JP2018127410A - Curable composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that can form a cured product with a high refractive index, and a cured product of the curable composition.SOLUTION: A curable composition has a cationic polymerizable compound, and polysilane. The cationic polymerizable compound contains a first cationic polymerizable compound represented by the formula (1) (where Arand Ar, and Zand Zeach represent an arene ring, Rand R, and Rand Reach represent a substituent, Rand Reach represent a linear or branched alkylene group, Rand Reach represent a hydrogen atom or a substituent, k1 and k2, m1 and m2 and n1 and n2 each represent an integer of 0 or greater).SELECTED DRAWING: None

Description

  The present invention relates to a curable composition comprising a cationically polymerizable compound containing an oxetane compound having a bisarylfluorene (including bisarylbenzofluorene and bisaryldibenzofluorene, the same shall apply hereinafter) skeleton, and polysilane, and a cured product thereof. .

  In recent years, organic-inorganic hybrid materials that combine organic and inorganic materials at the molecular level have characteristics derived from organic materials (for example, lightness, ease of processing, flexibility, etc.) and properties derived from inorganic materials ( It is attracting attention as a material that can achieve both heat resistance, weather resistance, high elastic modulus, and the like.

  For example, JP-A-2006-20472 (Patent Document 1) includes a photocationically polymerizable compound (A), a polysilane (B), and a photoacid generator (C) that absorbs visible light to generate an acid. A photopolymerizable resin composition is disclosed. This composition has excellent photosensitivity even when irradiated with visible light in order to suppress decomposition of polysilane, and can improve the hardness of a cured product. It is described that it can be used for a photoresist, a printing plate making material, and the like. In an example of this document, photopolymerization including 9,9-bis [3,4-diglycidyloxy-phenyl] fluorene, polymethylphenylsilane or hyperbranched phenylsilane oligomer, and a predetermined photoacid generator. A functional resin composition is prepared.

  However, the refractive index and insolubilization rate (or curability) of a cured product obtained from such a composition may not be sufficient, and cannot be used for applications requiring high levels of these characteristics.

  JP-A-2000-336082 (Patent Document 2) discloses an oxetane compound having a 9,9-bisphenylfluorene skeleton as a compound capable of cationic polymerization. However, Patent Document 2 does not specifically describe the refractive index and insolubilization rate in the cured product of the oxetane compound, but also forms a curable composition by combining the oxetane compound and polysilane. Is not described at all.

JP, 2006-20472, A (claim, example, paragraph [0001] [0009]) JP 2000-336082 A (Claims, Examples)

  Therefore, the objective of this invention is providing the curable composition which can form the hardened | cured material which has a high refractive index, and its hardened | cured material.

  Another object of the present invention is to provide a curable composition and a cured product thereof that can achieve a high insolubilization rate (or curability) even when a cationic polymerizable compound having a small number of polymerizable functional groups is used.

  Still another object of the present invention is to provide a curable composition capable of forming a cured product that can achieve both a high insolubilization rate and a high flexibility (or toughness), and a cured product thereof.

  Another object of the present invention is to provide a curable composition having a high solubility in a solvent and excellent handleability even if it contains a condensed polycyclic aromatic skeleton, and a cured product thereof.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors not only can form a cured product having a high refractive index when combining a cationic polymerizable compound containing an oxetane compound having a bisarylfluorene skeleton with a polysilane. The inventors have found that even when a cationic polymerizable compound having a small number of polymerizable functional groups is used, a high insolubilization rate can be achieved, and the present invention has been completed.

  That is, the curable composition of the present invention is a curable composition containing a cationically polymerizable compound and polysilane, and the cationically polymerizable compound is a first cationically polymerizable compound represented by the following formula (1). Contains compounds.

(In the formula, Ar ¹ and Ar ² and Z ¹ and Z ² are each an arene ring, R ^1a and R ^1b and R ^2a and R ^2b are each a substituent, and R ^3a and R ^3b are each linear or branched. An alkylene group, R ^4a and R ^4b are each a hydrogen atom or a substituent, k1 and k2, m1 and m2, and n1 and n2 are each an integer of 0 or more).

In the formula (1), Ar ¹ and Ar ² are each a C _6-10 arene ring (eg, a benzene ring), Z ¹ and Z ² are C _6-12 arene rings (eg, a naphthalene ring), R ^3a and R ^3b is a linear or branched C _2-6 alkylene group (for example, a linear or branched C _2-4 alkylene group), and R ^4a and R ^4b are a hydrogen atom or a C _1-6 alkyl group, respectively. (For example, C _1-4 alkyl group), k1 and k2 are each an integer of about 0 to 4 (for example, 0 to 2), m1 and m2 are each an integer of about 0 to 6 (for example, 0 to 2), n1 And n2 may each be an integer of about 0 to 20 (for example, 0 to 8).

  Moreover, the said cationically polymerizable compound may further contain the 2nd cationically polymerizable compound represented by following formula (2).

(In the formula, Ar ³ and Ar ⁴ and Z ³ and Z ⁴ are each an arene ring, R ^5a and R ^5b and R ^6a and R ^6b are each a substituent, and R ^7a and R ^7b are each linear or branched. An alkylene group, R ^8a and R ^8b are each a hydrogen atom or a methyl group, p1 and p2, q1 and q2, and r1 and r2 are each an integer of 0 or more, and s1 and s2 are each an integer of 1 to 4.

In the formula (2), Ar ³ and Ar ⁴ are each a C _6-10 arene ring, Z ³ and Z ⁴ are C _6-12 arene rings, and R ^7a and R ^7b are each linear or branched C _{2 -6} alkylene group, p1 and p2 are each an integer of about 0 to 4, q1 and q2 are each an integer of about 0 to 6, r1 and r2 are each an integer of about 0 to 20, and s1 and s2 are 1 or 2. May be. The ratio of the first cationic polymerizable compound to the second cationic polymerizable compound may be the former / the latter (weight ratio) = 50/50 to 99/1.

The polysilane may contain a linear poly C _1-6 alkyl C _6-14 aryl silane. The ratio of the cationic polymerizable compound to the polysilane may be about the former / the latter (weight ratio) = 90/10 to 20/80.

  The present invention also includes a cured product obtained by curing the curable composition. The cured product may have a refractive index of about 1.65 to 1.75 at a temperature of 25 ° C. and a wavelength of 589 nm.

  In the present specification and claims, the term “compound having a fluorene skeleton” means not only a fluorene skeleton but also a compound having an aromatic skeleton with an inherent fluorene ring such as a benzofluorene skeleton or a dibenzofluorene skeleton. Used for.

  Since the curable composition of the present invention contains a cationic polymerizable compound containing a predetermined oxetane compound and polysilane, a cured product having a high refractive index can be formed. Moreover, even if a cationically polymerizable compound having a small number of polymerizable functional groups is used, not only a high insolubilization rate (or curability) can be achieved, but also a high insolubilization rate and flexibility (or toughness) can be achieved. Furthermore, even if the oxetane compound contains a condensed polycyclic aromatic skeleton, the solubility in a solvent is high, so that handleability can be improved.

  The curable composition of the present invention includes a cationic polymerizable compound containing an oxetane compound having a bisarylfluorene skeleton (also referred to as a first cationic polymerizable compound) and polysilane.

[Cationically polymerizable compound]
(First cationic polymerizable compound)
The first cationically polymerizable compound is represented by the following formula (1).

(In the formula, Ar ¹ and Ar ² and Z ¹ and Z ² are each an arene ring, R ^1a and R ^1b and R ^2a and R ^2b are each a substituent, and R ^3a and R ^3b are each linear or branched. An alkylene group, R ^4a and R ^4b are each a hydrogen atom or a substituent, k1 and k2, m1 and m2, and n1 and n2 are each an integer of 0 or more).

In the formula (1), examples of the arene ring (aromatic hydrocarbon ring) represented by the rings Ar ¹ and Ar ² include C _6-14 arene rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. C _6-10 arene rings (particularly benzene rings) such as benzene ring and naphthalene ring are preferable. The types of arene rings represented by the rings Ar ¹ and Ar ² may be the same or different from each other.

Rings Ar ¹ and Ar ² are a condensed ring skeleton with a 5-membered ring interposed therebetween, for example, a fluorene skeleton in which both of the rings Ar ¹ and Ar ² are benzene rings; one is a benzene ring and the other is a naphthalene ring A certain benzofluorene skeleton (eg, benzo [a] fluorene skeleton, benzo [b] fluorene skeleton, benzo [c] fluorene skeleton, etc.); a dibenzofluorene skeleton (eg, dibenzo [b, h] fluorene skeleton, both of which are naphthalene rings An aromatic skeleton (preferably a fluorene skeleton or a benzofluorene skeleton, particularly a fluorene skeleton) in which a fluorene ring is present may be formed.

In the formula (1), examples of the arene ring represented by the rings Z ¹ and Z ² include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, and the like. In the polycyclic arene ring, A condensed polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring), a ring assembly arene ring (ring assembly aromatic hydrocarbon ring) and the like are included.

Examples of the condensed polycyclic arene ring include a condensed bicyclic arene ring (for example, a condensed bicyclic C _10-16 arene ring such as a naphthalene ring and an indene ring), and a condensed tricyclic arene ring (for example, an anthracene ring). And condensed bi- to tetra-cyclic arene rings and the like. Preferred examples of the rings Z ¹ and Z ² include condensed polycyclic C _10-16 arene rings (preferably condensed polycyclic C _10-14 arene rings) such as naphthalene ring and anthracene ring. preferable.

Examples of the ring-assembled arene ring include a bearene ring (for example, a bi-C _6-12 arene ring such as a biphenyl ring, a binaphthyl ring, and a phenylnaphthalene ring (such as a 1-phenylnaphthalene ring and a 2-phenylnaphthalene ring)), a tellarene ring ( For example, a tel C _6-12 arene ring such as a terphenylene ring) can be exemplified. A preferable ring assembly arene ring includes a bi-C _6-10 arene ring, and a biphenyl ring is particularly preferable.

The types of rings Z ¹ and Z ² may be the same or different from each other and are usually the same. Of the rings Z ¹ and Z ² , C _6-12 arene rings such as benzene ring, naphthalene ring, biphenyl ring and the like are preferable, and among them, C _6-10 arene rings such as benzene ring and naphthalene ring, particularly high refractive index. A naphthalene ring is preferable from the viewpoint of being able to be converted.

In addition, the substitution position of the rings Z ¹ and Z ² bonded to the 5-membered ring is not particularly limited. For example, when the rings Z ¹ and Z ² are naphthalene rings, either the 1-position or the 2-position may be used. Further, when the rings Z ¹ and Z ² are biphenyl rings, they may be in any of the 2-position, 3-position and 4-position.

In the formula (1), the substituents R ^1a and R ^1b may be hydrocarbon groups [eg, alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, etc.] Linear or branched C _1-6 alkyl group, etc.), aryl group (eg, C _6-10 aryl group such as phenyl group), etc.], cyano group, halogen atom (eg, fluorine atom, chlorine atom) , Bromine atoms, etc.). Of these groups R ^1a and R ^1b , an alkyl group (for example, a linear or branched C _1-4 alkyl group), a cyano group, and a halogen atom are preferable, and an alkyl group (particularly, a C group such as a methyl group). _1-3 alkyl group) is preferred.

The number of substitutions k1 and k2 of the groups R ^1a and R ^1b is an integer of 0 or more, for example, an integer of about 0 to 8 (for example, 0 to 4), preferably an integer of about 0 to 2, more preferably 0 or 1 , Especially 0. The substitution numbers k1 and k2 may be the same or different from each other. In addition, the types of the groups R ^1a and R ^1b that are substituted on the rings Ar ¹ and Ar ² may be the same or different from each other. When k1 and k2 are 2 or more, they are substituted on the same rings Ar ¹ and Ar ² . The two or more groups R ^1a and R ^1b may be the same or different from each other. Further, the substitution positions of the groups R ^1a and R ^1b are not particularly limited. For example, when the rings Ar ¹ and Ar ² and the 5-membered ring form a fluorene ring, the 2-position to the 7-position (2-position, 3-position and 7-position).

In the formula (1), the substituents R ^2a and R ^2b include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a hydrocarbon group {for example, an alkyl group (methyl group, ethyl group, Linear or branched C _1-10 alkyl group such as propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, preferably linear or branched C _1-6 alkyl Group, more preferably linear or branched C _1-4 alkyl group, etc.); cycloalkyl group (eg, C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group, etc.); aryl group [eg, phenyl group, alkylphenyl group (e.g., methylphenyl group (tolyl group), a dimethylphenyl group (xylyl), etc.), C _6, such as biphenylyl group, a naphthyl group _-12 aryl group, etc.]; aralkyl group (eg, C _6-10 aryl-C _1-4 alkyl group such as benzyl group, phenethyl group, etc.)}, alkoxy group (eg, methoxy group, ethoxy group, propoxy group, etc.) a linear or branched C _1-10 alkoxy group such as an n-butoxy group, an isobutoxy group, an s-butoxy group or a t-butoxy group, or a cycloalkyloxy group (for example, a C ₅₋ such as a cyclohexyloxy group). ₁₀ cycloalkyloxy group), aryloxy group (for example, C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (for example, C _6-10 aryl-C _1-4 alkyl such as benzyloxy group) Oxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, n-butyl) C _1-10 alkylthio such as thio group and t-butylthio group), cycloalkylthio group (such as C _5-10 cycloalkylthio group such as cyclohexylthio group), arylthio group (such as C ₆ such as thiophenoxy group) _-10 arylthio group), aralkylthio group (eg, C _6-10 aryl-C _1-4 alkylthio group such as benzylthio group), acyl group (eg, C _1-6 acyl group such as acetyl group), Nitro group, cyano group, substituted amino group [for example, dialkylamino group (for example, diC _1-4 alkylamino group such as dimethylamino group), bis (alkylcarbonyl) amino group (for example, bis such as diacetylamino group) (C _1-4 alkyl-carbonyl) amino group and the like)] and the like.

Of these groups R ^2a and R ^2b , typically, a halogen atom, a hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group), alkoxy group, acyl group, nitro group, cyano group, substituted An amino group etc. are mentioned. Preferred groups R ² include an alkyl group (such as a linear or branched C _1-6 alkyl group such as a methyl group), an aryl group (such as a C _6-14 aryl group such as a phenyl group), an alkoxy group (methoxy A linear or branched C _1-4 alkoxy group such as a group), in particular, an alkyl group (particularly a linear or branched C _1-4 alkyl group such as a methyl group), an aryl group (phenyl group) C _6-10 aryl groups such as

The substitution numbers m1 and m2 of the groups R ^2a and R ^2b may be integers of 0 or more, and can be appropriately selected according to the types of the rings Z ¹ and Z ² . For example, it may be an integer of about 0 to 8, preferably an integer of about 0 to 4 (for example, 0 to 3), more preferably an integer of about 0 to 2 (for example, 0 or 1), particularly 0. There may be. The substitution numbers m1 and m2 may be the same or different from each other. The types of the groups R ^2a and R ^2b may be the same or different from each other. When the number of substitutions m1 and m2 is 2 or more, two or more groups R ^2a substituted on the same ring Z ^{1 or} Z ² And R ^2b may be the same or different from each other. The substitution positions of the groups R ^2a and R ^2b are not particularly limited, and may be substituted at a position other than the substitution position of the oxetane ring-containing group.

In the formula (1), the groups R ^3a and R ^3b include a linear or branched alkylene group. Examples of the linear alkylene group include an ethylene group, a trimethylene group, and a tetramethylene group. And a linear C _2-6 alkylene group (preferably a linear C _2-4 alkylene group, more preferably a linear C _2-3 alkylene group, particularly an ethylene group). Examples of the branched alkylene group include Examples thereof include branched C _3-6 alkylene groups (preferably branched C _3-4 alkylene groups, particularly propylene groups) such as propylene group, 1,2-butanediyl group, 1,3-butanediyl group and the like. It is done. Of these groups R ^3a and R ^3b, a linear or branched C _2-6 alkylene group (for example, a linear or branched C _2-4 alkylene group) is preferable, and a linear chain is more preferable. Or a branched C _2-3 alkylene group (particularly an ethylene group). In addition, in each oxetane ring-containing group substituted with different rings Z ¹ and Z ² , the types of the groups R ^3a and R ^3b may be the same or different from each other.

The number of repetitions n1 and n2 of the oxyalkylene group (OR ^3a and OR ^3b ) can be selected from the range of an integer of 0 or more (for example, an integer of about 0 to 20), for example, about 0 to 15 (1 to 10). An integer, preferably an integer of about 0 to 8 (for example, 2 to 7), more preferably an integer of about 0 to 5 (for example, 3 to 5), particularly an integer of about 0 to 2 (for example, 0 or 1, particularly 0). If n1 and n2 are too large, the refractive index may decrease. N1 and n2 may be the same or different from each other. In the oxetane ring-containing group, when the repeating numbers n1 and n2 are 2 or more, the types of the two or more groups R ^3a and R ^3b may be different from each other, but are preferably the same.

  In the present specification, unless otherwise specified, “the number of repeating oxyalkylene groups” (and “the total number of oxyalkylene groups (total number of additions)” described later) refers to oxyalkylene in one molecule of a compound. It is used to mean both the number of groups (integer) and the average value of the number of oxyalkylene groups in the molecular assembly of the compound [ie, the average number of added moles]. Therefore, the repeating numbers n1 and n2 may be an average value (arithmetic average or arithmetic average) in the molecular assembly of the compound represented by the formula (1), and the range is preferably the range of the integer. It may be the same level including the aspect.

  In the formula (1), the total number of repeating numbers n1 and n2 means the total number (total number of additions) of oxyalkylene groups in one molecule of the compound represented by the formula (1), and simply n1 + n2 There is a case. n1 + n2 can be selected, for example, from an integer range of about 0 to 30, for example, an integer of about 0 to 25 (eg, 1 to 20), preferably an integer of about 0 to 15 (eg, 2 to 10), Preferably, it may be an integer of about 0 to 8 (for example, 4 to 6), particularly an integer of about 0 to 4 (for example, 0 to 2, particularly 0). N1 + n2 may be an integer as described above, but may be an average added mole number in the molecular assembly of the compound represented by the formula (1), and the range thereof is, for example, the integer It may be comparable, including the range and preferred embodiments. If the value of n1 + n2 is too large, the bisarylfluorene skeleton content (for example, the number of moles contained) per unit amount (for example, unit weight) of the cured product is lowered, so that a high refractive index and high heat resistance derived from the skeleton are obtained. There is a risk that excellent properties such as property may deteriorate. N1 + n2 can be measured by a conventional method. For example, in the preparation of the compound represented by the formula (1), the amount of the hydroxy compound having a bisarylfluorene skeleton as a raw material and consumed in the reaction. It can measure by the method (For example, the method of the international publication 2013/022065 etc.) etc. which calculate as a value of an arithmetic mean or an arithmetic mean from the ratio with the quantity of an alkylene oxide (alkylene carbonate or haloalkanol).

In the formula (1), the groups R ^4a and R ^4b are a hydrogen atom or a substituent, and examples of the substituent include a hydrocarbon group {for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, linear or branched C _1-10 alkyl group such as n-butyl group, isobutyl group, s-butyl group, t-butyl group, etc., preferably linear or branched C _1-6 alkyl group, Preferably a linear or branched C _1-4 alkyl group); a cycloalkyl group (eg, C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group, etc.); an aryl group [eg, phenyl group, alkyl C _6-12 aryl group such as phenyl group (for example, methylphenyl group (tolyl group), dimethylphenyl group (xylyl group), etc.), biphenylyl group, naphthyl group, etc. Aralkyl group (eg, C _6-10 aryl-C _1-4 alkyl group such as benzyl group, phenethyl group, etc.); Allyl group etc.}; Fluorine-containing group [eg, fluorine atom; A fluorinated hydrocarbon group such as a C _1-6 fluorinated alkyl group such as a fluoromethyl group]; a heteroaryl group (for example, a furyl group, a thienyl group, etc.) and the like.

Preferred groups R ^4a and R ^4b include a hydrogen atom or a hydrocarbon group (for example, a hydrogen atom or an alkyl group), and more preferably a hydrogen atom or a C _1-6 alkyl group (for example, a hydrogen atom or C _{1- 4} alkyl group), particularly a hydrogen atom or a C _1-2 alkyl group (for example, a methyl group or an ethyl group, particularly a methyl group). The types of the groups R ^4a and R ^4b may be different from each other and are usually the same.

The substitution position of the oxetane ring-containing group is not particularly limited, can be replaced in a suitable position on the ring Z ¹ and Z ^2, for example, when ring Z ¹ and Z ² is a benzene ring, the corresponding phenyl group 3 It is often substituted at the -position or 4-position (particularly the 4-position). In addition, when the rings Z ¹ and Z ² are naphthalene rings, they are often substituted at any of the corresponding 5- to 8-positions of the naphthyl group, for example, between the rings Ar ¹ and Ar ² . With respect to the intervening 5-membered ring, the 1-position or 2-position of the naphthalene ring is substituted (replaced in relation to 1-naphthyl or 2-naphthyl), and the 1,5-position relative to this substitution position In many cases, the oxetane ring-containing group is substituted by a relationship such as 2,6-position (particularly, a relationship of 2,6-position).

As the first cationically polymerizable compound represented by the formula (1), for example, in the formula (1), (A) a compound in which the rings Ar ¹ and Ar ² are benzene rings, (B) a ring Ar ¹ and Examples include compounds in which at least one of Ar ² is a naphthalene ring. These compounds can be used alone or in combination of two or more. Of these compounds, (A) a compound in which the rings Ar ¹ and Ar ² are benzene rings is preferred.

(A) typically as a compound rings Ar ¹ and Ar ² is a benzene ring in the compound rings Ar ¹ and Ar ² is a benzene ring Formula (1), for example, (A1) Ring ^{Z 1} and ^{Z 2} Bisphenylfluorenes in which is a benzene ring, (A2) bisnaphthylfluorenes in which rings Z ¹ and Z ² are naphthalene rings, and the like.

Specific examples of (A1) bisphenylfluorenes include, for example, (A1-1) 9,9-bis [(3-oxetanyl) methoxy-phenyl] fluorene in which n1 and n2 are 0 in the formula (1). Class {e.g., 9,9-bis [(3-oxetanyl) methoxy-phenyl] fluorene (e.g., 9,9- in which in the formula (1), m1 and m2 are 0, and ^R4a and ^R4b are hydrogen atoms) Bis [4-((3-oxetanyl) methoxy) -phenyl] fluorene and the like); In the above formula (1), 9,9-bis [(3 wherein m1 and m2 are 0, and R ^4a and R ^4b are alkyl groups -Alkyl-3-oxetanyl) methoxy-phenyl] fluorene (eg, 9,9-bis [4-((3-methyl-3-oxetanyl) methoxy) -phenyl] fluorene, 9, - bis [4 - ((3-ethyl-3-oxetanyl) methoxy) - phenyl] fluorene such as 9,9-bis _{[(3-C 1-6} alkyl-3-oxetanyl) methoxy - phenyl] fluorene, etc.); In the formula (1), 9,9-bis [(3-oxetanyl) methoxy- (mono or 1), wherein m1 and m2 are 1 or 2, R ^2a and R ^2b are alkyl groups, and R ^4a and R ^4b are hydrogen atoms. Di) alkylphenyl] fluorene (eg, 9,9-bis [4-((3-oxetanyl) methoxy) -3-methylphenyl] fluorene, 9,9-bis [4-((3-oxetanyl) methoxy)- 9,9-bis [(3-oxetanyl) methoxy- (mono or di) C _1-6 alkylphenyl] fluorene and the like) such as 3,5-dimethylphenyl] fluorene; 9,9-bis [(3-alkyl-3-oxetanyl) methoxy wherein m1 and m2 are 1 or 2, R ^2a and R ^2b are alkyl groups, and R ^4a and R ^4b are alkyl groups in the formula (1) -(Mono or di) alkylphenyl] fluorene (eg, 9,9-bis [4-((3-methyl-3-oxetanyl) methoxy) -3-methylphenyl] fluorene, 9,9-bis [4- ( 9,9 such as (3-ethyl-3-oxetanyl) methoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-methyl-3-oxetanyl) -3,5-dimethylphenyl] fluorene - bis _{[(3-C 1-6} alkyl-3-oxetanyl) methoxy - (mono or _{di) C 1-6} alkyl phenyl] fluorene, etc.); in the formula (1), m1 and m But ^{1, R 2a} and ^{R 2b} is an aryl ^{group, R 4a} and ^{R 4b} are hydrogen atoms 9,9-bis [(3-oxetanyl) methoxy - aryl phenyl] fluorene (e.g., 9,9-bis [4- (9,9-bis [(3-oxetanyl) methoxy-C _6-10 arylphenyl] fluorene and the like such as (3-oxetanyl) methoxy) -3-phenylphenyl] fluorene); in the formula (1), m1 and 9,9-bis [(3-alkyl-3-oxetanyl) methoxy-arylphenyl] fluorene (for example, 9,9), wherein m2 is 1, R ^2a and R ^2b are aryl groups, and R ^4a and R ^4b are alkyl groups. -Bis [4-((3-methyl-3-oxetanyl) methoxy) -3-phenylphenyl] fluorene, 9,9-bis [4-((3-ethyl 3-oxetanyl) methoxy) -3-phenylphenyl] fluorene such as 9,9-bis _{[(3-C 1-6} alkyl-3-oxetanyl) such as methoxy _{-C 6-10} aryl phenyl] fluorene), etc.}; (A1-2) In the formula (1), n1 and n2 are 1 or more [eg, 1 to 20, preferably 2 to 10 (eg, 3 to 8), more preferably about 4 to 7], 9-bis [(3-oxetanyl) methoxy (poly) alkoxy-phenyl] fluorenes (ie, compounds in which n1 and n2 are 1 or more corresponding to the compounds exemplified in the above (A1-1)) {for example, In formula (1), 9,9-bis [(3-oxetanyl) methoxy (poly) alkoxy-phenyl] fluorene (for example, in which m1 and m2 are 0, and R ^4a and R ^4b are hydrogen atoms) 9,9-bis [4- (2-((3-oxetanyl) methoxy) ethoxy) -phenyl] fluorene, 9,9-bis [4- (2-((3-oxetanyl) methoxy) propoxy)- 9,9-bis [(3-oxetanyl) methoxy (mono) such as phenyl] fluorene, 9,9-bis [4- (2- (2-((3-oxetanyl) methoxy) ethoxy) ethoxy) -phenyl] fluorene to _{icosa) C 2-6} alkoxy - phenyl] fluorene, etc.); in the formula (1), m1 and m2 are ^{0, R 4a} and ^{R 4b} is an alkyl group of 9,9-bis [(3-alkyl -3 -Oxetanyl) methoxy (poly) alkoxy-phenyl] fluorene (eg, 9,9-bis [4- (2-((3-methyl-3-oxetanyl) methoxy) ethoxy)- Eniru] fluorene, 9,9-bis [4- (2- (2 - ((3-ethyl-3-oxetanyl) methoxy) ethoxy) ethoxy) - phenyl] fluorene such as 9,9-bis [(3-C _{1-6-alkyl-3-oxetanyl)} methoxy (mono- to _{icosa) C 2-6} alkoxy - phenyl] fluorene, etc.); the formula (1), m1 and m2 are 1 or ^{2, R 2a} and ^{R 2b} is an alkyl group , R ^4a and R ^4b are hydrogen atoms 9,9-bis [(3-oxetanyl) methoxy (poly) alkoxy- (mono or di) alkylphenyl] fluorene (eg, 9,9-bis [4- (2 -((3-Oxetanyl) methoxy) ethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (2-((3-oxetanyl) methoxy) eth) ) Ethoxy) -3,5-dimethylphenyl] fluorene such as 9,9-bis [(3-oxetanyl) methoxy (mono- to _{icosa) C 2-6} alkoxy - (mono or _{di) C 1-6} alkyl phenyl] 9,9-bis [(3-alkyl-3) wherein m1 and m2 are 1 or 2, R ^2a and R ^2b are alkyl groups, and R ^4a and R ^4b are alkyl groups; -Oxetanyl) methoxy (poly) alkoxy- (mono or di) alkylphenyl] fluorene (eg, 9,9-bis [4- (2-((3-methyl-3-oxetanyl) methoxy) ethoxy) -3-methyl Phenyl] fluorene, 9,9-bis [4- (2- (2-((3-ethyl-3-oxetanyl) methoxy) ethoxy) ethoxy) -3,5-dimethylphenol Sulfonyl] fluorene such as 9,9-bis _{[(3-C 1-6} alkyl-3-oxetanyl) methoxy (mono- to _{icosa) C 2-6} alkoxy - (mono or _{di) C 1-6} alkyl phenyl] fluorene In the above formula (1), 9,9-bis [(3-oxetanyl) methoxy (poly) alkoxy in which m1 and m2 are 1, R ^2a and R ^2b are aryl groups, and R ^4a and R ^4b are hydrogen atoms 9,9-bis [(3-oxetanyl) methoxy such as 9,9-bis [4- (2-((3-oxetanyl) methoxy) ethoxy) -3-phenylphenyl] fluorene (Mono to icosa) C _2-6 alkoxy-C _6-10 arylphenyl] fluorene etc.); In the above formula (1), m1 and m2 are 1, R ² 9,9-bis [(3-alkyl-3-oxetanyl) methoxy (poly) alkoxy-arylphenyl] fluorene (for example, 9,9-), wherein ^a and R ^2b are aryl groups, and R ^4a and R ^4b are alkyl groups Bis [4- (2-((3-methyl-3-oxetanyl) methoxy) ethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2- (2-((3-ethyl-3 9,9-bis [(3-C _1-6 alkyl-3-oxetanyl) methoxy (mono to icosa) C _2-6 alkoxy-C such as -oxetanyl) methoxy) ethoxy) ethoxy) -3-phenylphenyl] fluorene _6-10 arylphenyl] fluorene and the like} and the like.

(A2) Specific examples of bisnaphthylfluorenes include, for example, (A2-1) 9,9-bis [(3-oxetanyl) methoxy-naphthyl] fluorene in which n1 and n2 are 0 in the formula (1) Class {e.g., 9,9-bis [(3-oxetanyl) methoxy-naphthyl] fluorene (e.g., 9,9- in which m1 and m2 are 0 and ^R4a and ^R4b are hydrogen atoms in the formula (1) In the above formula (1), bis [6-((3-oxetanyl) methoxy) -2-naphthyl] fluorene, 9,9-bis [5-((3-oxetanyl) methoxy) -1-naphthyl] fluorene, etc.); , m1 and m2 are ^{0, R 4a} and ^{R 4b} is an alkyl group of 9,9-bis [(3-alkyl-3-oxetanyl) methoxy - naphthyl] fluorene (e.g., 9,9 [6-((3-methyl-3-oxetanyl) methoxy) -2-naphthyl] fluorene, 9,9-bis [6-((3-ethyl-3-oxetanyl) methoxy) -2-naphthyl] fluorene, 9,9-bis [5-((3-methyl-3-oxetanyl) methoxy) -1-naphthyl] fluorene, 9,9-bis [5-((3-ethyl-3-oxetanyl) methoxy) -1- 9,9-bis [(3-C _1-6 alkyl-3-oxetanyl) methoxy-naphthyl] fluorene, etc.) such as naphthyl] fluorene); (A2-2) In the formula (1), n1 and n2 are 1 or more [For example, 9,9-bis [(3-oxetanyl) methoxy (poly) alkoxy-naphthyl] ful which is 1 to 20, preferably 2 to 10 (for example, about 3 to 8 and more preferably about 4 to 7)] Len acids (i.e., the (compound corresponding to exemplified compounds n1 and n2 is 1 or more A2-1)) {e.g., in the formula (1), m1 and m2 are ^{0, R 4a} and ^{R 4b} Is a hydrogen atom 9,9-bis [(3-oxetanyl) methoxy (poly) alkoxy-naphthyl] fluorene (eg, 9,9-bis [6- (2-((3-oxetanyl) methoxy) ethoxy)- 2-naphthyl] fluorene, 9,9-bis [6- (2-((3-oxetanyl) methoxy) propoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2- (2-(( 9, such as 3-oxetanyl) methoxy) ethoxy) ethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-((3-oxetanyl) methoxy) ethoxy) -1-naphthyl] fluorene - bis [(3-oxetanyl) methoxy (mono- to _{icosa) C 2-6} alkoxy - naphthyl] fluorene, etc.); in the formula (1), m1 and m2 are ^{0, R 4a} and ^{R 4b} is an alkyl group 9 , 9-bis [(3-alkyl-3-oxetanyl) methoxy (poly) alkoxy-naphthyl] fluorene (eg, 9,9-bis [6- (2-((3-methyl-3-oxetanyl) methoxy) ethoxy) ) -2-naphthyl] fluorene, 9,9-bis [6- (2-((3-methyl-3-oxetanyl) methoxy) propoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2 -((3-Ethyl-3-oxetanyl) methoxy) ethoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2- (2-((3-methyl-3-oxetanyl) 9,9, such as) methoxy) ethoxy) ethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-((3-methyl-3-oxetanyl) methoxy) ethoxy) -1-naphthyl] fluorene -Bis [(3-C _1-6 alkyl-3-oxetanyl) methoxy (mono to icosa) C _2-6 alkoxy-naphthyl] fluorene etc.) etc.}.

  In addition, in the compound of the said illustration, the compound whose k1 and k2 in the said Formula (1) are one or more is also included. In the present specification and claims, “(poly) alkoxy” is used to mean including both an alkoxy group and a polyalkoxy group.

These first cationic polymerizable compounds represented by the formula (1) can be used alone or in combination of two or more. Preferred examples of the first cationically polymerizable compound include (A1) 9 such as bisphenylfluorenes [for example, 9,9-bis [4-((3-methyl-3-oxetanyl) methoxy) -phenyl] fluorene. , 9-bis _{[(3-C 1-4} alkyl-3-oxetanyl) methoxy - phenyl] fluorene; 9,9-bis [4- (2 - ((3-methyl-3-oxetanyl) methoxy) ethoxy) - 9,9-bis [(3-C _1-4 alkyl-3-oxetanyl) methoxy (mono to deca) C _2-4 alkoxy-phenyl] fluorene, etc.] such as phenyl] fluorene; (A2) bisnaphthylfluorenes, etc. Among them, in order to increase the refractive index and solubility in a solvent, (A2) bisnaphthylfluorenes [for example, 9,9-bis _{(3-C 1-4} alkyl-3-oxetanyl) methoxy - naphthyl] such as fluorene (A2-1) 9,9-bis [(3-oxetanyl) methoxy - naphthyl] fluorenes; 9,9-bis [( _{3-C 1-4} alkyl-3-oxetanyl) methoxy (mono- to _{deca) C 2-6} alkoxy - naphthyl] fluorene such as (A2-2) 9,9-bis [(3-oxetanyl) methoxy (poly) alkoxy -Naphthyl] fluorenes, etc.] are preferred, especially 9,9-bis [(3-C, such as 9,9-bis [6-((3-methyl-3-oxetanyl) methoxy) -2-naphthyl] fluorene. _1-2 alkyl-3-oxetanyl) methoxy-naphthyl] fluorene is preferred.

  These first cationically polymerizable compounds may be commercially available products, or may be prepared by conventional methods (for example, the method described in JP-A-2000-336082). As a typical method, for example, a method of preparing a compound represented by the following formula (1A) and a compound represented by the following formula (1B) may be used.

(In the formula, Ar ¹ and Ar ² , Z ¹ and Z ² , R ^1a and R ^1b , R ^2a and R ^2b , R ^3a and R ^3b , k1 and k2, m1 and m2, and n1 and n2 are preferable embodiments, respectively. The same as the above formula (1)).

(In the formula, X represents a halogen atom, and R ⁴ represents a hydrogen atom or a substituent).

Specifically, as the compound represented by the formula (1A), for example, the (3-oxetanyl) methyl group or (3- Alkyl-3-oxetanyl) methyl group substituted with a hydrogen atom, and the like. As the compound represented by the formula (1A), a commercially available product may be used, and a conventional method [for example, a fluorenone compound (including benzofluorenone or dibenzofluorenone) corresponding to rings Ar ¹ and Ar ² , A method of reacting phenol or alcohol corresponding to Z ¹ and Z ² in the presence of an acid catalyst such as sulfuric acid or a co-catalyst such as β-mercaptopropionic acid may be prepared.

In the formula (1B), the hydrogen atom or substituent represented by R ⁴ is the same as R ^4a and R ^4b in the formula (1), including preferred embodiments.

  In the formula (1B), examples of the halogen atom represented by X include chlorine, bromine, iodine and the like, and chlorine is preferable.

Specific examples of the compound represented by the formula (1B) include 3-halomethyl-oxetane such as 3-chloromethyl-oxetane; 3-chloromethyl-3-methyloxetane, 3-chloromethyl-3-ethyl. And 3-halomethyl-3-C _1-6 alkyloxetane such as oxetane. Among these compounds represented by the formula (1B), 3-halomethyl-3-C _1-4 alkyloxetane (in particular, 3-halomethyl-3-C _{1- 1} such as 3-chloromethyl-3-methyloxetane). _2- alkyl oxetane etc.) are preferred. A commercial item etc. can be used for the compound represented by said Formula (1B).

  The proportion of the compound represented by the formula (1B) is, for example, 0.5 to 10 mol, preferably 1 to 5 mol (for example, 1 mol) relative to 1 mol of the hydroxyl group of the compound represented by the formula (1A). 1 to 2 mol), more preferably about 1.05 to 1.5 mol (for example, 1.1 to 1.3 mol).

  The reaction may be performed in the presence of an alkali metal or an alkali metal compound. Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium and the like. Examples of the alkali metal compound include alkali metal hydrides (sodium hydride, potassium hydride, etc.); alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.); alkali metal carbonates (eg, sodium carbonate, carbonic acid, etc.) Potassium etc.).

  These alkali metals or alkali metal compounds can be used alone or in combination of two or more. Of these alkali metals or alkali metal compounds, alkali metal carbonates such as potassium carbonate are preferred. The ratio of the alkali metal or the alkali metal compound is, for example, 1 to 2 mol, preferably 1.1 to 1.5 mol, more preferably 1 mol with respect to 1 mol of the hydroxyl group of the compound represented by the formula (1A). About 1.2-1.4 mol may be sufficient.

The reaction may be performed in the presence of a phase transfer catalyst. Examples of the phase transfer catalyst include organic ammonium halides such as tetraalkylammonium halides (for example, tetra C _1-8 alkylammonium halides such as tetramethylammonium bromide and tetrabutylammonium bromide). These phase transfer catalysts may be used alone or in combination of two or more. Of these phase transfer catalysts, tetra _C1-4 alkyl ammonium halides such as tetramethyl ammonium bromide are preferred. The ratio of the phase transfer catalyst is, for example, 0.001 to 1 mol, preferably 0.01 to 0.1 mol, more preferably 0, relative to 1 mol of the hydroxyl group of the compound represented by the formula (1A). It may be about .02 to 0.05 mol.

  The reaction may be performed in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons (toluene, xylene, etc.); ethers (chain ethers such as dibutyl ether, cyclic ethers such as tetrahydrofuran, dioxane, etc.); amides (N, N-dimethylformamide) (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone and the like); Sulfoxides (dimethylsulfoxide (DMSO) and the like); Water and the like. These solvents can be used alone or in combination of two or more. Of these solvents, aromatic hydrocarbons such as toluene, cyclic ethers such as dioxane, amides such as DMF, and the like may be used. The proportion of the solvent is, for example, about 100 to 1000 parts by weight, preferably about 200 to 800 parts by weight, and more preferably about 400 to 600 parts by weight with respect to 100 parts by weight of the compound represented by the formula (1A). Also good.

  The reaction may be performed in the presence of a reaction accelerator. Examples of the reaction accelerator include alkali metal iodides such as potassium iodide. The ratio of the reaction accelerator is, for example, 0.01 to 0.1 mol, preferably 0.02 to 0.08 mol, more preferably, relative to 1 mol of the hydroxyl group of the compound represented by the formula (1A). May be about 0.04 to 0.06 mol.

  The reaction may be performed in air or in an inert gas (for example, nitrogen; a rare gas such as argon or helium). The reaction may be performed under normal pressure, increased pressure, or reduced pressure. The reaction temperature may be, for example, about 50 to 150 ° C, preferably about 70 to 120 ° C. The reaction time is not particularly limited, and may be, for example, 1 to 12 hours, preferably about 5 to 7 hours. After completion of the reaction, the reaction product is separated and purified by conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, or a combination of these. May be.

(Second cationically polymerizable compound)
The cationically polymerizable compound may contain a second cationically polymerizable compound represented by the following formula (2) as necessary from the viewpoint of easily improving the insolubilization rate.

(In the formula, Ar ³ and Ar ⁴ and Z ³ and Z ⁴ are each an arene ring, R ^5a and R ^5b , R ^6a and R ^6b are each a substituent, and R ^7a and R ^7b are each linear or branched. An alkylene group, R ^8a and R ^8b are each a hydrogen atom or a methyl group, p1 and p2, q1 and q2, and r1 and r2 are each an integer of 0 or more, and s1 and s2 are each an integer of 1 to 4.

In the formula (2), Ar ³ and Ar ⁴ , Z ³ and Z ⁴ , R ^5a and R ^5b , R ^6a and R ^6b , R ^7a and R ^7b , p1 and p2, q1 and q2, and r1 and r2 are: Corresponds to Ar ¹ and Ar ² , Z ¹ and Z ² , R ^1a and R ^1b , R ^2a and R ^2b , R ^3a and R ^3b , k1 and k2, m1 and m2, and n1 and n2 in the formula (1), respectively. It may be the same, including preferred embodiments such as the type of ring or group, the bonding position, and the numerical range.

In the formula (2), R ^8a and R ^8b are preferably hydrogen atoms. The types of R ^8a and R ^8b may be different from each other but are usually the same.

  In the formula (2), s1 and s2 may be, for example, an integer of 1 to 3, preferably 1 or 2, and more preferably 1. In the present invention, even if s1 and s2 are small (or even if the number of polymerizable functional groups is small), the insolubilization rate can be effectively improved.

  Further, the total number of oxyalkylene groups in one molecule of the compound represented by the formula (2) (total addition number) [may be simply referred to as r1 × s1 + r2 × s2] depends on the values of s1 and s2. For example, it can be selected from an integer range of about 0 to 60, for example, an integer of about 0 to 40 (for example, 2 to 30), preferably an integer of about 0 to 20 (for example, 4 to 16), Preferably, it may be an integer of about 0 to 12 (for example, 6 to 10), particularly an integer of about 0 to 4 (for example, 0 to 2, particularly 0).

As the second cationically polymerizable compound represented by the formula (2), specifically, for example, (3-oxetanyl) of the compound exemplified as the first cationically polymerizable compound represented by the formula (1). And a diglycidyl compound in which a methyl group or a (3-alkyl-3-oxetanyl) methyl group is substituted with a glycidyl group. These second cationically polymerizable compounds can be used alone or in combination of two or more. Among the second cationic polymerizable compounds, 9,9-bis (glycidyloxynaphthyl) fluorene; 9,9-bis [glycidyloxy (poly) alkoxy from the viewpoint of easily increasing the refractive index of the curable composition and the cured product. naphthyl] fluorene (e.g., 9,9-bis [6- (2-glycidyloxyethoxy) -2-naphthyl] fluorene such as 9,9-bis [glycidyloxy (mono- to _{deca) C 2-4} alkoxy-naphthyl] fluorene And the like, and 9,9-bis (glycidyloxynaphthyl) fluorene such as 9,9-bis [6-glycidyloxy-2-naphthyl] fluorene is particularly preferable.

  As the second cationically polymerizable compound represented by the formula (2), a commercially available product may be used, and a conventional method [for example, a method described in JP2012-102228A, that is, the formula ( 2) a dihydroxy compound corresponding to the compound represented by 2) (compound represented by the formula (1A)) and epichlorohydrin in the presence of a base such as sodium hydroxide]. May be.

  The ratio of the first cation polymerizable compound and the second cation polymerizable compound can be selected from the range of the former / the latter (weight ratio) = 50/50 to 99/1, for example, 70/30 to It may be 97/3, preferably 80/20 to 95/5, and more preferably about 85/15 to 95/5.

  The cationic polymerizable compound is not necessarily required, but may contain other cationic polymerizable compounds that do not belong to the first and second cationic polymerizable compounds (also simply referred to as third cationic polymerizable compounds). Good. Examples of the third cationically polymerizable compound include oxetane ring-containing compounds (for example, monofunctional oxetane compounds such as (3-ethyl-3-oxetanyl) methanol; p-bis [(3-ethyl-3-oxetanyl)) Multifunctional oxetane compounds such as methoxymethyl] benzene); conventional epoxy resins (for example, glycidyl ether type epoxy resins such as bisphenol type epoxy resins; glycidyl ester type epoxy resins; glycidyl amine type epoxy resins; alicyclic epoxy resins) Vinyl ether group-containing compounds (for example, 9,9-bis [4- (2-vinyloxyethoxy) phenyl] fluorene, 9,9-bis [6- (2-vinyloxyethoxy) -2-naphthyl] fluorene) 9,9-bis [vinyloxy (poly) alkoxy Aryl] fluorene; 9,9-bis [4- (2-vinyloxyethoxy) -2-methylphenyl] fluorene, 9,9-bis [4- (2-vinyloxyethoxy) -3-methylphenyl] fluorene, etc. 9,9-bis [vinyloxy (poly) alkoxy- (mono or di) alkylphenyl] fluorene etc.) and the like.

  The ratio of the total amount of the first cation polymerizable compound and the second cation polymerizable compound is, for example, in the range of about 10% by weight or more (for example, 30 to 100% by weight) with respect to the whole cation polymerizable compound. For example, 50% by weight or more (for example, 50 to 99% by weight), preferably 70% by weight or more (for example, 70 to 97% by weight), more preferably 90% by weight or more (for example, 90 to 95% by weight). ) Or about 100% by weight (embodiment not including the third cationic polymerizable compound).

[Polysilane]
The polysilane is not particularly limited as long as it is a linear, cyclic, branched, or network compound having a Si—Si bond, but is usually a structural unit represented by the following formulas (3a) and (3b) Of these, it is often composed of polysilane having at least one structural unit.

(In formula, R < ⁹ > -R < ¹¹ > is the same or different, and shows a hydrogen atom, a hydroxyl group, an organic group, or a silyl group).

In the formulas (3a) and (3b), examples of the organic group represented by R ^{9 to} R ¹¹ include a hydrocarbon group (an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group). ), Ether groups (alkoxy groups, cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, etc.) corresponding to these hydrocarbon groups. Usually, the organic group is often a hydrocarbon group such as an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Also, hydrogen atoms, hydroxyl groups, alkoxy groups, silyl groups, etc. are often substituted at the ends.

Examples of the alkyl group include a C _1-14 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a pentyl group, and a hexyl group (preferably a C _1-10 alkyl group, more preferably _{C 1-6} alkyl groups).

Examples of the alkoxy group include C _1-14 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a t-butoxy group, and a pentyloxy group.

Examples of the alkenyl group include C _2-14 alkenyl groups such as a vinyl group, an allyl group, a butenyl group, and a pentenyl group.

Examples of the cycloalkyl group include C _5-14 cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a methylcyclohexyl group. _{Examples of the} cycloalkyloxy group include C _5-14 cycloalkyloxy groups such as a cyclopentyloxy group and a cyclohexyloxy group. Examples of the cycloalkenyl group include C _5-14 cycloalkenyl groups such as a cyclopentenyl group and a cyclohexenyl group.

As the aryl group, a C _6-20 aryl group such as a phenyl group, a methylphenyl group (tolyl group), a dimethylphenyl group (xylyl group), a naphthyl group (preferably a C _6-15 aryl group, more preferably a C _{6-6 12} aryl group) and the like. Examples of the aryloxy group include C _6-20 aryloxy groups such as a phenoxy group and a naphthyloxy group. Examples of the aralkyl group include C _6-20 aryl-C _1-4 alkyl groups such as benzyl group, phenethyl group, and phenylpropyl group. Examples of the aralkyloxy group include C _6-20 aryl-C _1-4 alkyloxy groups such as benzyloxy group, phenethyloxy group, and phenylpropyloxy group.

Examples of the silyl group include Si _1-10 silanyl groups (preferably Si _1-6 silanyl groups) such as silyl group, disilanyl group, and trisilanyl group.

Also, R ⁹ to R ¹¹ are, the organic group (alkyl group, aryl group, etc.) when it is or silyl group, at least one of its hydrogen atoms, optionally substituted by a substituent (or functional group) Good. Such a substituent (or functional group) may be the same as the above exemplified groups such as a hydroxyl group, an alkyl group, an aryl group, and an alkoxy group.

Among these, R ^{9 to} R ¹¹ are often an alkyl group (eg, a C _1-4 alkyl group such as a methyl group), an aryl group (eg, a C _6-20 aryl group such as a phenyl group), or the like. .

  When the polysilane has an acyclic structure (chain (straight chain, branched chain), network), the terminal group (terminal substituent) is usually a hydrogen atom, a hydroxyl group, a halogen atom (chlorine atom, etc.), alkyl It may be a group, an aryl group, an alkoxy group, a silyl group, or the like. Of these, hydroxyl group, methyl group, and phenyl group are often used. Among them, phenyl group and methyl group are preferable because they can improve photocurability without trapping the acid generated from the photoacid generator. Preferably, the end group may be a trimethylsilyl group.

  Specific examples of the polysilane include, for example, a linear or cyclic polysilane having a structural unit represented by the formula (3a), a polysilane having a structural unit represented by the formula (3b) (branched or network-like). Polysilane) and polysilane (branched or network polysilane) having a combination of the structural units represented by the formulas (3a) and (3b). In these polysilanes, the structural units represented by the formulas (3a) and (3b) may be used alone or in combination of two or more. The branched or network polysilane may further contain a structural unit represented by the following formula (3c).

  Typical polysilanes include linear or cyclic polysilanes such as polydialkylsilanes [eg polydimethylsilane, polymethylpropylsilane, polymethylbutylsilane, polymethylpentylsilane, polydibutylsilane, polydihexylsilane, dimethylsilane. -Methylhexylsilane copolymer, etc.]; polyalkylarylsilane [for example, polymethylphenylsilane, methylphenylsilane-phenylhexylsilane copolymer, etc.]; polydiarylsilane (for example, polydiphenylsilane, etc.); dialkylsilane- Alkylarylsilane copolymers (eg, dimethylsilane-methylphenylsilane copolymer, dimethylsilane-phenylhexylsilane copolymer, dimethylsilane-methylnaphthylsilane copolymer), etc. And the like. These polysilanes can be used alone or in combination of two or more.

Among these, R ⁹ is an aryl group (particularly a C _6-20 aryl group) and R ¹⁰ is an aryl group (particularly a C _6-6 ) from the viewpoint that the stability of the cured product can be improved without inhibiting cationic polymerization. ₂₀ aryl group) or an alkyl group (especially a C _1-6 alkyl group) having a structural unit (3a) (especially a chain or cyclic polysilane), for example, a poly C _1-6 alkyl C _6-20 arylsilane ( For example, poly C _1-3 alkyl C _6-10 aryl silane) and polydi C _6-20 aryl silane (for example, polydi C _6-10 aryl silane) are preferable. Furthermore, chain polyalkylaryl silane (for example, chain poly C _1-6 alkyl C _6-14 aryl silane, etc.) and cyclic diaryl silane are preferable from the viewpoint of compatibility with a cationically polymerizable compound. Polyalkylaryl silanes (particularly chained poly C _1-3 alkyl C _6-10 aryl silanes such as polymethylphenylsilane) are preferred.

  The polysilane used in the present invention is preferably a polysilane in which at least one hydroxyl group is directly bonded to the terminal silicon atom of the polysilane, that is, a polysilane having at least one silanol group (hydroxyl group) at the terminal. The hydroxyl group directly bonded to the silicon atom exhibits good reactivity with the oxetanyl group (and epoxy group) of the cationic polymerizable compound, and is highly enhanced between the cationic polymerizable compound and the polysilane by ultraviolet light irradiation and / or heating. A cross-linked structure is formed. The hydroxyl group content is, for example, about 0.005-2.5 on average per silicon atom, preferably about 0.01-1 on average, more preferably 0.05-0.5 on average. Degree. If the content ratio of the silanol group (hydroxyl group) is too large, there is a possibility that the acid polymerization by the photoacid generator is trapped or the cationic polymerization is inhibited.

  The average degree of polymerization of the polysilane is, for example, 2 to 200 (for example, 4 to 150), preferably 8 to 100 (10 to 50) in terms of silicon atoms (that is, the average number of silicon atoms per molecule). Preferably, it may be about 12-30 (especially 15-20). The number average molecular weight Mn of polysilane is, for example, 100 to 50,000 (for example, 200 to 30,000), preferably 300 to 10,000, more preferably 400 to 8,000 (for example, 500 to 5,000) in the measurement method by GPC (polystyrene conversion). The degree may be sufficient and it may be about 700-4000 (for example, 1000-3000) normally. In the measuring method by GPC (polystyrene conversion), the weight average molecular weight Mw of polysilane is 1000-100000 (for example, 3000-50000), Preferably it is 5000-30000, More preferably, it is 7000-20000 (for example, 9000-15000). It may be a degree. If the degree of polymerization and the molecular weight are too small, the reactivity in the curable composition and the refractive index, heat resistance and water repellency of the cured product may be reduced. If the degree of polymerization and the molecular weight are too large, the mechanical properties of the cured product may be reduced. There is a risk that the characteristics will deteriorate.

  The polysilane may be solid or liquid at room temperature (for example, about 15 to 25 ° C.). For example, the polysilane may be solid from the viewpoint of handleability and is uniform in the composition. Liquid polysilane may be used from the viewpoint of easy dispersion.

  The ratio of the cationic polymerizable compound (for example, the total amount of the first and second cationic polymerizable compounds) and the polysilane is, for example, the wide range of the former / the latter (weight ratio) = 99/1 to 10/90. For example, 90 / 10-20 / 80 (eg 80 / 20-25 / 75), preferably 70 / 30-30 / 70 (eg 65 / 35-35 / 65), more preferably 60 It may be about / 40 to 40/60 (for example, 55/45 to 45/55). If the proportion of polysilane is too small, the cured product may have a high refractive index, heat resistance and water repellency may be reduced, and if too large, the mechanical properties of the cured product may be reduced.

[Other ingredients]
(Photoacid generator)
The curable composition of the present invention often contains a photoacid generator as a polymerization initiator. As the photoacid generator, conventional photoacid generators, for example, imidyl sulfonate compounds, thioxanthone oxime ester compounds, onium salts, metallocene complexes, sulfonimide compounds, disulfone compounds, sulfonate ester compounds, triazine compounds, quinonediazide compounds, Although it may be a diazomethane compound, it is preferably a photoacid generator that absorbs visible light and generates an acid from the viewpoint of suppressing decomposition or deterioration of polysilane by light irradiation.

  Examples of the photoacid generator that generates an acid by absorbing visible light include phenylthiophenes [for example, bis (4-methylphenyl) (5-phenyl-thiophen-2-yl) sulfonium hexafluorophosphate, etc. Phenylthiophenesulfonium salts, etc.]; dioxolophenyltriazines [eg, dioxolophenyl-bis (haloalkyl) -triazines such as 2-dioxolophenyl-4,6-bis (trichloromethyl) -triazine] Benzothiophenes [e.g. benzothiophene sulfonium salts such as bis (4-n-butoxyphenyl) (benzothiophen-2-yl) sulfonium hexafluorophosphate]; thianthrenes [e.g. N-trifluoromethanesulfonyloxy -7-t-butylthianthrene N-haloalkanesulfonyloxy-thiantylene dicarboxylic acid imide such as 2,3-dicarboxylic acid imide; 7-t-butyl-5- (4-methoxyphenyl) thiantrenium-2,3-dicarboxylic acid imide trifluoromethanesulfone Acid salt, 7-t-butyl-5- (4-methoxyphenyl) thiantrenium-2,3-dicarboxylic acid imide, thiantrenium dicarboxylic acid imide salt such as hexafluorophosphate, etc.]; phenoxazines; Satiins; and phenothiazines.

  Of these photoacid generators, from the viewpoint of photocurability and the like, thianthrenes conjugated (condensed) with an imide ring are preferable, and a photoacid generator represented by the following formula (4) is particularly preferable.

(Wherein R ¹² represents a fluorohydrocarbon group, and R ¹³ represents an alkyl group).

In the formula (4), examples of the fluorohydrocarbon group of R ¹² include a perfluoro C _1-4 alkyl group such as a trifluoromethyl group, a pentafluoroethyl group, and a nonafluorobutyl group, and a pentafluorophenyl group. Perfluoro C _6-14 aryl group, and the like. Of these fluorohydrocarbon groups, perfluoro C _1-2 alkyl groups (particularly trifluoromethyl groups) are preferred.

Examples of the substituent R ¹³ include C _1-10 alkyl groups such as a methyl group, an ethyl group, an n-butyl group, and a t-butyl group. Among these alkyl groups, a C _1-4 alkyl group such as a methyl group or a t-butyl group is preferable, and a t-butyl group is particularly preferable. The substitution position of the substituent R ¹³ is preferably, for example, any position of 6-9-position, particularly preferably 7-position or 8-position.

Among the photoacid generators represented by formula (4), N-perfluoro such as N-trifluoromethanesulfonyloxy-7-t-butylthianthrene-2,3-dicarboxylic acid imide is used from the viewpoint of photocurability. C _1-2 alkylsulfonyloxy-C _1-4 alkylthianthrene-2,3-dicarboxylic imide is particularly preferred.

  The ratio of the photoacid generator can be selected from a range of about 0.1 to 30 parts by weight, for example, 0.3 to 20 parts by weight, preferably 1 with respect to 100 parts by weight of the total amount of the cationic polymerizable compound and polysilane. ˜15 parts by weight, more preferably about 2 to 10 parts by weight (particularly 3 to 8 parts by weight). If the ratio of the photoacid generator is too small, the crosslinking density cannot be improved and the strength of the cured product may be reduced. On the other hand, if the ratio of the photoacid generator is too large, the stability and coating properties of the composition may be reduced.

(solvent)
The photopolymerizable composition of the present invention may contain a solvent from the viewpoint of improving handleability and coating property. Examples of the solvent include hydrocarbons (hexane, cyclohexane, toluene, etc.); alcohols (ethanol, propanol, etc.); ethers [diethyl ether, tetrahydrofuran (THF), etc.]; ketones [ethyl methyl ketone (2-butanone). ), Cyclohexanone, etc.]; esters (ethyl acetate, butyl acetate, etc.); diols (ethylene glycol, propylene glycol, polyethylene glycol, etc.); cellosolves [methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether (dimethoxyethane), propylene glycol Monomethyl ether, etc.]; carbitols [carbitol, diethylene glycol dimethyl ether (diglyme), diethylene glycol methyl ethyl ether, etc.]; B cellosolve acetates (such as propylene glycol methyl acetate).

  These solvents can be used alone or in combination of two or more. Of these solvents, ethers, ketones, cellosolves, carbitols, cellosolve acetates and the like are preferable.

  The solvent may be used in an appropriate amount so as to obtain a coating solution viscosity suitable for coating. As a ratio of a typical solvent, for example, 100 to 10,000 parts by weight, preferably 200 to 1000 parts by weight, and more preferably about 300 to 500 parts by weight with respect to 100 parts by weight of the total amount of the cationically polymerizable compound and polysilane. There may be.

(Other additives)
The curable composition of the present invention may further contain other conventional additives. Examples of other additives include sensitizers (coumarins, quinolines, quinones, phenoxazines, aromatic hydrocarbons (pyrenes, etc.), amines, etc.), reactive polymers (phenolic resins, etc.) Polymers with reactive groups for oxetanyl groups (and / or epoxy groups), colorants (dyeing pigments), thickeners, stabilizers (anti-aging agents, antioxidants, ozone degradation inhibitors, etc.), Examples include foaming agents, leveling agents, dispersants, flame retardants, antistatic agents, fillers, and lubricants. These additives can be used alone or in combination of two or more. The proportion of these additives can be appropriately selected according to the type of the additive. For example, it is 100 parts by weight or less (for example, 0.1 to 50 parts by weight), preferably 100 parts by weight with respect to the cationically polymerizable compound. Is about 0.3 to 30 parts by weight, more preferably about 0.5 to 20 parts by weight.

  The curable composition contains a cationically polymerizable compound, polysilane, and other components (a photoacid generator, a conventional additive, etc.) as necessary, and is dissolved and dispersed in a solvent or a dispersant as necessary. And by mixing uniformly by mixing or the like.

[Hardened product and production method thereof]
In the present invention, a cured product (three-dimensional cured product, cured film or cured pattern) is produced by a production method including a photocuring step of irradiating the curable composition with light (eg, visible light) to form a photocured product. Or the like may be produced.

  In the photocuring step, a photocured product (photocured film, photocured pattern, etc.) is applied with the curable composition on a substrate to form a coating film, and then irradiated with light (for example, visible light) ( You may form by exposing. Therefore, you may use a curable composition for manufacture of the coating film (thin film) on a base material, for example. When a curable composition is applied to a substrate to produce a coating film, a curable composition containing a solvent (a solution in which a cationic polymerizable compound, polysilane, a photoacid generator, or the like is dissolved or dispersed in the solvent or Dispersion) may be applied to the substrate.

  Examples of the coating method include a flow coating method, a spin coating method, a spray coating method, a screen printing method, a casting method, a bar coating method, a curtain coating method, a roll coating method, a gravure coating method, a dipping method, and a slit method. It is done.

  The thickness of a coating film can be normally selected from the range of about 0.01 micrometer-10 mm according to the use of hardened | cured material. In the case of a photoresist, the thickness of the coating film is usually about 0.05 to 10 μm, for example, about 0.1 to 5 μm. In the case of a printed wiring board, the thickness of the coating film is usually about 10 μm to 5 mm, for example, about 100 μm to 1 mm. In the case of an optical thin film, the thickness of the coating film is usually about 0.1 to 100 μm, for example, about 0.3 to 50 μm.

  The wavelength of light may be appropriately selected according to the type of photoacid generator, and is preferably visible light from the viewpoint that decomposition or degradation of polysilane can be suppressed. The wavelength of visible light may be 380 to 780 nm. However, from the viewpoint of easily generating an acid and improving photocurability, for example, 380 to 600 nm, preferably 385 to 500 nm, more preferably 390 to 450 nm ( Particularly, h-line (405 nm) that can be irradiated with a high-pressure mercury lamp, LED laser, or the like is particularly preferable.

The light irradiation amount (exposure amount) can be selected from a range in which the curable composition can be cured according to the thickness of the coating film, and is, for example, 10 mJ / cm ² or more (for example, 10 to 10,000 mJ / cm ² ). it may also be, for example 100~5000mJ / cm ^2, preferably 500~3000mJ / cm ^2, more preferably 1000~2500mJ / cm ² may be (especially 1500~2000mJ / cm ²⁾ approximately. If the exposure amount is too small, the photocurability may be lowered.

  Examples of the light source include a high-pressure mercury lamp, a deuterium lamp, a halogen lamp, a metal halide lamp, a xenon lamp, and a laser beam (such as an LED laser).

  The curable composition may be used for forming a pattern or an image (production of a printed wiring board, etc.). When manufacturing a printed wiring board, a resin composition is apply | coated on a base material, a coating film may be formed, and the formed coating film may be irradiated with light (pattern exposure). The pattern exposure may be performed by laser-light scanning or may be performed by light irradiation through a photomask. A pattern or an image may be formed by developing (or dissolving) and removing a non-irradiated region (unexposed portion) generated by pattern exposure with a developer. Examples of the developer include water, an aqueous alkaline solution, a hydrophilic solvent (for example, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves and cellosolve acetates). Or a mixture thereof.

  In this invention, in order to further improve the intensity | strength of hardened | cured material, you may heat-process in addition to photocuring. In the photocuring step, the heat treatment may be performed by heating the curable composition together with light irradiation or by providing a heating step for heating the photocured product that has undergone the photocuring step. The polymerization reaction is accelerated by heating, and a high degree of three-dimensional crosslinking occurs, so that a high-strength cured product can be obtained. Among these, a method of providing a heating step is preferable from the viewpoint that the crosslinking strength and insolubilization rate of the cured product can be improved.

  In particular, when the curable composition is used for forming a pattern or an image, the coating film may be heated after pattern exposure. When the coating film is heated after pattern exposure, it may be heated after being developed, or may be developed after being heated. Higher crosslinking may be performed in the irradiation region (exposed portion) of the coating film remaining on the substrate by heating. By heating, a fine and highly accurate pattern can be formed on the substrate even for visible light. Therefore, you may use the curable composition of this invention for the use which requires a precise pattern, for example, manufacture of the printed wiring board of an electronic device, etc.

  The heating temperature may be, for example, about 80 to 200 ° C, preferably 110 to 180 ° C, more preferably about 140 to 160 ° C (particularly 145 to 155 ° C). The heating time may be, for example, about 5 seconds to 1 hour, preferably about 30 seconds to 20 minutes, more preferably about 1 to 10 minutes (particularly 3 to 8 minutes). In the present invention, a strong cured product can be formed even by irradiation with visible light.

  When forming an optical thin film, you may form two or more layers of a curable composition on a base material. Moreover, after forming another functional layer etc. on a base material, you may form the layer of a curable composition on the functional layer. Since the resin composition of the present invention is excellent in visible light transmittance, has a high refractive index, and is excellent in optical characteristics, it is particularly suitable for a high refractive index layer of an antireflection film such as a liquid crystal display, a reflector, etc. You may use for an optical thin film.

  The material of the base material is selected according to the application. For example, in the case of a printed wiring board or an optical thin film, a semiconductor (silicon, gallium arsenide, gallium nitride, silicon carbide, etc.), metal (aluminum, copper, etc.), ceramic (Zirconium oxide, titanium oxide, lead zirconate titanate (PZT), etc.), transparent inorganic materials (glass, quartz, magnesium fluoride, calcium fluoride, etc.), transparent resins (polymethyl methacrylate, polymethyl acrylate, polystyrene, polycarbonate) Etc.).

  The obtained cured product has excellent cross-linking strength, and the insolubilization rate with tetrahydrofuran (THF) may be 20% or more (for example, about 30 to 100%), for example, 50 to 100%, preferably 60 It is about -100% (for example, 65-99.9%), More preferably, it is about 70-100% (especially 75-99.9%) grade. In the present invention, the insolubilization rate can be calculated from the film thickness ratio before and after immersing in THF for 10 minutes, as in the method described in Examples described later. Although the cured product tends to become brittle when the insolubilization rate increases, the obtained cured product has unexpectedly excellent flexibility (or toughness). Therefore, the cured product of the present invention can achieve both a high insolubilization rate and flexibility.

  Moreover, since the curable composition and cured product of the present invention have a large difference in insolubilization ratio before and after light irradiation, they exhibit excellent contrast (developability) in pattern formation. Therefore, the insolubilization rate before light irradiation is, for example, 30% or less (for example, 0 to 20%), preferably 10% or less (for example, 0 to 5%), more preferably 1% or less (for example, substantially 0%). Further, the difference in the insolubilization rate before and after the light irradiation may be, for example, 30% or more (for example, 40 to 100%), preferably about 50% or more (for example, 60 to 99.9%).

  The obtained cured product has a high refractive index, and may be 1.6 or more (for example, about 1.62 to 1.8) at a temperature of 25 ° C. and a wavelength of 589 nm, for example, 1.64 to 1.77 (eg 1.65 to 1.75), preferably 1.66 to 1.74 (eg 1.67 to 1.73), more preferably 1.68 to 1.72 (particularly 1. 69 to 1.71).

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Various evaluation methods and raw materials used are shown below.

[Evaluation method]
(Insolubilization rate)
The cured products obtained in Examples and Comparative Examples were immersed in tetrahydrofuran (THF) at 20 ° C. for 10 minutes and then left to stand for 1 hour to dry, and the ratio of the average thickness of the cured product before and after immersion (after drying) (After immersion / before immersion) was calculated as the insolubilization rate. In addition, the average thickness of hardened | cured material was computed by the arithmetic average of the thickness measured in nine places using the non-contact-type film thickness measuring apparatus (Nanometrics Japan Co., Ltd. product "Nanospec / AFT M-3000").

(contrast)
The insolubilization rate was evaluated on the thin film before light irradiation (thin film formed by removing the solvent after application of the curable composition) formed in the examples and comparative examples, and the contrast (development) according to the following criteria. Sex).

○: Difference in insolubilization rate before and after light irradiation is 60% or more.

(Refractive index)
Using a multi-wavelength Abbe refractometer (manufactured by Atago Co., Ltd., “DR-M4”), the refraction at D line (wavelength 589 nm) of the cured products obtained in the examples and comparative examples under the condition of a temperature of 25 ° C. The rate nD was measured. For the measurement, an interference filter having a wavelength of 589 nm was used.

(Flexibility or toughness)
From the feeling of touching the cured products obtained in Examples and Comparative Examples with a finger, evaluation was performed according to the following criteria.

○: The film is soft and difficult to break. ×: The film is brittle.

[material]
(Cationically polymerizable compound)
BNFO: 9,9-bis [6- (3-methyl-3-oxetanyl) methoxy-2-naphthyl] fluorene, synthesized according to Synthesis Example 1 described later BPEF-9EO-O: 9,9-bis [4- (2 -Hydroxyethoxy) -phenyl] fluorene, an bis ((3-methyl-3-oxetanyl) methyl) ether adduct obtained by adding 9 mol of ethylene oxide on average, synthesized by Synthesis Example 2 described later BNFG: 9,9- Bis (6-glycidyloxy-2-naphthyl) fluorene, synthesized according to Synthesis Example 1 of JP2012-102228 BPFG: 9,9-bis (4-glycidyloxyphenyl) fluorene, JP2012-102228 Synthesis according to Synthesis Example 2 of the publication BCAFG: 9,9-bis (3,4-diglycidyloxy-phenyl) fluorene "BCAFG" manufactured by Osaka Gas Chemical Co., Ltd.
(Polysilane)
PMPS: Polymethylphenylsilane, “PMPS” manufactured by Osaka Gas Chemical Co., Ltd., number average molecular weight Mn = 2100, weight average molecular weight Mw = 11000, chain polysilane having a terminal hydroxyl group (photoacid generator)
SIN-11: N-trifluoromethanesulfonyloxy-7-t-butyl-thianthrene-2,3-dicarboxylic imide, “SIN-11” manufactured by Sanpo Chemical Laboratory
(solvent)
Cyclohexanone: manufactured by Nacalai Tesque.

[Synthesis Example 1]
9,9-bis (6-hydroxy-2-naphthyl) fluorene (BNF, Osaka Gas Chemical Co., Ltd., 91 g, 202 mmol) was dissolved in N, N-dimethylformamide (DMF, 455 g) and then potassium carbonate. (72.6 g, 525 mmol) and potassium iodide (KI, 3.35 g, 19.8 mmol) were added and stirred at 60 ° C. To this solution, 3-chloromethyl-3-methyloxetane (58.8 g, 487 mmol) was added dropwise at 60 ° C., and after completion of the addition, the temperature was raised to 80 ° C. and reacted for 5 hours, and further heated to 100 ° C. And reacted for 1 hour. After completion of the reaction, 1.4 L of water was added, and extraction with 300 g of ethyl acetate was performed three times. Subsequently, washing with 300 g of water was performed 6 times, and the obtained organic phase (ethyl acetate phase) was concentrated under reduced pressure to obtain 122 g (yield 97.6%) of the compound in the form of pale orange crystals. When the obtained compound was analyzed by ¹ H NMR, 9,9-bis [6- (3-methyl-3-oxetanyl) methoxy-2-naphthyl] fluorene (BNFO, a compound represented by the following formula (1a) )Met.

[Example 1]
In a sample tube, 45 parts by weight of BNFO, 5 parts by weight of BNFG, 50 parts by weight of PMPS, 360 parts by weight of cyclohexanone (solvent) and 5 parts by weight of SIN-11 as a photopolymerization initiator were stirred and mixed uniformly. The obtained mixed solution was spin-coated on a silicon substrate at 2000 rpm for 20 seconds, pre-baked on a hot plate at 60 ° C. for 2 minutes to remove the solvent, and a thin film having a thickness of 0.5 to 2.0 μm. Formed. The obtained thin film was irradiated with 1600 mJ / cm ² of visible light having a wavelength of 405 nm using an LED laser (“BP300” manufactured by Ball Semiconductor, 300 mW), and then heated at 150 ° C. for 5 minutes. The obtained cured product had a refractive index of 1.7027 and an insolubilization rate of 79%.

[Example 2]
A cured product was prepared in the same manner as in Example 1 except that 60.3 parts by weight of BNFO, 6.7 parts by weight of BNFG, 33 parts by weight of PMPS, 360 parts by weight of cyclohexanone and 5 parts by weight of SIN-11 were used. . The obtained cured product had a refractive index of 1.6983 and an insolubilization rate of 75%.

[Example 3]
A cured product was prepared in the same manner as in Example 1 except that 67.5 parts by weight of BNFO, 7.5 parts by weight of BNFG, 25 parts by weight of PMPS, 360 parts by weight of cyclohexanone and 5 parts by weight of SIN-11 were used. . The obtained cured product had a refractive index of 1.6817 and an insolubilization rate of 64%.

[Synthesis Example 2]
9,9-bis [4- (hydroxypolyethoxy) phenyl] fluorene (9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene adduct obtained by adding 9 mol of ethylene oxide on average, BPEF-9EO , Osaka Gas Chemical Co., 125 g, 150 mmol) was dissolved in dioxane (161 g) and toluene (40.6 g), then tetramethylammonium bromide (1.5 g, 9.75 mmol), 3-chloromethyl- 3-Methyloxetane (181 g, 1.5 mol) was mixed and dissolved at 70 ° C., then 30 g (750 mmol) of fine powdered sodium hydroxide was added dropwise over 13 minutes, and the mixture was stirred at 60 ° C. for 11 h. After completion of the reaction, methyl isobutyl ketone (MIBK, 370 g) was added, and extraction with 100 g of water was performed 6 times. The resulting organic phase (MIBK phase) was concentrated under reduced pressure to give 122 g (yield 81.3%) of the compound in the form of a brown gum. When the obtained compound was analyzed by ¹ H NMR, 9,9-bis [4- (3-methyl-3-oxetanyl) methoxypolyethoxy-phenyl] fluorene (BPEF-9EO-O, represented by the following formula (1b) Compound).

(In the formula, n1 + n2 represents 11 as an average value).

[Example 4]
Cured in the same manner as in Example 1 except that a mixed solution of 60.3 parts by weight of BPEF-9EO-O, 6.7 parts by weight of BNFG, 33 parts by weight of PMPS, 360 parts by weight of cyclohexanone and 5 parts by weight of SIN-11 was used. A product was prepared. The obtained cured product had a refractive index of 1.6698 and an insolubilization rate of 71%.

[Comparative Example 1]
A cured product was prepared in the same manner as in Example 1 except that a mixed solution of 67 parts by weight of BNFG, 33 parts by weight of PMPS, 360 parts by weight of cyclohexanone and 5 parts by weight of SIN-11 was used. The cured product could not be formed because it was low, and the insolubilization rate was 0%.

[Comparative Example 2]
A cured product was prepared in the same manner as in Example 1 except that a mixed solution of 67 parts by weight of BCAFG, 33 parts by weight of PMPS, 360 parts by weight of cyclohexanone and 5 parts by weight of SIN-11 was used. The obtained cured product had a refractive index of 1.6185 and an insolubilization rate of 92%.

[Reference Example 1]
A cured product was prepared in the same manner as in Example 1 except that a mixed solution of 90 parts by weight of BNFO, 10 parts by weight of BCAFG, 360 parts by weight of cyclohexanone and 5 parts by weight of SIN-11 was used without adding PMPS. The insolubilization rate of the obtained cured product was 60%.

[Reference Example 2]
A cured product was prepared in the same manner as in Example 1 except that a mixed solution of 90 parts by weight of BNFO, 10 parts by weight of BNFG, 360 parts by weight of cyclohexanone and 5 parts by weight of SIN-11 was used without adding PMPS. The obtained cured product had a refractive index of 1.6684 and an insolubilization rate of 70%.

  Table 1 shows the results obtained in the examples and comparative examples.

  As is clear from Table 1, the refractive index of the example was higher than that of the comparative example. Further, in the example, although a bifunctional cationically polymerizable compound was used as in Comparative Example 1, a surprisingly high insolubilization rate was exhibited and the contrast was good. Furthermore, in the Example, it was excellent also in the softness | flexibility compared with the comparative example 2, and it was able to make compatible the high insolubilization rate and a softness | flexibility.

  The curable composition of the present invention and the cured product thereof are paints, electric wire coating materials, electronic device sealing materials and insulating materials, printed wiring boards, protective films, photoresists, printing plate making materials, inks, adhesives, and adhesive materials. It can be suitably used for applications such as optical thin films (high refractive index layers of antireflection films such as liquid crystal displays, reflectors, etc.).

Claims (10)

A curable composition comprising a cationically polymerizable compound and polysilane, wherein the cationically polymerizable compound is represented by the following formula (1):

(In the formula, Ar ¹ and Ar ² and Z ¹ and Z ² are each an arene ring, R ^1a and R ^1b and R ^2a and R ^2b are each a substituent, and R ^3a and R ^3b are each linear or branched. An alkylene group, R ^4a and R ^4b are each a hydrogen atom or a substituent, k1 and k2, m1 and m2, and n1 and n2 each represent an integer of 0 or more.)
The curable composition containing the 1st cationically polymerizable compound represented by these. In the formula (1), Ar ¹ and Ar ² are each a C _6-10 arene ring, Z ¹ and Z ² are each a C _6-12 arene ring, and R ^3a and R ^3b are each a linear or branched C _{2− 6} alkylene group, R ^4a and R ^4b are each a hydrogen atom or a C _1-6 alkyl group, k1 and k2 are each an integer of 0 to 4, m1 and m2 are each an integer of 0 to 6, and n1 and n2 are each 0 to 0 The curable composition according to claim 1, which is an integer of 20. In Formula (1), Ar ¹ and Ar ² are each a benzene ring, Z ¹ and Z ² are naphthalene rings, R ^3a and R ^3b are each a linear or branched C _2-4 alkylene group, R ^4a and R ^4. Each of ^4b is a C _1-4 alkyl group, k1 and k2 are each an integer of 0 to 2, m1 and m2 are each an integer of 0 to 2, and n1 and n2 are each an integer of 0 to 3. Curable composition. The cationically polymerizable compound further comprises the following formula (2)

(In the formula, Ar ³ and Ar ⁴ and Z ³ and Z ⁴ are each an arene ring, R ^5a and R ^5b and R ^6a and R ^6b are each a substituent, and R ^7a and R ^7b are each linear or branched. An alkylene group, R ^8a and R ^8b are each a hydrogen atom or a methyl group, p1 and p2, q1 and q2, and r1 and r2 are each an integer of 0 or more, and s1 and s2 are integers of 1 to 4.
The curable composition in any one of Claims 1-3 containing the 2nd cationically polymerizable compound represented by these. In the formula (2), Ar ³ and Ar ⁴ are each a C _6-10 arene ring, Z ³ and Z ⁴ are each a C _6-12 arene ring, and R ^7a and R ^7b are each a linear or branched C _{2− 6} alkylene group, an integer of 0 to 4 p1 and p2 are each an integer Less than six q1 and q2 are each an integer of 0 to 20 r1 and r2, respectively, according to claim 4, wherein s1 and s2 is 1 or 2 Curable composition.   The curable composition according to claim 4 or 5, wherein the ratio of the first cationic polymerizable compound to the second cationic polymerizable compound is the former / the latter (weight ratio) = 50/50 to 99/1. The curable composition according to any one of claims 1 to 6, wherein the polysilane contains a linear poly C _1-6 alkyl C _6-14 aryl silane.   The curable composition according to any one of claims 1 to 7, wherein a ratio of the cationic polymerizable compound and the polysilane is the former / the latter (weight ratio) = 90/10 to 20/80.   Hardened | cured material which the curable composition in any one of Claims 1-8 hardened | cured.   The cured product according to claim 9, which has a refractive index of 1.65 to 1.75 at a temperature of 25 ° C and a wavelength of 589 nm.