, chloroform, carbon tetrachloride, tetrachloroethane , Halogenated hydrocarbons such as trichloroethane), and the like nitriles (such as acetonitrile). These solvents may be used alone or in combination of two or more.

  The reaction may be performed in the presence of a catalyst. As the catalyst, the type of functional group (mercapto group or amino group) of the compound represented by the formula (3), the compound represented by the formula (2), and the compound represented by the formula (3) It can be suitably selected according to the type of reaction type. For example, among the compounds represented by the formula (3), a compound in which X is a sulfur atom (a compound having a mercapto group) is added to the compound represented by the formula (2) by a Michael addition type reaction. In this case, the catalyst may be a tertiary amine [for example, a trialkylamine such as triethylamine, a chain tertiary amine such as benzyldimethylamine; pyridine, methylpyridine, N, N-dimethylpiperazine, triethylenediamine, etc. Base catalysts such as cyclic tertiary amines and the like may be used. These catalysts may be used alone or in combination of two or more.

  The proportion of the catalyst used can also be appropriately selected depending on the reaction type and the like. For example, 0.0001 to 2 mol, preferably 0.0005 to 1 mol per 1 mol of the compound represented by the formula (3). The mole may be about 0.001 to 0.5 mole, more preferably about 0.01 to 0.1 mole.

  The reaction may be carried out under cooling or at ordinary temperature, and may be carried out under heating (for example, 40 to 150 ° C., preferably 50 to 120 ° C., more preferably about 60 to 100 ° C.). The reaction may be performed in air or in an inert atmosphere (such as nitrogen or a rare gas), or may be performed under normal pressure, increased pressure, or reduced pressure.

  In this way, the compound represented by the formula (1) is obtained. The reaction product (compound represented by the above formula (1)) is separated by a conventional method, for example, filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination of these. May be separated and purified from the reaction mixture.

(Use)
The silicon compound of the present invention has a 9,9-bisarylfluorene skeleton and a silicon skeleton, and has excellent properties such as high heat resistance, high transparency, and a high refractive index, and therefore can be applied to various applications. it can. For example, since the silicon compound of the present invention has a polymerizable group (hydrolytic condensable group) bonded to a silicon atom and can be polymerized, it can be used as a resin component.

  In particular, since the silicon compound of the present invention has a polymerizable group (hydrolytic condensable group), it can constitute a polymerizable composition. The polymerizable composition will be described in detail below.

(Polymerizable composition)
In the polymerizable composition, the polymerization component (hydrolytic condensable component) may be composed only of the silicon compound, and the silicon compound and the hydrolytic condensable organometallic compound (specifically, the category of the silicon compound). And other hydrolytic condensable organometallic compounds and other hydrolytic condensable organometallic compounds).

Examples of the hydrolytic condensable organometallic compound include hydrolytic condensable organosilicon compounds {for example, monoalkoxysilanes such as vinyldimethylethoxysilane; dialkyl dialkoxysilanes (for example, diC _1-4 alkyldiC such as dimethyldimethoxysilane). _1-4 alkoxysilane etc.), functional groups [epoxy group, amino group, mercapto group, halogen atom (chlorine atom etc.), polymerizable unsaturated group (eg (meth) acryloyl group, vinyl group etc.)] Alkoxysilane {for example, 3-glycidyloxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, vinyldimethylethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane Dialkoxysilane such as; trialkoxysilanes (e.g., tri C _1-4 alkoxysilane such as trimethoxysilane), alkyltrialkoxysilane (e.g., C _1-4 alkyl tri C such as methyltrimethoxysilane _{1- 4-} alkoxysilane etc.), aryltrialkoxysilane (eg phenyltrimethoxysilane etc.), functional group [epoxy group, amino group, mercapto group, halogen atom (chlorine atom etc.), polymerizable unsaturated group (eg (meta ) Acryloyl group, vinyl group, etc.] [for example, 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3- ( (Meta) acryloyl Trialkoxysilanes such as trimethoxysilane, etc.); tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc. tetra C _1-4 alkoxysilane such as tetrabutoxysilane) tetraalkoxysilanes such as Oligomers (or partial condensates of these mono to tetraalkoxysilanes)}, hydrolytic condensable non-silicon organometallic compounds, and the like. These hydrolytic condensable organometallic compounds may be used alone or in combination of two or more.

  When improving or improving the characteristics of the polymerizable composition (or a cured product thereof), it is preferable that the hydrolytic condensable organometallic compound is composed of at least a hydrolytic condensable non-silicon based organometallic compound. For example, when the refractive index of the polymerizable composition (or its cured product) is further improved or improved, a hydrolytic condensable organometallic compound, a hydrolytic condensable organic titanium compound, a hydrolytic condensable organic zirconium compound, etc. You may comprise at least (especially a hydrolytic condensable organic titanium compound).

Examples of the hydrolytic condensable non-silicon-based organometallic compound (hereinafter sometimes simply referred to as non-silicon-based metal compound) include non-silicon based metal alkoxides or partial condensates thereof. Examples of the non-silicon metal alkoxide include metal alkoxides of non-silicon metals selected from titanium, zirconium, aluminum, and zinc, for example, metal alkoxides represented by the following formula (4).
M (OR ¹¹ ) _q (R ¹² ) _r (4)
[Wherein M represents titanium, zirconium, aluminum or zinc. R ¹¹ is an alkyl group or a group-[(R ¹³ O) _s -R ¹⁴ ] (wherein R ¹³ is an alkylene group, R ¹⁴ is an alkyl group, and s represents an integer of 1 or more) , R ¹² represents a hydrogen atom, a hydroxyl group, a halogen atom or an optionally substituted hydrocarbon group, q represents an integer of 1 or more, and r represents 0 or an integer of 1 or more. ]
In the formula (4), examples of the alkyl group represented by the group R ¹¹ (and the group R ¹⁴ ) include C _1-18 alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, preferably C _1-10 alkyl group, more preferably a _{C 1-6} alkyl group _{(e.g., C 1-4} alkyl group), and others. Examples of the halogen atom represented by the group R ¹² include a chlorine atom, a bromine atom, and an iodine atom. Further, in the polyalkoxy group represented by the group —O — [(R ¹³ O) _s —R ¹⁴ ], the alkylene group represented by the group R ¹³ is not limited, but for example, a C _2-4 alkylene group. (Ethylene group, trimethylene group, propylene group, butane-1,2-diyl group, etc.) and the like can be exemplified, and a _C2-3 alkylene group (particularly, ethylene group, propylene group) is particularly preferable. The addition number s of alkyleneoxy (R ¹³ O) units may be 1 or more, and may be, for example, 1 to 4, preferably 1 to 2, and more preferably 1. Preferred polyalkoxy groups include C _1-4 alkoxy C _2-4 alkoxy groups (particularly C _1-2 alkoxyethoxy groups) such as 2-methoxyethoxy group and 2-ethoxyethoxy group.

Moreover, the preferable number of substitution q is about 2-4, for example according to the kind of metal atom M. In addition, when the substitution number q is plural, the plural groups R ¹¹ may be the same or different.

Examples of the hydrocarbon group represented by the group R ¹² include the same hydrocarbon groups as described above, for example, an alkyl group (for example, a C _1-6 alkyl group), an aryl group (for example, a C _6-10 aryl group). Etc. are included. In addition, the hydrocarbon group represented by the group R ¹² is a substituent {for example, a halogen atom (a chlorine atom, a bromine atom, etc., particularly a chlorine atom), an amino group or an N-substituted amino group [for example, an aminoalkylamino group. (Such as amino _C2-4 alkylamino group such as 2-aminoethylamino group), alkenylamino group (such as _C2-4 alkenylamino group such as allylamino group), alkenylaminoalkyl group (such as allylaminopropyl group), etc. ], A mercapto group (or substituted mercapto group), an epoxy group-containing group [epoxy cycloalkyl group (epoxy C _3-8 cyclohexyl group such as 3,4-epoxy cyclohexyl group, preferably epoxy C _5-8 cycloalkyl group, preferably the epoxy _{C 5-6} cycloalkyl group), glycidyl group, (meth) Acryloyloxy may have a group like}. These substituents may be substituted singly or in combination of two or more. In addition, the preferable substitution number r is 0-2. When the number of substitutions r is plural, the plural groups R ¹² may be the same or different.

Typical non-silicon metal alkoxides include aluminum alkoxides [for example, trialkoxyaluminum (trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, tri-n-butoxyaluminum, tris-butoxyaluminum, tri-t-butoxyaluminum. tri C _1-4 alkoxy aluminum, etc.), etc.], such as titanium alkoxides [e.g., dialkoxy titanium dialkyl dialkoxy titanium (di C _1-4 alkyl di C _1-4 alkoxy titanium such as diethyl diethoxy titanium); Trialkoxy titanium (for example, tri C _1-4 alkoxy titanium such as trimethoxy titanium), alkyl trialkoxy titanium (for example, methyl trimethoxy titanium, ethyl trimethoxy tita) Alkyl tri C _1-4 alkoxy titanium such as emissions), aryl trialkoxy titanium (e.g., trialkoxy titanium such Arirutori C _1-4 alkoxy titanium), such as phenyl trimethoxy titanium; tetraalkoxy titanium (e.g., tetramethoxysilane titanium, Tetraethoxytitanium, tetrapropoxytitanium, tetraisopropoxytitanium, tetraisobutoxytitanium, tetra-n-butoxytitanium, tetrat-butoxytitanium, tetranonyloxytitanium, tetrakis (2-ethylhexyloxy) titanium, tetrakis (methoxypropoxy) titanium Tetra C _1-18 alkoxy titanium such as _{tetrastearyloxy} titanium, tetraisostearyloxy titanium, preferably tetra C _1-10 alkoxy titanium, more preferably Te Tiger C _1-6 alkoxy such as titanium), etc.], zirconium alkoxides [e.g., tetraalkoxy zirconium (e.g., tetramethoxysilane zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetraisobutoxy zirconium, tetra-n- butoxy zirconium, tetra t Tetra-C _1-18 alkoxy zirconium such as butoxy zirconium, tetrakis (2-ethylhexyloxy) zirconium, tetrakis (2-methyl-2-butoxy) zirconium, preferably tetra C _1-10 alkoxy zirconium, more preferably tetra C _{1 -6} alkoxyzirconium etc.)], zinc alkoxides (eg bismethoxyethoxy zinc etc.) and the like.

  The non-silicon metal alkoxide may form a complex (metal complex). In the complex, the ligand (or the compound forming the ligand) is not particularly limited. For example, an organic compound [a chelate-forming organic compound (for example, a β-diketone structure such as acetylacetone or acetoacetate) is used. Compound etc.)] and the like.

  Moreover, as a partial condensate (or oligomer) of a non-silicon-type metal alkoxide, the oligomer (or condensate) of metal alkoxide (for example, tetraalkoxy titanium etc.) represented by the said Formula (4) is mentioned. Such an oligomer may be an oligomer of a single non-silicon metal alkoxide, or a condensate of a plurality of non-silicon metal alkoxides (eg, an oligomer of trialkoxy titanium and tetraalkoxy titanium, a heterogeneous tetraalkoxy). Or an oligomer of titanium).

  The number average degree of polymerization of the oligomer may be, for example, 2 to 10, preferably 2 to 8, and more preferably about 3 to 6. The oligomer may be a chain (or straight chain) condensate (or partial condensate).

  Typical oligomers include oligomers (partial condensates) of non-silicon metal alkoxides having 3 or more alkoxy groups (for example, trialkoxy titanium, tetraalkoxy titanium, tetraalkoxy zirconium, etc.). For example, the tetraalkoxytitanium oligomer includes a linear alkoxytitanium oligomer represented by the following formula (5).

(In the formula, t represents an integer of 2 or more, and R ¹¹ is the same as described above.)
In the above formula (5), the group R ¹¹ is the same as described above. Preferred groups R ¹¹ include alkyl groups (eg, C _1-10 alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, etc., preferably C _1-4 alkyl groups). As described above, the plurality of groups R ¹¹ may be the same group or different groups. Moreover, t should just be 2 or more, for example, 2-15, Preferably it is 2-10, More preferably, about 3-6 may be sufficient.

As described above, preferable hydrolytic condensable non-silicon-based organometallic compounds are titanium alkoxides, zirconium alkoxides, oligomers thereof (especially titanium alkoxides or oligomers thereof), etc. from the viewpoint of increasing the refractive index. Is preferred. In particular, from the viewpoint of reactivity, oligomers of titanium alkoxides are preferable. Also preferred are titanium alkoxides having a relatively large hydrocarbon group (for example, tetra C _2-10 alkoxy titanium, preferably tetra C _3-6 alkoxy titanium) and oligomers thereof.

  The hydrolytic condensable non-silicon-based organometallic compounds may be used alone or in combination of two or more.

  In the polymerizable composition, the ratio of the hydrolytic condensable non-silicon-based organometallic compound (for example, the hydrolytic condensable organic titanium compound) is, for example, the compound represented by the formula (1) (or the silicon compound) 1 0.01 to 20 parts by weight (for example, 0.05 to 10 parts by weight), preferably 0.1 to 8 parts by weight, more preferably 0.3 to 5 parts by weight, and particularly 0.5 parts by weight. It may be about ˜4 parts by weight (for example, 0.6 to 3.5 parts by weight).

  The ratio of the hydrolytic condensable non-silicon-based organometallic compound (for example, hydrolytic condensable organotitanium compound) is, for example, a metal atom with respect to 1 mol of silicon atom of the compound represented by the formula (1). In terms of (for example, titanium atom), 0.01 to 20 mol (for example, 0.05 to 10 mol), preferably 0.1 to 8 mol, more preferably 0.3 to 5 mol, particularly 0.5 to About 4 mol (for example, 0.6 to 3.5 mol) may be sufficient.

  The polymerizable composition may further contain an acid catalyst for the sol-gel reaction of the silicon compound (and the hydrolytic condensable organometallic compound). Examples of the acid catalyst include inorganic acids (for example, sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid, etc.), organic acids [sulfonic acid (such as alkanesulfonic acid such as methanesulfonic acid, trifluoromethanesulfonic acid, etc.)], solid acid, and the like. Can be mentioned. Such an acid catalyst is mixed with the silicon compound (and the hydrolysis-condensable organometallic compound) so that the sol-gel reaction proceeds. Therefore, the acid catalyst is mixed immediately before use (immediately before curing) to form a polymerizable composition. May be.

The acid catalyst also includes a photoacid generator. Since such a photoacid generator does not generate an acid under non-exposure, even if the polymerizable composition is constituted before use, the sol-gel reaction does not proceed, which is advantageous in terms of handling properties. The photoacid generator is not particularly limited as long as it is a compound (component) that generates an acid by the action of light, and a conventional compound can be used. For example, an onium salt, a metallocene complex, and the like can be preferably used. Examples of the onium salt include a diazonium salt, a sulfonium salt, an iodonium salt, a phosphonium salt, a selenium salt, and the counter ions include CF ₃ SO ₃ ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ^−. Anions such as PF ₆ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ are used.

Typical photoacid generators include sulfonium salts {for example, triarylsulfonium salts [triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, (4-phenylthiophenyl) diphenylsulfonium Hexafluoroantimonate, triphenylsulfonium salts such as (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate], bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluoroantimonate, bis [4- (Diphenylsulfonio) phenyl] sulfide-bis-hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium hexafluoroan Monate), etc.}, diazonium salts (eg 4-chlorobenzenediazonium hexafluorophosphate), iodonium salts {eg bis (aryl) iodonium salts [eg bis (4-t-butylphenyl) iodonium hexafluorophosphate, diaryliodonium tetrakis ( Pentafluorophenyl) borate and the like], alkoxycarbonylalkoxyaryl-trialkylaryliodonium salts [e.g. 4-[(1-ethoxycarbonyl-ethoxy) phenyl]-(2,4,6-trimethylphenyl) -iodonium hexafluorophosphate Etc.], bis (alkoxyaryl) iodonium salts [for example, bis (alkanes such as (4-methoxyphenyl) phenyliodonium hexafluoroantimonate Kishifeniru) such iodonium salt], etc.}, phosphonium salts (such as benzyl triphenyl phosphonium hexafluoroantimonate), such as selenium salts (triphenyl selenium hexafluorophosphate), metallocene complex [for example, (eta ⁵ or eta ⁶ - isopropylbenzene) (Η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate etc.] and the like.

  Of these photoacid generators, onium salts [particularly sulfonium salts (such as triarylsulfonium salts), iodonium salts (such as bis (aryl) iodonium salts)] and the like are preferable. You may use a photo-acid generator individually or in combination of 2 or more types.

  The ratio of the acid catalyst (for example, photoacid generator) can be selected from the range of about 0.1 to 10 parts by weight with respect to 100 parts by weight of the compound represented by the formula (1). It may be about 10 to 10 parts by weight (for example, 1 to 10 parts by weight), preferably 0.5 to 5 parts by weight, and more preferably about 1 to 5 parts by weight (for example, 1 to 3 parts by weight). When the polymerizable composition contains a hydrolytic condensable organometallic compound, the ratio of the photoacid generator is 100 parts by weight of the total amount of the compound represented by the formula (1) and the hydrolytic condensable organometallic compound. Is, for example, 0.1 to 8 parts by weight (for example, 0.2 to 7 parts by weight), preferably 0.2 to 5 parts by weight, and more preferably 0.3 to 3 parts by weight (for example, 0. It may be about 5 to 2 parts by weight.

  In addition, the composition of this invention may contain the additive as needed. Examples of additives include pigments, colorants, thickeners, sensitizers, antifoaming agents, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, light Stabilizers, etc.), ultraviolet absorbers, plasticizers, surfactants, dissolution accelerators, fillers, antistatic agents, curing agents and the like. These additives may be used alone or in combination of two or more.

  The composition may contain a solvent. A composition containing such a solvent can be suitably used as, for example, a coating liquid (coating liquid) for forming a film (cured film) on a substrate. The solvent constituting such a coating solution is not particularly limited, and conventional solvents such as hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, and heptane, alicyclic hydrocarbons such as cyclohexane, Aromatic hydrocarbons such as toluene and xylene), halogenated solvents (haloalkanes such as dichloromethane and chloroform, haloarenes such as chlorobenzene), alcohols (such as alkanols such as methanol, ethanol, isopropanol), diols (ethylene (Poly) alkylene glycols such as glycol, propylene glycol, diethylene glycol and polyoxyethylene glycol), ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and oxolane), Steals (for example, acetates such as methyl acetate and ethyl acetate), ketones (dialkyl ketones such as acetone and ethyl methyl ketone, cyclohexanone, etc.), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate) And cellosolve acetate), glycol ethers (for example, methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, diglyme, etc.). These solvents may be used alone or in combination of two or more. In the composition containing a solvent, each solid component may be dissolved or dispersed in the solvent. Moreover, in order to accelerate | stimulate hydrolysis, the polymeric composition may contain water.

  Moreover, in the polymerizable composition containing a solvent, the ratio of the total amount of the compound represented by the formula (1) and the hydrolytic condensable organometallic compound can be appropriately adjusted according to the viscosity of the coating solution, for example, It may be 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.15 to 3 parts by weight, and particularly about 0.2 to 1 part by weight with respect to 1 part by weight of the solvent. .

  The polymerizable composition of the present invention is prepared by a conventional method, for example, the compound represented by the formula (1), the hydrolysis-condensable organometallic compound, the acid catalyst (such as a photoacid generator), and the like. If necessary, it can be prepared by mixing with other components (such as a solvent).

  Moreover, when using a hydrolytic condensable organometallic compound as a partial condensate, the partial condensate may be a commercially available product, and a monomer and / or oligomer corresponding to the partial condensate may be used appropriately. Presence of an acid catalyst (an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as formic acid or oxalic acid) dispersed or dissolved in a suitable solvent (for example, the above-mentioned solvents such as tetrahydrofuran, propylene glycol monomethyl ether acetate, or ethyl lactate) It can prepare by heating (heat processing) under. In the preparation of such a partial condensate, if necessary, water or the like may be mixed to promote hydrolysis condensation.

  Such a polymerizable composition of the present invention has polymerizability (hydrolytic condensation property) and can be used as a composition for forming a cured product (organic-inorganic hybrid cured product). In particular, such a polymerizable composition of the present invention has characteristics such as a high refractive index, and has a good balance of characteristics such as high adhesion to a substrate, hard coat properties, and transparency (or transparency to visible light). This is useful for obtaining a high-performance cured product (hybrid cured product).

(Cured product)
The cured product of the present invention (cured product obtained by curing (or crosslinking) the polymerizable resin composition) can be produced or prepared by hydrolytic condensation (curing or crosslinking) the composition. In particular, a polymerizable composition in which the acid catalyst is composed of a photoacid generator can be produced or prepared by irradiating the polymerizable composition with light and hydrolytic condensation. That is, in this polymerizable composition, hydrolysis condensation proceeds by an acid generated by light irradiation.

  The cured product (organic-inorganic hybrid cured product) is not particularly limited, and may be a three-dimensional cured product, a one-dimensional or two-dimensional cured product such as a cured film or a cured pattern, or a dot or dot-shaped cured product. . Such a cured product (particularly a cured film) of the present invention has excellent properties such as a high refractive index and high transparency to visible light, and also has excellent adhesion to a substrate. Since the polymerizable composition has small cure shrinkage and is suitable for producing a thin film on a substrate, the cured product of the present invention may be in the form of a cured film. Hereinafter, the cured film will be described in detail.

  A cured film is produced by applying the polymerizable composition on a substrate to form a coating film, followed by hydrolytic condensation (curing treatment) by an appropriate method according to the type of the acid catalyst. it can.

  The material of the substrate can be selected according to the application, for example, semiconductors such as silicon, gallium arsenide, gallium nitride, and silicon carbide; metals such as aluminum and copper; ceramics such as zirconium oxide, titanium oxide, and PZT; transparent inorganic materials (Glass, quartz, magnesium fluoride, calcium fluoride, etc.); Transparent resins (polymethyl methacrylate, polymethyl acrylate, polystyrene, etc.) and the like.

  Examples of the coating method include flow coating method, spin coating method, spray coating method, screen printing method, cast method, bar coating method, curtain coating method, roll coating method, gravure coating method, dipping method, slit method and the like. be able to.

  The thickness of the coating film (or cured film) can be selected from a range of about 0.01 μm to 10 mm depending on the use of the cured film. For example, in the case of a thin film (such as an antireflection film) for optical use, May be about 0.1 to 100 μm (preferably 0.3 to 50 μm). In particular, the cured film of the present invention is excellent in flexibility, does not generate cracks, and has a smooth surface even with a relatively large thickness. Therefore, the thickness (or average thickness) of the cured film (such as a thin film for optical use) of the present invention is, for example, 300 nm or more (for example, 300 nm to 10 μm), preferably 400 nm or more (for example, 500 nm to 5 μm), more preferably. It may be about 500 nm or more (for example, 600 nm to 3 μm, particularly about 650 nm or more (for example, 700 nm to 2 μm)).

  Examples of the hydrolysis condensation treatment (curing treatment) of the coating film include heating (treatment) and light irradiation (treatment) according to the type of the acid catalyst, and these may be combined. When heating and light irradiation are combined, heating and light irradiation may be performed in parallel, or after heating, light irradiation may be performed, or after light irradiation, heating may be performed. In the case of heat treatment, the heating temperature may be, for example, 60 to 250 ° C, preferably 80 to 200 ° C, more preferably about 100 to 160 ° C.

In the case of light irradiation, the light to be irradiated or exposed may be, for example, gamma rays, X-rays, ultraviolet rays, visible rays, etc., and is usually visible light or ultraviolet rays, particularly ultraviolet rays in many cases. The wavelength of light is, for example, about 150 to 800 nm, preferably 150 to 600 nm, more preferably about 200 to 400 nm (particularly 300 to 400 nm). The amount of irradiation light varies depending on the thickness of the coating film, but may be, for example, ^{2 to} 5000 mJ / cm ² , preferably about 5 to 3000 mJ / cm ² . The light source can be selected according to the type of light beam to be exposed. For example, in the case of ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a deuterium lamp, a halogen lamp, laser light (helium-cadmium laser, Excimer laser etc.) can be used.

  When the acid catalyst is composed of a photoacid generator, as described above, in addition to light irradiation, the coating film is further heated to accelerate the curing or cross-linking reaction (and sol-gel reaction). Original cross-linking occurs, and a cured product (cured coating film) with higher hardness can be obtained. Heating of the coating film is usually performed after light irradiation or with light irradiation, and is usually performed after light irradiation (after-cure) in many cases. The heating temperature can be selected from the same range as described above. The heating (after cure) time can be selected from a range of 3 seconds or more (for example, about 3 seconds to 5 hours), and may be, for example, 5 seconds to 2 hours, preferably about 20 seconds to 30 minutes. Usually, it may be about 1 minute to 3 hours (for example, 5 minutes to 2.5 hours).

  In addition, when forming a pattern or an image (for example, when manufacturing a printed wiring board etc.), you may carry out pattern exposure of the coating film formed on the base material, and this pattern exposure is performed by scanning of a laser beam. Alternatively, light irradiation may be performed through a photomask. A pattern or an image can be formed by developing (or dissolving) a non-irradiated region (unexposed portion) generated by such pattern exposure with a developer. Developers include water, alkaline aqueous solutions, hydrophilic solvents (for example, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves, cellosolve acetates, etc.) A mixture of these can be used.

  In the case of forming an optical thin film, a plurality of layers of the polymerizable resin composition may be formed on a substrate. For example, the antireflection film is manufactured by laminating a plurality of high refractive index thin films and low refractive index thin films. The cured film of the present invention is suitable as the high refractive index thin film. Moreover, as described above, the cured film of the present invention does not generate cracks even when the thickness is increased, so that a relatively thick high-refractive-index thin film can be produced. This is very advantageous in terms of cost.

  In the above example, the cured film is formed directly on the base material. However, after forming another functional layer on the base material, the cured film is formed on the functional layer. May be.

  The silicon compound having a novel fluorene skeleton of the present invention has excellent properties such as high transparency and a high refractive index, and can be suitable for various applications. For example, since it has a polymerizable group (hydrolytic condensable group) bonded to silicon, this polymerizable group can be polymerized by sol-gel reaction or the like, or it can be reacted with other monomers. And can be used as one of resin components having high optical properties. Furthermore, it is possible to use a polymerizable group bonded to silicon as a raw material for producing a compound having a new fluorene skeleton.

  Moreover, the silicon compound of the present invention has hydrolytic condensability and is advantageous for constituting a polymerizable composition. Such polymerizable compositions include paints, electrical equipment insulating materials, wire coating materials, electronic equipment sealing materials, printed wiring boards, protective films, photoresists, printing plate making materials, inks, adhesives, adhesives, It can be used for a wide range of applications such as a high-refractive index layer of an antireflection film such as a liquid crystal display and a reflector. In particular, the cured film of the present invention does not generate cracks even if it is a thick film, and has excellent optical properties such as a high refractive index, so an optical thin film (for example, a high refractive index of an antireflection film). Layer).

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

  In the examples, various characteristics were measured as follows.

(Infrared spectrum)
The measurement was performed using a Fourier transform infrared spectrophotometer ("Niclet 4700" manufactured by Thermo Nicolet) and a diamond ATR apparatus ("DuraSamplel II" manufactured by Smiths). The transmission spectrum was applied on a silicon wafer and measured as it was.

( ¹ H-NMR spectrum)
Measurement was performed using a nuclear magnetic resonance apparatus (“AL-300” manufactured by JEOL Ltd.).

(Refractive index, film thickness)
The refractive index at a wavelength of 633 nm and the film thickness were measured using a reflection spectral film thickness meter (manufactured by Otsuka Electronics Co., Ltd., “FE-3000”). The measurement was performed 10 times in each example, and the average values were taken as the refractive index and the film thickness.

(Haze)
Measurement was carried out using an integrating sphere and haze measurement software attached to an ultraviolet-visible spectrophotometer (“V-560” manufactured by JASCO Corporation).

(Example 1) Synthesis of bisphenylfluorene derivative To an eggplant-shaped flask, 20 ml of triethylamine (hereinafter referred to as TEA) and about 60 potassium hydroxide were added, and TEA was distilled. The molecular sieves dried by microwaves were added to the distilled TEA and dehydrated. Next, 1.79 g of 3-mercaptopropyltrimethoxysilane (hereinafter referred to as MPTMS) (2.5 mol with respect to BPEFA) was weighed into a two-necked eggplant-shaped flask and dissolved in 2.0 ml of tetrahydrofuran (THF). 2.00 g of 9-bis [4- (2-acryloylethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEFA) was added. It heated at 70 degreeC, stirring in presence of 63.4 microliters of TEA distilled as a catalyst (5 mol% with respect to MPTMS).

The reaction was traced with a Fourier transform infrared spectrophotometer using the solution at a heating time of 0 hour, 1 hour, 2 hours, and 3 hours, and a bisphenylfluorene derivative having alkoxysilane groups at both ends was produced. I checked. A ¹ H-NMR spectrum was measured with a nuclear magnetic resonance apparatus using 1 drop of liquid concentrated by an evaporator and 1 ml of deuterated chloroform, and a bis having alkoxysilane groups at both ends represented by the following formula. Formation of phenylfluorene derivatives was confirmed.

The measurement result of ¹ H-NMR is shown below.

¹ H-NMR δ (ppm): 7.73 (d, 2H, aromatic proton), 7.25-7.37 (m, 6H, aromatic proton), 7.09 (d, 4H, aromatic proton) ), 6.73 (d, 4H, aromatic proton), 4.40 (t, 4H, —OCH ₂ CH ₂ O—), 4.10 (m, 4H, —OCH ₂ CH ₂ O—), 3 .55 (s, 18H, SiO—CH ₃ ), 2.73 (t, 4H, COCH ₂ ), 2.59 (t, 4H, CH ₂ —S—CH ₂ ), 2.50 (t, 4H, _{CH 2 -S-CH 2),} 1.69 (quint, 4H, S-CH 2 "CH 2" CH 2 -Si), 0.73 (t, 4H, S-CH 2 CH 2 "CH 2" - Si)
(Example 2) Production of titania-fluorene organic / inorganic hybrid film 0.20 g of tetramer of titanic acid tetrabutoxide (tetra-n-butoxytitanium) (made by Wako Pure Chemical Industries, Ltd., hereinafter referred to as TBXT) in a brown bottle 1.00 g of a propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) solution in which the bisphenylfluorene derivative obtained in Example 1 was dissolved at a concentration of 20% by weight was added and stirred at room temperature for 3 hours. Further, 0.80 g of PGMEA and 1 drop of diaryliodonium tetrakis (pentafluorophenyl) borate (“Silicolys CATA211”, manufactured by Arakawa Chemical Industries, Ltd.) as a photoacid generator were added and stirred at room temperature for 1 hour. Then, it filtered with the syringe with a membrane filter.

  After filtration, about 15 drops of the obtained coating solution were dropped on a glass substrate and rotated at 500 rpm for 30 seconds by a spin coater to prepare a film. After drying in an oven at 120 ° C. for 1 minute, UV light was irradiated for 20 seconds with a high-pressure mercury lamp to generate an acid in the film, and hybridization with titania was performed by a sol-gel reaction. Furthermore, it was gelled by heating and curing in an oven at 120 ° C. for 30 minutes, and a transparent titania-fluorene organic / inorganic hybrid film having excellent smoothness and no cracks was produced. The obtained hybrid film had a refractive index of 1.638, a film thickness of 849 nm, and a haze value of 0.3%. In addition, about hybridization, the presence of Si-O-Ti bond, Ti-O-Ti bond, Si-O-Si bond was confirmed by Fourier transform infrared spectrophotometer using the liquid before and after UV irradiation. .

  The adhesion was evaluated by a cross cutting test. On the hybrid membrane, 100 squares with a side of 1 mm were made with a super cutter guide, and peeling with cellophane tape was performed, but there was no peeling at all. This also revealed that the hybrid film is excellent in adhesion to the glass substrate.

(Example 3) Production of titania-fluorene organic / inorganic hybrid film PGMEA solution in which TBXT 0.30 g was weighed into a brown bottle and the bisphenylfluorene derivative obtained in Example 1 was dissolved at a concentration of 20% by weight. 1.00g was added and it stirred at normal temperature for 3 hours. Further, 0.80 g of PGMEA and 1 drop of diaryliodonium tetrakis (pentafluorophenyl) borate (“Silicolites CATA211”, manufactured by Arakawa Chemical Industries, Ltd.) which is a photoacid generator were added and stirred at room temperature for 1 hour. Then, it filtered with the syringe with a membrane filter.

  After filtration, about 15 drops of the obtained coating solution were dropped onto a glass substrate and rotated at 500 rpm for 30 seconds by a spin coater to prepare a film. After drying in an oven at 120 ° C. for 1 minute, UV light was irradiated for 20 seconds with a high-pressure mercury lamp to generate an acid in the film, and hybridization with titania was performed by a sol-gel reaction. Furthermore, it was gelled by heating and curing in an oven at 120 ° C. for 30 minutes, and a transparent titania-fluorene organic / inorganic hybrid film having excellent smoothness and no cracks was produced. The obtained hybrid film had a refractive index of 1.665, a film thickness of 868 nm, and a haze value of 0.4%.

(Example 4) Production of titania-fluorene organic-inorganic hybrid film PGMEA solution in which 0.40 g of TBXT was weighed into a brown bottle and the bisphenylfluorene derivative obtained in Example 1 was dissolved at a concentration of 20% by weight. 1.00g was added and it stirred at normal temperature for 3 hours. Further, 0.80 g of PGMEA and 1 drop of diaryliodonium tetrakis (pentafluorophenyl) borate (“Silicolites CATA211”, manufactured by Arakawa Chemical Industries, Ltd.) which is a photoacid generator were added and stirred at room temperature for 1 hour. Then, it filtered with the syringe with a membrane filter.

  After filtration, about 15 drops of the obtained coating solution were dropped onto a glass substrate and rotated at 500 rpm for 30 seconds by a spin coater to prepare a film. After drying in an oven at 120 ° C. for 1 minute, UV light was irradiated for 20 seconds with a high-pressure mercury lamp to generate an acid in the film, and hybridization with titania was performed by a sol-gel reaction. Furthermore, it was gelled by heating and curing in an oven at 120 ° C. for 30 minutes to produce a transparent titania-fluorene-based organic-inorganic hybrid film having excellent smoothness and no cracks. The obtained hybrid film had a refractive index of 1.678, a film thickness of 1038 nm, and a haze value of 0.2%.

(Example 5) Production of titania-fluorene-based organic-inorganic hybrid film PGMEA solution in which 0.50 g of TBXT was weighed into a brown bottle and the bisphenylfluorene derivative obtained in Example 1 was dissolved at a concentration of 20% by weight. 1.00g was added and it stirred at normal temperature for 3 hours. Further, 0.80 g of PGMEA and 1 drop of diaryliodonium tetrakis (pentafluorophenyl) borate (“Silicolites CATA211”, manufactured by Arakawa Chemical Industries, Ltd.) which is a photoacid generator were added and stirred at room temperature for 1 hour. Then, it filtered with the syringe with a membrane filter.

  After filtration, about 15 drops of the obtained coating solution were dropped onto a glass substrate and rotated at 500 rpm for 30 seconds by a spin coater to prepare a film. After drying in an oven at 120 ° C. for 1 minute, UV light was irradiated for 20 seconds with a high-pressure mercury lamp to generate acid in the film, and hybridization with titania was performed by a sol-gel reaction. Furthermore, it was gelled by heating and curing in an oven at 120 ° C. for 30 minutes to produce a transparent titania-fluorene-based organic-inorganic hybrid film having excellent smoothness and no cracks. The obtained hybrid film had a refractive index of 1.638, a film thickness of 1054 nm, and a haze value of 0.4%.

(Example 6) Production of titania-fluorene organic / inorganic hybrid film PGMEA solution in which 0.60 g of TBXT was weighed into a brown bottle and the bisphenylfluorene derivative obtained in Example 1 was dissolved at a concentration of 20% by weight. 1.00g was added and it stirred at normal temperature for 3 hours. Further, 0.80 g of PGMEA and 1 drop of diaryliodonium tetrakis (pentafluorophenyl) borate (“Silicolites CATA211”, manufactured by Arakawa Chemical Industries, Ltd.) which is a photoacid generator were added and stirred at room temperature for 1 hour. Then, it filtered with the syringe with a membrane filter.

  After filtration, about 15 drops of the obtained coating solution were dropped onto a glass substrate and rotated at 500 rpm for 30 seconds by a spin coater to prepare a film. After drying in an oven at 120 ° C. for 1 minute, UV light was irradiated for 20 seconds with a high-pressure mercury lamp to generate an acid in the film, and hybridization with titania was performed by a sol-gel reaction. Furthermore, it was gelled by heating and curing in an oven at 120 ° C. for 30 minutes to produce a transparent titania-fluorene-based organic-inorganic hybrid film having excellent smoothness and no cracks. The obtained hybrid film had a refractive index of 1.700, a film thickness of 1213 nm, and a haze value of 0.2%.

(Comparative Example 1)
According to Example 7 of JP 2007-91870 A, a thick hybrid film was prepared as follows.

  2 g of 3-acryloyloxypropyltrimethoxysilane (APTMS), 2 g of phenyltrimethoxysilane (PTMS) and 20 g of tetraisopropoxytitanium were dissolved in 10 ml of tetrahydrofuran (THF), 60 mg of formic acid was added, and the mixture was stirred at 60 ° C. for 2 hours. After cooling, a partially condensed sol was prepared (solid content about 17%).

  The obtained partially condensed sol 1.0 g, 0.2 g of BPEFA, and 4 g of PGMEA, a photo radical initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Ciba Specialty Chemicals Co., Ltd.) , Trade name “Darocur 1173”) 2 mg, and photoacid generator [4- (1-ethoxycarbonylethoxy) phenyl-2 ′, 4 ′, 6′-trimethylphenyliodonium hexafluorophosphate, manufactured by Nippon Soda Co., Ltd.] About 15 drops of the coating solution prepared by adding 2 mg was dropped onto a glass substrate and rotated at 500 rpm for 30 seconds by a spin coater to prepare a film.

The obtained coating film was irradiated with ultraviolet rays (1300 mJ / cm ² ), and a hybrid film was prepared by curing of acrylate and sol-gel reaction. The obtained hybrid film was after-cured at 150 ° C. for 1.5 hours to obtain a film (film thickness of 950 nm), but the film surface was extremely rough and the transparency was low.

Claims (12)

Following formula (1)

{Wherein, ring Z represents an aromatic hydrocarbon ring, R ¹ represents an alkylene group, R ² represents a hydrogen atom or a methyl group, and Y represents a group — (XR ³ ) _p —SiR ⁴ R ⁵ R ^6. [Wherein, X represents a sulfur atom or an imino group, R ³ represents an alkylene group, and R ⁴ , R ⁵ and R ⁶ are the same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, a group —OR ^7. (Wherein R ⁷ represents a hydrocarbon group) or a hydrocarbon group, and p represents an integer of 1 or more. However, at least one of R ⁴ , R ^5, and R ⁶ is a hydrogen atom, a hydroxyl group, a halogen atom, or a group —OR ⁷ . M is an integer of 0 or more, n1 is an integer of 1 or more, and n2 is an integer of 0 or more. }
A silicon compound having a fluorene skeleton represented by: Ring Z is a benzene ring or a naphthalene ring, R ¹ is a C _2-4 alkylene group, m is 1-4, R ³ is a C _2-4 alkylene group, and the group —SiR ⁴ R ⁵ R ^6, _{di-C 1-4} alkyl _{C 1-4} alkoxysilyl _{group, C 1-4} alkyl di _{C 1-4} alkoxysilyl group, or a _{tri-C 1-4} alkoxysilyl group in which claim 1 silicon compound as described.   The silicon compound according to claim 1 or 2, wherein X is a sulfur atom.   The silicon compound according to claim 1, wherein X is a sulfur atom, p is 1, n1 is 1 to 2, and n2 is 1 to 2. Following formula (2)

(In the formula, Z, R ¹ , R ² , m, n1, and n2 are the same as above.)
And a compound represented by the following formula (3)
^{R 4 R 5 R 6 Si- (} R 3 X) p -H (3)
(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , X and p are the same as above.)
The method of manufacturing the silicon compound in any one of Claims 1-4 by making the compound represented by these react.   The manufacturing method of Claim 5 with which the compound represented by Formula (2) and the compound represented by Formula (3) whose X is a sulfur atom are made to react in presence of a base catalyst.   A silicon compound according to any one of claims 1 to 4 and at least one hydrolytic condensable organic non-silicon metal compound selected from a hydrolytic condensable organic titanium compound and a hydrolytic condensable organic zirconium compound. Constructed polymerizable composition.   The polymerizable composition according to claim 7, wherein the hydrolytic condensable organic non-silicon metal compound is composed of at least an oligomer of a titanium alkoxide.   The ratio of the hydrolytic condensable non-silicon-based organometallic compound is 0.3 to 5 parts by weight with respect to 1 part by weight of the silicon compound according to any one of claims 1 to 4. A polymerizable composition.   Furthermore, the polymeric composition in any one of Claims 7-9 containing the acid catalyst comprised with the photo-acid generator.   Hardened | cured material which the polymeric composition in any one of Claims 7-10 hardened | cured.   The cured product according to claim 11, which is a cured film having a thickness of 300 nm or more.