JP6843352B2 - Curable composition and its cured product - Google Patents

Description

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

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

For example, Japanese Patent Application Laid-Open No. 2016-20472 (Patent Document 1) includes a photocationically polymerizable compound (A), polysilane (B), and a photoacid generator (C) that absorbs visible light to generate acid. A photopolymerizable resin composition has been disclosed, and this composition has excellent light sensitivity even when irradiated with visible light in order to suppress the decomposition of polysilane, and can improve the hardness of the cured product. , Photoresist, printing plate making material, etc. In the examples of this document, photopolymerization containing 9,9-bis [3,4-diglycidyloxy-phenyl] fluorene, polymethylphenylsilane or hyperbranched phenylsilane oligomer, and a predetermined photoacid generator. A sex resin composition is being prepared.

However, the refractive index and insolubilization rate (or curability) of the cured product obtained from such a composition may not be sufficient, and it cannot be applied to applications in which the required level for these characteristics is high.

Japanese Patent Application Laid-Open No. 2000-336802 (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 of the cured product of the oxetane compound, but also describes the combination of the oxetane compound and polysilane to form a curable composition. Is not mentioned at all.

Japanese Unexamined Patent Publication No. 2016-20472 (Claims, Examples, Paragraphs [0001] [0009]) Japanese Unexamined Patent Publication No. 2000-336882 (Claims, Examples)

Therefore, an object of the present invention is to provide a curable composition capable of forming a cured product having a high refractive index and a cured product thereof.

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

Still another object of the present invention is to provide a curable composition capable of forming a cured product capable of achieving 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 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 diligent studies to achieve the above problems, the present inventors not only can form a cured product having a high refractive index by combining a cationically polymerizable compound containing an oxetane compound having a bisarylfluorene skeleton with polysilane. We have found that a high insolubilization rate can be achieved even by using a cationically polymerizable compound having a small number of polymerizable functional groups, and completed the present invention.

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 the 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 arene rings, R ^1a and R ^1b and R ^{2a and R 2b} are substituents, respectively, and R ^3a and R ^3b are linear or branched chains, respectively. The alkylene group, R ^4a and R ^4b are hydrogen atoms or substituents, respectively, and k1 and k2, m1 and m2 and n1 and n2 each represent an integer of 0 or more).

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

Further, the cationically polymerizable compound may further contain a second cationically polymerizable compound represented by the following formula (2).

(In the formula, Ar ³ and Ar ⁴ and Z ³ and Z ⁴ are arene rings, R ^5a and R ^5b and R ^{6a and R 6b} are substituents, respectively, and R ^7a and R ^7b are linear or branched chains, respectively. The alkylene group, R ^8a and R ^8b are hydrogen atoms or methyl groups, respectively, p1 and p2, q1 and q2 and r1 and r2 are integers of 0 or more, respectively, and s1 and s2 are integers of 1 to 4).

In the above formula (2), Ar ³ and Ar ⁴ are C _6-10 arene rings, Z ³ and Z ⁴ are C _6-12 arene rings, and R ^7a and R ^{7 b} are linear or branched C _{2 respectively. -6} alkylene groups, p1 and p2 are integers of about 0 to 4, q1 and q2 are integers of about 0 to 6, respectively, r1 and r2 are integers of about 0 to 20, respectively, and s1 and s2 are 1 or 2. You may. Further, the ratio of the first cationically polymerizable compound to the second cationically polymerizable compound may be about 50/50 to 99/1 of the former / the latter (weight ratio).

The polysilane may contain a chain _{polyC 1-6} alkyl C 6-14 arylsilane. Further, the ratio of the cationically polymerizable compound to the polysilane may be about 90/10 to 20/80 of the former / the latter (weight ratio).

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, "compound having a fluorene skeleton" means not only a compound having a fluorene skeleton but also a compound having an aromatic skeleton having a fluorene ring such as a benzofluorene skeleton and a dibenzofluorene skeleton. Used for.

Since the curable composition of the present invention contains a cationically polymerizable compound containing a predetermined oxetane compound and polysilane, a cured product having a high refractive index can be formed. Further, 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 at the same time. Further, even if the oxetane compound contains a condensed polycyclic aromatic skeleton, the handleability can be improved because the oxetane compound has high solubility in a solvent.

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

[Cationally polymerizable compound]
(First cationically 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 arene rings, R ^1a and R ^1b and R ^{2a and R 2b} are substituents, respectively, and R ^3a and R ^3b are linear or branched chains, respectively. The alkylene group, R ^4a and R ^4b are hydrogen atoms or substituents, respectively, and k1 and k2, m1 and m2 and n1 and n2 each represent an integer of 0 or more).

In the above formula (1), the ^{arene rings (aromatic hydrocarbon rings) represented by the rings Ar 1} and Ar ² _{include, for example, a C 6-14} arene ring such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. _{A C 6-10} arene ring (particularly, a benzene ring) such as a benzene ring and a naphthalene ring is preferable. The types of arene rings represented by rings Ar ¹ and Ar ² may be the same or different from each other.

The rings Ar ¹ and Ar ² have a fused ring skeleton together with a 5-membered ring intervening, 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 benzofluorene skeleton (eg, benzo [a] fluorene skeleton, benzo [b] fluorene skeleton, benzo [c] fluorene skeleton, etc.); a dibenzofluorene skeleton in which both are naphthalene rings (eg, dibenzo [b, h] fluorene skeleton). An aromatic skeleton (preferably a fluorene skeleton or a benzofluorene skeleton, particularly a fluorene skeleton) in which a fluorene ring is contained may be formed.

In the above 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, and the polycyclic arene ring includes a polycyclic arene ring. Condensed polycyclic arene rings (condensed polycyclic aromatic hydrocarbon rings), ring-assembled arene rings (ring-assembled aromatic hydrocarbon rings), and the like are included.

Examples of the fused polycyclic arene ring include a fused bicyclic arene ring (for example, a fused bicyclic C _10-16 arene ring such as a naphthalene ring and an inden ring) and a fused tricyclic arene ring (for example, an anthracene ring). , Phenanthrene ring, etc.) and other fused bicyclic arene rings. Preferred 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, and naphthalene ring is particularly preferable. preferable.

_{The ring-assembled arene ring includes a bi-C 6-12} arene ring (for example, a bi-C 6-12 arene ring such as a biphenyl ring, a binaphthyl ring, a phenylnaphthalene ring (1-phenylnaphthalene ring, 2-phenylnaphthalene ring, etc.)), a tellarene ring (for example, a biphenyl ring, a binaphthyl ring, a 2-phenylnaphthalene ring, etc.) For example, a Tel C _6-12 arene ring such as a terphenylene ring) can be exemplified. Preferred ring-set arene rings include a biC _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 often the same. Of the rings Z ¹ and Z ² _{, C 6-12} arene rings such as benzene ring, naphthalene ring, and biphenyl ring _{are preferable, and C 6-10} arene ring such as benzene ring and naphthalene ring, particularly high refractive index. A naphthalene ring is preferable because it can be formed.

The substitution positions of ^{the rings Z 1} and Z ² bonded to the 5-membered ring are not particularly limited. For example, when rings Z ¹ and Z ² are naphthalene rings, they may be in either the 1-position or the 2-position. 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 above formula (1), the substituents R ^1a and R ^1b include a hydrocarbon group [for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, etc.). Linear or branched C _1-6 alkyl groups, etc.), aryl groups (eg, C _6-10 aryl groups such as phenyl groups), etc.], cyano groups, halogen atoms (eg, fluorine atoms, chlorine atoms, etc.) , Bromine atom, 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, or a halogen atom is preferable, and an alkyl group (particularly, a C such as a methyl group) is preferable. _1-3 alkyl group) is preferable.

The substitution numbers k1 and k2 of the groups R ^1a and R ^1b are integers 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, and more preferably 0 or 1. , Especially 0. The substitution numbers k1 and k2 may be the same or different from each other. ^{Further, the types of the groups R 1a} and R ^1b to be replaced with the rings Ar ¹ and Ar ² may be the same or different from each other, and when k1 and k2 are 2 or more, they are replaced with the ^{same rings Ar 1} and Ar ^2. The types of the two or more groups R ^1a and R ^1b are the same or different from each other. 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 7-position (2-position, It may be in the 3-position and the 7-position, etc.).

In the above 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) and a hydrocarbon group {for example, an alkyl group (methyl group, ethyl group, _{Linear or branched C 1-10} alkyl groups such as propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, preferably linear or branched C _1-6 alkyl Groups, more preferably linear or branched C _1-4 alkyl groups); cycloalkyl groups (eg, cyclopentyl groups, C _5-10 cycloalkyl groups such as cyclohexyl groups); aryl groups [eg, phenyl group, alkylphenyl group (e.g., methylphenyl group (tolyl group), such as a dimethylphenyl group (xylyl)), a biphenylyl group, a C _6-12 aryl group such as a naphthyl group]; aralkyl groups (e.g., benzyl group, _{C 6-10} aryl-C _1-4 alkyl groups such as phenethyl groups}, alkoxy groups (eg, methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t- Linear or branched C _1-10 alkoxy groups such as butoxy groups), cycloalkyloxy groups (eg C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryloxy groups (eg phenoxy) C _6-10 aryloxy groups such as groups), aralkyloxy groups (eg C _6-10 aryl-C _1-4 alkyloxy groups such as benzyloxy groups), alkylthio groups (eg methylthio groups, ethylthio groups) , Cpropylthio group, n-butylthio group, C _1-10 alkylthio group such as t-butylthio group), cycloalkylthio group (for example, C _5-10 cycloalkylthio group such as cyclohexylthio group), arylthio group (for example, thio _{C 6-10} arylthio groups such as phenoxy groups), aralkylthio groups (eg C _6-10 aryl-C _1-4 alkylthio groups such as benzylthio groups), acyl groups (eg C _{1- such as acetyl groups) 6} Acyl groups, etc.), nitro groups, cyano groups, substituted amino groups [eg, dialkylamino groups (eg, diC _1-4 alkylamino groups such as dimethylamino groups), bis (alkylcarbonyl) amino groups (eg, eg) Bis (C _1-4 alkyl-carbonyl) amino groups such as diacetylamino groups) Do] etc. can be exemplified.

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

Substituents which m1 and m2 of the radicals ^{R 2a} and ^{R 2b} may be any integer of 0 or more, can be appropriately selected depending on the type of ring ^{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. Further, the types of the groups R ^2a and R ^2b may be the same or different from each other, and when the substitution numbers m1 and m2 are 2 or ^{more, the groups R 2a of} 2 or more are substituted with the ^{same rings Z 1} and Z ^2. And R ^2b types 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 positions other than the substitution positions of the oxetane ring-containing group.

In the above formula (1), the groups R ^3a and R ^3b include a linear or branched alkylene group, and examples of the linear alkylene group include an ethylene group, a trimethylene group and a tetramethylene group. Examples thereof include a linear C _2-6 alkylene group (preferably a linear C _2-3 alkylene group, more preferably a linear C _2-3 alkylene group, particularly an ethylene group), and examples of the branched alkylene group include a linear C 2-3 alkylene group. _{Examples thereof include a branched C 3-6} alkylene group (preferably a branched C _3-4 alkylene group, particularly a propylene group) such as a propylene group, a 1,2-butandyl group and a 1,3-butanjiyl group. Be done. Of these groups R ^3a and R ^3b , preferably a linear or branched C _2-6 alkylene group (eg, a linear or branched C _2-4 alkylene group), more preferably a straight chain. _{It may be a C 2-3} alkylene group (particularly an ethylene group) in the form of a branched chain or a branched chain. In each oxetane ring-containing group substituted with different rings Z ¹ and Z ^{2 , the types of 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 groups (OR ^3a and OR ^3b ) can be selected from the range of integers of 0 or more (for example, integers of about 0 to 20), and for example, about 0 to 15 (1 to 10). An integer, preferably an integer of about 0-8 (eg, 2-7), more preferably an integer of about 0-5 (eg, 3-5), particularly an integer of about 0-2 (eg, 0 or 1, especially. It may be 0). If n1 and n2 are too large, the refractive index may decrease. Further, n1 and n2 may be the same or different from each other. In the oxetane ring-containing group, when the number of repetitions n1 and n2 is 2 or more, ^{the types of the groups R 3a} and R ^3b of 2 or more may be different from each other, but are preferably the same.

In the present specification, unless otherwise specified, the "repetition number of oxyalkylene groups" (and the "total number of oxyalkylene groups (total addition number)" described later) means oxyalkylene in one molecule of the compound. It is used to include both the number of groups (integer) and the average value of the number of oxyalkylene groups in the molecular assembly of the compound [that is, the average number of added moles]. Therefore, the repetition numbers n1 and n2 may be average values (arithmetic mean or arithmetic mean) in the molecular assembly of the compound represented by the formula (1), and the range is preferably the range of the integers. It may be about the same including the aspect.

Further, in the formula (1), the total number of repetitions n1 and n2 means the total number (total addition number) of oxyalkylene groups in one molecule of the compound represented by the formula (1), and is simply n1 + n2. In some cases. n1 + n2 can be selected from a range of integers of, for example, about 0 to 30, for example, an integer of about 0 to 25 (for example, 1 to 20), preferably an integer of about 0 to 15 (for example, 2 to 10), and further. 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, especially 0). Further, n1 + n2 may be an integer as described above, but may be the average number of moles added in the molecular assembly of the compound represented by the formula (1), and the range thereof is, for example, the integer. It may be about the same including the range and the preferred embodiment. 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 decreases, so that the high refractive index and high heat resistance derived from the skeleton are reduced. Excellent properties such as sex may deteriorate. In addition, n1 + n2 can be measured by a conventional method, for example, in the preparation of the compound represented by the above formula (1), it is consumed in the reaction with the amount of the hydroxy compound having a bisarylfluorene skeleton as a raw material. It can be measured by a method of calculating as an arithmetic mean or an arithmetic mean value from the ratio with the amount of the alkylene oxide (alkylene carbonate or haloalkanol) (for example, the method described in International Publication No. 2013/022065).

In the above formula (1), the groups R ^4a and R ^4b are hydrogen atoms or substituents, and the substituents include, for example, a hydrocarbon group {for example, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, _{A linear or branched C 1-10} alkyl group such as an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, preferably a linear or branched C _1-6 alkyl group, and further. Preferred is a linear or branched C _1-4 alkyl group); cycloalkyl group (eg, C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group); aryl group [eg, phenyl group, alkyl phenyl group (e.g., methylphenyl group (tolyl group), a dimethylphenyl group (xylyl), etc.), a biphenylyl group, a C _6-12 aryl group such as a naphthyl group]; aralkyl groups (e.g., benzyl group, phenethyl group C _6-10 aryl-C _1-4 alkyl group, etc.); Allyl group, etc.}; Fluorine-containing group [for example, fluorine atom; alkyl fluoride group (C _1-6 alkyl fluoride group such as trifluoromethyl group) Fluorinated hydrocarbon groups such as]; heteroaryl groups (eg, frill group, 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 groups), especially hydrogen atoms or _C1-2 alkyl groups (eg, methyl or ethyl groups, especially methyl groups). The types of 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 replaced with the − position or the 4-position (particularly the 4-position). Further, when the rings Z ¹ and Z ² are naphthalene rings, they are often substituted with any of the 5-8-positions of the corresponding naphthyl groups, for example, between the ^{rings Ar 1} and Ar ^2. The 1-position or 2-position of the naphthalene ring is substituted (replaced in the relationship of 1-naphthyl or 2-naphthyl) with respect to the intervening 5-membered ring, and the 1,5-position with respect to this substitution position. In many cases, the oxetane ring-containing group is substituted in a relationship such as the 2,6-position (particularly the relationship at the 2,6-position).

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

(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} There bisphenyl fluorenes is a benzene ring, (A2) ring Z ¹ and Z ² are like bisnaphthyl fluorenes is a naphthalene ring.

Specifically, as the (A1) bisphenylfluorenes, for example, in (A1-1) the above formula (1), 9,9-bis [(3-oxetanyl) methoxy-phenyl] fluorene in which n1 and n2 are 0. Class {For example, in the above formula (1), 9,9-bis [(3-oxetanyl) methoxy-phenyl] fluorene (for example, 9,9- ^{) in which m1 and m2 are 0 and R 4a} and R ^{4b are hydrogen atoms.} Bis [4-((3-oxetanyl) methoxy) -phenyl] fluorene, etc.); In the above formula (1), m1 and m2 are 0, and ^{R4a and R4b} are alkyl groups 9,9-bis [(3). -Alkyl-3-oxetanyl) methoxy-phenyl] fluorene (eg, 9,9-bis [4-((3-methyl-3-oxetanyl) methoxy) -phenyl] fluorene, 9,9-bis [4-(((3-methyl-3-oxetanyl) methoxy) -phenyl] fluorene, _{9,9-bis [(3-C 1-6} alkyl-3-oxetanyl) methoxy-phenyl] fluorene, etc., such as 3-ethyl-3-oxetanyl) methoxy) -phenyl] fluorene; 9,9-bis [(3-oxetanyl) methoxy- (mono or di) alkylphenyl] fluorene in which m1 and m2 are 1 or 2, R ^2a and R ^2b are alkyl groups, and R ^4a and R ^{4b are hydrogen atoms.} For example, 9,9-bis [4-((3-oxetanyl) methoxy) -3-methylphenyl] fluorene, 9,9-bis [4-((3-oxetanyl) methoxy) -3,5-dimethylphenyl] 9,9-bis [(3-oxetanyl) methoxy- (mono or di) C _1-6 alkylphenyl] fluorene, etc.) such as fluorene; in the above formula (1), m1 and m2 are 1 or 2, R ^2a and 9,9-bis [(3-alkyl-3-oxetanyl) methoxy- (mono or di) alkylphenyl] fluorene (eg, 9,9-bis) in which R ^2b is an alkyl group and R ^4a and R ^{4b are an alkyl group.} [4-((3-Methyl-3-oxetanyl) methoxy) -3-methylphenyl] fluorene, 9,9-bis [4-((3-ethyl-3-oxetanyl) methoxy) -3-methylphenyl] fluorene _{, 9,9-bis [(3-C 1-6} alkyl-3-oxetanyl) methoxy-, such as 9,9-bis [4- (3-methyl-3-oxetanyl) -3,5-dimethylphenyl] fluorene (Mono or di) C _1-6 alkylphenyl] fluorene, etc.); In (1), 9,9-bis [(3-oxetanyl) methoxy-arylphenyl] fluorene (for example, 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) -3-phenylphenyl] fluorene, etc. 9,9-bis [(3-oxetanyl) methoxy-C _6-10 arylphenyl] fluorene, etc.); In formula (1), 9,9-bis [(3-alkyl-3-oxetanyl) methoxy-arylphenyl) in which m1 and m2 are 1, R ^2a and R ^2b are aryl groups, and R ^4a and R ^{4b are alkyl groups.} ] Fluorene (eg, 9,9-bis [4-((3-methyl-3-oxetanyl) methoxy) -3-phenylphenyl] fluorene, 9,9-bis [4-((3-ethyl-3-oxetanyl) methoxy) ) Methoxy) -3-phenylphenyl] fluorene, etc. 9,9-bis [(3-C _1-6 alkyl-3-oxetanyl) methoxy-C _6-10 arylphenyl] fluorene, etc.)}; (A1-2) ) In the above formula (1), 9,9-bis [for example, n1 and n2 are 1 or more [for example, 1 to 20, preferably 2 to 10 (for example, 3 to 8), more preferably about 4 to 7]]. (3-oxetanyl) methoxy (poly) alkoxy-phenyl] fluorenes (that is, compounds in which n1 and n2 are 1 or more corresponding to the compound exemplified in (A1-1) above) {For example, the above formula (1) In 9,9-bis [(3-oxetanyl) methoxy (poly) alkoxy-phenyl] fluorene in which m1 and m2 are 0 and R ^4a and R ^{4b are hydrogen atoms (for example, 9,9-bis [4- ().} 2-((3-oxetanyl) methoxy) ethoxy) -phenyl] fluorene, 9,9-bis [4-(2-((3-oxetanyl) methoxy) propoxy) -phenyl] fluorene, 9,9-bis [4 -(2- (2-((3-oxetanyl) methoxy) ethoxy) ethoxy) -phenyl] 9,9-bis [(3-oxetanyl) methoxy (mono to icosa) C _2-6 alkoxy-phenyl] such as fluorene] Fluolene, etc.); In the above formula (1), 9,9-bis [(3-alkyl-3-oxetanyl) methoxy (poly) alkoxy-phenyl] in which ^{m1 and m2 are 0 and R 4a} and R ^{4b are alkyl groups.} Phenyl (eg, 9,9-bis [4- (2) -((3-Methyl-3-oxetanyl) methoxy) ethoxy) -phenyl] fluorene, 9,9-bis [4- (2-(2-((3-ethyl-3-oxetanyl) methoxy) ethoxy) ethoxy) -Phenyl] 9,9-bis such as fluorene [(3-C _1-6 alkyl-3-oxetanyl) methoxy (mono to icosa) C _2-6 alkoxy-phenyl] fluorene, etc.); 9,9-bis [(3-oxetanyl) methoxy (poly) alkoxy- (mono or di) alkyl, where m1 and m2 are 1 or 2, R ^2a and R ^2b are alkyl groups, and R ^4a and R ^{4b are hydrogen atoms.} Phenyl] fluorene (eg, 9,9-bis [4- (2-((3-oxetanyl) methoxy) ethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (2- (2- (2-( (3-oxetanyl) methoxy) ethoxy) ethoxy) -3,5-dimethylphenyl] 9,9-bis [(3-oxetanyl) methoxy (mono to icosa) C _2-6 alkoxy- (mono or di) such as fluorene C _1-6 alkylphenyl] fluorene, etc.); In the above formula (1), m1 and m2 are 1 or 2, R ^2a and R ^2b are alkyl groups, and R ^4a and R ^4b are alkyl groups 9,9-bis. [(3-Alkyl-3-oxetanyl) methoxy (poly) alkoxy- (mono or di) alkylphenyl] fluorene (eg, 9,9-bis [4- (2-((3-methyl-3-oxetanyl) methoxy) ) Ethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-(2-((3-ethyl-3-oxetanyl) methoxy) ethoxy) ethoxy) -3,5-dimethylphenyl] 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 alkylphenyl] fluorene, etc.); In formula (1), 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 (poly) alkoxy-arylphenyl ] Fluolene (eg, 9,9-bis [4-(2-((3-oxetanyl) methoxy) ethoxy) -3-phenylphenyl] 9,9-bis [(3-oxetanyl) methoxy (mono to Ikosa) C _{2-6 Alkyl-C 6 -10} arylphenyl] fluorene, etc.); In the above formula (1), 9,9-bis [(3-3-bis ^{) in which m1 and m2 are 1, R 2a} and R ^2b are aryl groups, and R ^4a and R ^{4b are alkyl groups.} Alkyl-3-oxetanyl) methoxy (poly) alkoxy-arylphenyl] fluorene (eg, 9,9-bis [4-(2-((3-methyl-3-oxetanyl) methoxy) ethoxy) -3-phenylphenyl] Fluorene, 9,9-bis [4- (2- (2-((3-ethyl-3-oxetanyl) methoxy) ethoxy) ethoxy) -3-phenylphenyl] 9,9-bis [(3-3-phenylphenyl)] such as fluorene. C _1-6 alkyl-3-oxetanyl) methoxy (mono to icosa) C _2-6 alkoxy-C _6-10 arylphenyl] fluorene, etc.} and the like.

Specific examples of (A2) bisnaphthylfluorenes include, for example, (A2-1) 9,9-bis [(3-oxetanyl) methoxy-naphthyl] fluorene in which n1 and n2 are 0 in the above formula (1). Class {For example, in the above formula (1), m1 and m2 are 0, and R ^4a and R ^4b are hydrogen atoms, 9,9-bis [(3-oxetanyl) methoxy-naphthyl] fluorene (for example, 9,9-). 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 are alkyl groups 9,9-bis [(3-alkyl-3-oxetanyl) methoxy-naphthyl] fluorene (eg, 9,9-bis [6-(((3-alkyl-3-oxetanyl) methoxy-naphthyl] fluorene. 3-Methyl-3-oxetanyl) methoxy) -2-naphthyl] fluorene, 9,9-bis [6-((3-ethyl-3-oxetanyl) methoxy) -2-naphthyl] fluorene, 9,9-bis [ 9 such as 5-((3-methyl-3-oxetanyl) methoxy) -1-naphthyl] fluorene, 9,9-bis [5-((3-ethyl-3-oxetanyl) methoxy) -1-naphthyl] fluorene, etc. , 9-bis [(3-C _1-6 alkyl-3-oxetanyl) methoxy-naphthyl] fluorene, etc.); (A2-2) In the above formula (1), n1 and n2 are 1 or more [for example, 1 to 20]. , Preferably 2 to 10 (for example, about 3 to 8), more preferably about 4 to 7] 9,9-bis [(3-oxetanyl) methoxy (poly) alkoxy-naphthyl] fluorenes (that is, the above-mentioned (that is, about 4 to 7). A compound in which n1 and n2 are 1 or more corresponding to the compound exemplified in A2-1) {For example, in the above formula (1), m1 and m2 are 0, and ^{R4a and R4b} are hydrogen atoms 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-((3-oxetanyl) methoxy) methoxy) ethoxy ) Ethoxy) -2-naphthyl] fluorene, 9,9-bis [5-(2-((3-oxetanyl) methoxy) ethoxy) -1-naphthic Lu] 9,9-bis such as fluorene [(3-oxetanyl) methoxy (mono to icosa) C _2-6 alkoxy-naphthyl] fluorene, etc.); in the above formula (1), m1 and m2 are 0, R ^4a and 9,9-bis [(3-alkyl-3-oxetanyl) methoxy (poly) alkoxy-naphthyl] fluorene in which R ^{4b is an alkyl group (for example, 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) methoxy) ethoxy) ethoxy) -2-naphthyl] fluorene, 9,9-bis [5-(2-((3-methyl-3-oxetanyl) methoxy) ethoxy) -1-naphthyl] fluorene, etc. 9, 9-Bis [(3-C _1-6 alkyl-3-oxetanyl) methoxy (mono to icosa) C _2-6 alkoxy-naphthyl] fluorene, etc.) and the like.

In addition, in the above-exemplified compound, the compound which k1 and k2 in the said formula (1) are 1 or more is also included. Further, in the present specification and claims, "(poly) alkoxy" is used to mean including both an alkoxy group and a polyalkoxy group.

These first cationically polymerizable compounds represented by the above formula (1) can be used alone or in combination of two or more. Preferred first cationically polymerizable compounds include, for example, 9 such as (A1) bisphenylfluorenes [eg, 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.]; (A2) bisnaphthylfluorene, etc. In particular, 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) (A2-1) 9,9-bis [(3-oxetanyl) methoxy-naphthyl] fluorenes such as −naphthyl] fluorene; 9,9-bis [(3-C _1-4 alkyl-3-oxetanyl) methoxy ( (Mono to deca) C _2-6 alkoxy-naphthyl] fluorene and the like (A2-2) 9,9-bis [(3-oxetanyl) methoxy (poly) alkoxy-naphthyl] fluorene and the like] are preferable, and in particular, 9, _{9,9-bis [(3-C 1-2} alkyl-3-oxetanyl) methoxy-naphthyl] fluorene such as 9-bis [6-((3-methyl-3-oxetanyl) methoxy) -2-naphthyl] fluorene Is preferable.

These first cationically polymerizable compounds may be commercially available products or may be prepared by a conventional method (for example, the method described in JP-A-2000-336082). As a typical method, for example, a method of reacting a compound represented by the following formula (1A) with 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 preferred embodiments, respectively. The same as the above equation (1) including.

(Wherein, X is a halogen atom, R ⁴ represents a hydrogen atom or a substituent).

Specifically, the compound represented by the formula (1A) is, for example, the (3-oxetanyl) methyl group or (3-oxetanyl) methyl group of the compound exemplified as the first cationically polymerizable compound represented by the formula (1). Examples thereof include a dihydroxy compound in which an alkyl-3-oxetanyl) methyl group is replaced with a hydrogen atom. As the compound represented by the formula (1A), a commercially available product may be used, and a conventional method [for example, ^{a fluorenone compound corresponding to rings Ar 1} and Ar ² (including benzofluorenone or dibenzofluorenone) and a ring It ^{may be prepared by 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].

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

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

Specifically, as the compound represented by the formula (1B), for example, 3-halomethyl-oxetane such as 3-chloromethyl-oxetane; 3-chloromethyl-3-methyloxetane, 3-chloromethyl-3-ethyl Examples thereof include 3-halomethyl-3-C _1-6 alkyl oxetane such as oxetane. Among these compounds represented by the formula (1B), 3-halomethyl-3-C _1-4 alkyl oxetane (particularly, 3-halomethyl-3-C _{1- such as 3-chloromethyl-3-methyloxetane) 2} Alkyl oxetane, etc.) is preferred. As the compound represented by the formula (1B), a commercially available product or the like can be used.

The ratio of the compound represented by the formula (1B) is, for example, 0.5 to 10 mol, preferably 1 to 5 mol (for example, 1 to 5 mol) with respect 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 carried out 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, carbonate). (Potass, etc.) and the like.

These alkali metals or alkali metal compounds may be used alone or in combination of two or more. Among these alkali metals or alkali metal compounds, alkali metal carbonates such as potassium carbonate are preferable. 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 1.1 to 1.5 mol, based on 1 mol of the hydroxyl group of the compound represented by the formula (1A). It may be about 1.2 to 1.4 mol.

The reaction may be carried out 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 can also be used alone or in combination of two or more. Among these phase transfer catalysts, tetra C _1-4 alkylammonium halides such as tetramethylammonium bromide are preferable. 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, based on 1 mol of the hydroxyl group of the compound represented by the formula (1A). It may be about 0.02 to 0.05 mol.

The reaction may be carried out in the presence of a solvent. Solvents include, for example, 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, etc.); Sulfoxides (dimethylsulfoxide (DMSO), etc.); 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, and amides such as DMF may be used. The ratio of the solvent is, for example, 100 to 1000 parts by weight, preferably 200 to 800 parts by weight, and more preferably 400 to 600 parts by weight with respect to 100 parts by weight of the compound represented by the formula (1A). May be good.

The reaction may be carried out 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 0.02 to 0.08 mol, based on 1 mol of the hydroxyl group of the compound represented by the formula (1A). May be on the order of 0.04 to 0.06 mol.

The reaction may be carried out in air or in an inert gas (eg, nitrogen; a rare gas such as argon or helium). Further, the reaction may be carried out under normal pressure, 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, about 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 and column chromatography, or a method combining these. You may.

(Second cationically polymerizable compound)
The cationically polymerizable compound may contain a second cationically polymerizable compound represented by the following formula (2), if 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 arene rings, R ^5a and R ^5b , R ^6a and R ^6b are substituents, respectively, and R ^7a and R ^7b are linear or branched chains, respectively. The alkylene group, R ^8a and R ^8b are hydrogen atoms or methyl groups, respectively, p1 and p2, q1 and q2 and r1 and r2 are integers of 0 or more, respectively, and s1 and s2 are integers of 1 to 4).

In the above 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 above formula (1), respectively. However, the same may be applied including preferable aspects 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. Further, ^{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, the insolubilization rate can be effectively improved even if s1 and s2 are small (or even if the number of polymerizable functional groups is small).

Further, the total number (total number of additions) of oxyalkylene groups in one molecule of the compound represented by the above formula (2) [may be simply r1 × s1 + r2 × s2] depends on the values of s1 and s2. It can be selected, for example, it can be selected from a range of integers 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), and further. 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, especially 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). ) Diglycidyl compounds in which a methyl group or a (3-alkyl-3-oxetanyl) methyl group is replaced with a glycidyl group can be mentioned. These second cationically polymerizable compounds can be used alone or in combination of two or more. Of the second cationically 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 (for example, 9,9-bis [6- (2-glycidyloxyethoxy) -2-naphthyl] fluorene and other 9,9-bis [glycidyloxy (mono to deca) C _2-4 alkoxynaphthyl] fluorene , Etc.) are preferable, 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, the method described in JP2012-102228A, that is, the formula (1). Prepared by the method of reacting a dihydroxy compound (compound represented by the above formula (1A)) corresponding to the compound represented by 2) and epichlorohydrin in the presence of a base such as sodium hydroxide]. You may.

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

The cationically polymerizable compound is not always necessary, but may contain other cationically polymerizable compounds (simply also referred to as a third cationically polymerizable compound) that do not belong to the first and second cationically polymerizable compounds. Good. The third cationically polymerizable compound includes, for example, a monofunctional oxetane compound such as an oxetane ring-containing compound (for example, (3-ethyl-3-oxetanyl) methanol; p-bis [(3-ethyl-3-oxetanyl)). Polyfunctional oxetane compounds such as methoxymethyl] benzene); conventional epoxy resins (eg, glycidyl ether type epoxy resins such as bisphenol type epoxy resins; glycidyl ester type epoxy resins; glycidylamine type epoxy resins; alicyclic epoxy resins Etc.); Vinyl ether group-containing compounds (eg, 9,9-bis [4- (2-vinyloxyethoxy) phenyl] fluorene, 9,9-bis [6- (2-vinyloxyethoxy) -2-naphthyl] fluorene) 9,9-Bis [vinyloxy (poly) alkoxyaryl] fluorene; 9,9-bis [4- (2-vinyloxyethoxy) -2-methylphenyl] fluorene, 9,9-bis [4- (2) Examples thereof include 9,9-bis [vinyloxy (poly) alkoxy- (mono or di) alkylphenyl] fluorene, etc.) such as −vinyloxyethoxy) -3-methylphenyl] fluorene.

The ratio of the total amount of the first cationically polymerizable compound and the second cationically polymerizable compound is, for example, from a range of about 10% by weight or more (for example, 30 to 100% by weight) with respect to the entire cationically polymerizable compound. It can be selected, 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), and more preferably 90% by weight or more (for example, 90 to 95% by weight). ), And may be substantially 100% by weight (a mode containing no third cationically polymerizable compound).

[Polysilane]
The polysilane is not particularly limited as long as it is a linear, cyclic, branched chain, 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 the formula, R ^{9 to} R ¹¹ represent a hydrogen atom, a hydroxyl group, an organic group or a silyl group, which are the same or different from each other).

In the formulas (3a) and (3b) ^{, examples of the organic group represented by R 9 to} R ¹¹ include a hydrocarbon group (alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group and aralkyl group. ), Ether groups corresponding to these hydrocarbon groups (alkoxy group, cycloalkyloxy group, aryloxy group, aralkyloxy group, etc.) and the like. 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. In addition, 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 (preferably a C _1-10 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. More preferably, C _1-6 alkyl group) is mentioned.

_{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 vinyl group, allyl group, butenyl group and pentenyl group.

_{Examples of the} cycloalkyl group include a C 5-14 cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a methylcyclohexyl group. _{Examples of the} cycloalkyloxy group include a C 5-14 cycloalkyloxy group such as a cyclopentyloxy group and a cyclohexyloxy group. _{Examples of the cycloalkenyl group include a C 5-14} cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group.

_{Examples of the aryl group include a C 6-20} aryl group (preferably a C _6-15 aryl group, more preferably a C _6- ) such as a phenyl group, a methyl phenyl group (tolyl group), a dimethyl phenyl group (xylyl group), and a naphthyl group. ₁₂ aryl group) and the like. The aryloxy group is a phenoxy group, such as C _6-20 aryloxy group such as naphthyloxy group. _{Examples of the aralkyl group include C 6-20} aryl-C _1-4 alkyl groups such as a benzyl group, a phenethyl group and a 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 a Si 1-10} silanyl group (preferably a Si _1-6 silanyl group) such as a silyl group, a disilanyl group, and a trisilanyl group.

Further, when R ^{9 to} R ¹¹ are the organic group (alkyl group, aryl group, etc.) or silyl group, at least one of the hydrogen atoms is substituted with a substituent (or functional group). Good. Such a substituent (or functional group) may be the same as the above-exemplified group such as, for example, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group and the like.

Of these, R ^{9 to} R ¹¹ are often alkyl groups (eg, C _1-4 alkyl groups such as methyl groups), aryl groups (eg, C _6-20 aryl groups such as phenyl groups), and the like. ..

When the polysilane has an acyclic structure (chain (linear, branched), network), the terminal group (terminal substituent) is usually a hydrogen atom, a hydroxyl group, a halogen atom (chlorine atom, etc.), an alkyl. It may be a group, an aryl group, an alkoxy group, a silyl group and the like. Of these, hydroxyl groups, methyl groups, and phenyl groups are often used. Among them, phenyl groups and methyl groups are selected from the viewpoint of improving photocurability without trapping the acid generated from the photoacid generator. Preferably, the terminal group may be a trimethylsilyl group.

Specific examples of the polysilane include a linear or cyclic polysilane having a structural unit represented by the formula (3a) and a polysilane having a structural unit represented by the formula (3b) (branched chain or network). Polysilane), polysilane (branched chain-shaped or network-shaped polysilane) having a combination of structural units represented by the formulas (3a) and (3b), and the like can be mentioned. 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 chain or network polysilane may further contain a structural unit represented by the following formula (3c).

Typical polysilanes include chain or cyclic polysilanes, such as polydialkylsilanes [eg, polydimethylsilanes, polymethylpropylsilanes, polymethylbutylsilanes, polymethylpentylsilanes, polydibutylsilanes, polydihexylsilanes, dimethylsilanes. -Methylhexylsilane copolymer, etc.]; Polyalkylarylsilane [eg, polymethylphenylsilane, methylphenylsilane-phenylhexylsilane copolymer, etc.]; Polydiarylsilane (eg, polydiphenylsilane, etc.); Dialkylsilane- Examples thereof include alkylarylsilane copolymers (for example, dimethylsilane-methylphenylsilane copolymer, dimethylsilane-phenylhexylsilane copolymer, dimethylsilane-methylnaphthylsilane copolymer, etc.). These polysilanes can be used alone or in combination of two or more.

^{Of these, R 9} is an aryl group (particularly C _6-20 aryl group) and R ¹⁰ is an aryl group (particularly C _6- ) because it does not inhibit cationic polymerization and can improve the stability of the cured product. Polysilanes (particularly chain or cyclic polysilanes) having structural units (3a) that are ₂₀ aryl groups) or alkyl groups (particularly C _{1-6 alkyl groups), such as poly C 1-6} alkyl C _6-20 aryl silanes (especially C 1-6 alkyl groups). For example, _{polyC 1-3} alkyl C 6-10 arylsilane) and polydi C _6-20 arylsilane (eg, polydi C _6-10 arylsilane) are preferred. Further, from the viewpoint of compatibility with cationically polymerizable compounds, chain polyalkylarylsilane (for example, chain poly C _1-6 alkyl C _6-14 arylsilane) and cyclic diarylsilane are preferable, and chain-like is particularly preferable. Polyalkylarylsilanes (particularly chain _{polyC 1-3 alkylC 6-10} arylsilanes such as polymethylphenylsilane) are preferred.

As the polysilane used in the present invention, polysilane in which at least one hydroxyl group is directly bonded to the silicon atom at the terminal of polysilane, that is, polysilane having at least one silanol group (hydroxyl group) at the terminal is preferable. The hydroxyl group directly bonded to the silicon atom shows good reactivity with the oxetanyl group (and epoxy group) of the cationically polymerizable compound, and is highly reactive between the cationically polymerizable compound and polysilane by ultraviolet light irradiation and / or heating. Bridge structure is formed. The content ratio of hydroxyl groups is, for example, about 0.005 to 2.5 on average, preferably about 0.01 to 1 on average, and more preferably 0.05 to 0.5 on average per silicon atom. Degree. If the content ratio of the silanol group (hydroxyl group) is too large, there is a risk of inhibiting the cationic polymerization, probably because the acid by the photoacid generator is trapped.

The average degree of polymerization of 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). It may be preferably about 12 to 30 (particularly 15 to 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 10000, and more preferably 400 to 8000 (for example, 500 to 5000) in the measurement method by GPC (polystyrene conversion). It may be about 700 to 4000 (for example, 1000 to 3000). The weight average molecular weight Mw of polysilane is measured by GPC (polystyrene conversion), for example, from 1000 to 100,000 (for example, 3000 to 50000), preferably from 5000 to 30000, and more preferably from 70000 to 20000 (for example, 90000 to 15000). It may be about. If the degree of polymerization and molecular weight are too small, the reactivity of the curable composition and the refractive index, heat resistance and water repellency of the cured product may decrease, and if the degree of polymerization and molecular weight are too large, the cured product may be mechanical. There is a risk that the characteristics will deteriorate.

Polysilane may be in a solid state or a liquid state at room temperature (for example, about 15 to 25 ° C.), and may be in a solid state from the viewpoint of handleability and is uniform in the composition. It may be a liquid polysilane because it is easily dispersed in the liquid.

The ratio of the cationically polymerizable compound (for example, the total amount of the first and second cationically polymerizable compounds) to polysilane is, for example, in a wide range of about 99/1 to 10/90 of the former / latter (weight ratio). Can be selected from, for example, 90/10 to 20/80 (for example, 80/20 to 25/75), preferably 70/30 to 30/70 (for example, 65/35 to 35/65), and 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 refractive index of the cured product may be increased, and the heat resistance and water repellency may be lowered. If the proportion of polysilane is too large, the mechanical properties of the cured product may be deteriorated.

[Other ingredients]
(Photoacid generator)
The curable composition of the present invention often contains a photoacid generator as a polymerization initiator. Examples of the photoacid generator include conventional photoacid generators such as imidazolate compounds, thioxanthone oxime ester compounds, onium salts, metallocene complexes, sulfonimide compounds, disulfone compounds, sulfonic acid ester compounds, triazine compounds and quinonediazide compounds. Although it may be a diazomethane compound or the like, it is preferably a photoacid generator that absorbs visible light to generate acid from the viewpoint of suppressing decomposition or deterioration of polysilane due to light irradiation.

Examples of the photoacid generator that absorbs visible light to generate acid include phenylthiophenes [for example, bis (4-methylphenyl) (5-phenyl-thiophen-2-yl) sulfonium hexafluorophosphate and the like. Phenylthiophene sulfonium salts, etc.]; Dioxorophenyltriazines [eg, dioxolophenyl-bis (haloalkyl) -triazine, etc., such as 2-dioxorophenyl-4,6-bis (trichloromethyl) -triazine] Benzothiophenes [eg, benzothiophene sulfonium salts such as bis (4-n-butoxyphenyl) (benzothiophen-2-yl) sulfonium hexafluorophosphate]; thiantolens [eg, N-trifluoromethanesulfonyloxy N-haloalkane sulfonyloxy-thiantorange carboxylic acid imides such as -7-t-butylthiantrene-2,3-dicarboxylic acidimide; 7-t-butyl-5- (4-methoxyphenyl) thiantrenium-2, 3-Dicarboxylic acid imide Trifluoromethanesulfonate, 7-t-butyl-5- (4-methoxyphenyl) thiantrenium-2,3-dicarboxylic acid imide Hexafluorophosphate and other thiantrenium dicarboxylic acid imide salts Etc.]; Phenoxazines; Phenoxatiins; Phenothiazines and the like.

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

(In the formula, R ¹² represents a fluorohydrocarbon group and R ¹³ represents an alkyl group).

In the formula (4), as a fluorohydrocarbon group R ^12, for example, a trifluoromethyl group, pentafluoroethyl group, or perfluoro C _1-4 alkyl groups such as nonafluorobutyl group, pentafluorophenyl group, etc. Perfurulo C _6-14 aryl group and the like. Of these fluorohydrocarbon groups, a perfluoroC _1-2 alkyl group (particularly a trifluoromethyl group) is preferable.

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. _{Of these alkyl groups, C 1-4} alkyl groups such as methyl group and t-butyl group are preferable, and t-butyl group is particularly preferable. The substitution position of the substituent R ¹³ is preferably, for example, any of the 6 to 9-positions, and particularly preferably the 7-position or the 8-position.

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

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

(solvent)
The photopolymerizable composition of the present invention may contain a solvent from the viewpoint of improving handleability and coatability. Solvents include, for example, hydrocarbons (hexane, cyclohexane, toluene, etc.); alcohols (ethanol, propanol, etc.); ethers [diethyl ether, tetrahydrofuran (THF), etc.]; ketones [ethylmethylketone (2-butanone, etc.) ), 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 (diglime), diethylene glycol methyl ethyl ether, etc.]; Cellosolve acetates (propylene glycol methyl acetate, etc.) and the like.

These solvents can be used alone or in combination of two or more. Among 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. The ratio of the typical solvent is, for example, 100 to 10000 parts by weight, preferably 200 to 1000 parts by weight, and more preferably 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 commonly used additives. Other additives include, for example, sensitizers (coumarins, quinolins, quinones, phenoxazines, aromatic hydrocarbons (pyrenes, etc.), amines, etc.), reactive polymers (phenolic resins, etc.) Oxetanyl group (and / or epoxy group) reactive group, colorant (dye pigment), thickener, stabilizer (antioxidant, antioxidant, ozone deterioration inhibitor, etc.), extinguishing Examples include foaming agents, leveling agents, dispersants, flame retardants, antistatic agents, fillers, lubricants and the like. These additives can be used alone or in combination of two or more. The ratio of these additives can be appropriately selected depending on the type of additive, and is preferably 100 parts by weight or less (for example, 0.1 to 50 parts by weight) with respect to 100 parts by weight of 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 and polysilane, and if necessary, other components (photoacid generator, conventional additive, etc.), and is dissolved and dispersed with a solvent or a dispersant as necessary. And it is obtained by uniformly mixing by mixing or the like.

[Cured product and its manufacturing method]
In the present invention, a cured product (three-dimensional cured product, cured film or cured pattern) is produced by a production method including a photo-curing step of irradiating the curable composition with light (for example, visible light) to form a photo-cured product. One-dimensional or two-dimensional cured product, point or dot-shaped cured product, etc.) may be produced.

In the photocuring step, the photocurable product (photocurable film, photocurable pattern, etc.) is irradiated with light (for example, visible light) after the curable composition is applied onto a substrate to form a coating film (for example, visible light). It may be formed by exposure). Therefore, the curable composition may be used, for example, for producing a coating film (thin film) on a substrate. When the curable composition is applied to a substrate to produce a coating film, a curable composition containing a solvent (a solution in which a cationically polymerizable compound, polysilane, a photoacid generator, etc. is dissolved or dispersed in the solvent or the like is used. Dispersion solution) may be applied to the base material.

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. Be done.

The thickness of the coating film can usually be selected from the range of about 0.01 μm to 10 mm depending on the intended use of the cured product. In the case of a photoresist, the thickness of the coating film is usually about 0.05 to 10 μm, and may be, 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, and may be, 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, and may be, for example, about 0.3 to 50 μm.

The wavelength of the light may be appropriately selected depending on the type of the photoacid generator, and is preferably visible light from the viewpoint of suppressing the decomposition or deterioration of polysilane. The wavelength of visible light may be 380 to 780 nm, but from the viewpoint of easily generating acid and improving photocurability, for example, 380 to 600 nm, preferably 385 to 500 nm, and more preferably 390 to 450 nm ( In particular, it is about 400 to 410 nm), and h-ray (405 nm) that can be irradiated with a high-pressure mercury lamp, an LED laser, or the like is particularly preferable.

The amount of light irradiation (exposure amount) can be selected from the range in which the curable composition can be cured according to the thickness of the coating film and the like. For example, 10 mJ / cm ² or more (for example, 10 to 10000 ^{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 amount of exposure is too small, the photocurability may decrease.

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 (LED laser, etc.).

The curable composition may be used for the formation of patterns and images (such as the manufacture of printed wiring boards). When producing a printed wiring board, a resin composition may be applied onto a base material to form a coating film, and the formed coating film may be irradiated with light (pattern exposure). The pattern exposure may be performed by scanning a laser beam or by irradiating light through a photomask. A pattern or image may be formed by removing (or dissolving) a non-irradiated region (unexposed portion) generated by pattern exposure with a developer. Examples of the developer include water, an aqueous alkaline solution, and a hydrophilic solvent (for example, alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves, cellosolve acetates, etc.). And a mixed solution of these.

In the present invention, in order to further improve the strength of the cured product, heat treatment may be performed in addition to photocuring. In the heat treatment, the curable composition may be heated together with the irradiation of light in the photocuring step, or may be heated by providing a heating step for heating the photocurable product that has undergone the photocuring step. The polymerization reaction is promoted by heating, a high degree of three-dimensional cross-linking occurs, and a high-strength cured product can be obtained. Of these, a method of providing a heating step is preferable from the viewpoint of improving the cross-linking strength and insolubilization rate of the cured product.

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. It may be highly crosslinked in the irradiation region (exposed area) of the coating film remaining on the substrate by heating. By heating, a fine and highly accurate pattern can be formed on the base material even with visible light. Therefore, the curable composition of the present invention may be used in applications that require a precise pattern, for example, in the manufacture of printed wiring boards for electronic devices.

The heating temperature may be, for example, about 80 to 200 ° C., preferably 110 to 180 ° C., more preferably 140 to 160 ° C. (particularly 145 to 155 ° C.). The heating time may be, for example, about 5 seconds to 1 hour, preferably 30 seconds to 20 minutes, and more preferably 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, a plurality of layers of a curable composition may be formed on a substrate. Further, after forming another functional layer or the like on the base material, a layer of the curable composition may be formed on the functional layer. The resin composition of the present invention has excellent transparency of visible light, high refractive index, and excellent optical characteristics. Therefore, in particular, a high refractive index layer of an antireflection film such as a liquid crystal display, a reflective plate, etc. It may be used 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 substrate or an optical thin film, a semiconductor (silicon, gallium arsenic, gallium nitride, silicon carbide, etc.), a metal (aluminum, copper, etc.), a ceramic (Zyrosine oxide, titanium oxide, lead zirconate titanate (PZT), etc.), transparent inorganic materials (glass, quartz, magnesium fluoride, calcium fluoride, etc.), transparent resins (polymethylmethacrylate, polymethylacrylate, 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 to 99.9%), more preferably 70 to 100% (particularly 75 to 99.9%). In the present invention, the insolubilization rate can be calculated from the film thickness ratio before and after immersion in THF for 10 minutes as in the method described in Examples described later. Although the cured product tends to become brittle as the insolubilization rate increases, the obtained cured product has surprisingly excellent flexibility (or toughness). Therefore, the cured product of the present invention can have both a high insolubilization rate and flexibility.

Further, the curable composition and the cured product of the present invention show excellent contrast (developability) in pattern formation because the difference in insolubilization rate before and after light irradiation is large. 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%), and more preferably 1% or less (for example, substantially). It may be about 0%). The difference in insolubilization rate before and after light irradiation may be, for example, about 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 1.64 to 1.8. 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.). It may be about 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. In addition, various evaluation methods and raw materials used are shown below.

[Evaluation methods]
(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 dry for 1 hour, and the ratio of the average thickness (after drying) of the cured product before and after immersion. (After immersion / Before immersion) was calculated as the insolubilization rate. The average thickness of the cured product was calculated by the arithmetic mean of the thickness measured at 9 points using a non-contact film thickness measuring device (“Nanospec / AFT M-3000” manufactured by Nanometrics Japan Co., Ltd.).

(contrast)
The insolubilization rate of the thin film formed in Examples and Comparative Examples before light irradiation (the thin film formed by removing the solvent after applying the curable composition) was evaluated, and the contrast (development) was performed according to the following criteria. Gender) was evaluated.

◯: The difference in insolubilization rate before and after light irradiation is 60% or more. ×: The difference in insolubilization rate before and after light irradiation is less than 60%.

(Refractive index)
Refraction of the cured product obtained in Examples and Comparative Examples at the D line (wavelength 589 nm) under the condition of a temperature of 25 ° C. using a multi-wavelength Abbe refractometer (“DR-M4” manufactured by Atago Co., Ltd.). The rate nD was measured. An interference filter having a wavelength of 589 nm was used for the measurement.

(Flexibility or toughness)
The cured products obtained in Examples and Comparative Examples were evaluated according to the following criteria from the feel of touching with a finger.

◯: The film is soft and hard to crack ×: The film is brittle and cracks.

[material]
(Cationopolymerizable compound)
BNFO: 9,9-bis [6- (3-methyl-3-oxetanyl) methoxy-2-naphthyl] fluorene, synthesized by Synthesis Example 1 described later BPEF-9EO-O: 9,9-bis [4- (2) -Hydroxyethoxy) -phenyl] Fluorene with an average of 9 mol of ethylene oxide added to the adduct bis ((3-methyl-3-oxetanyl) methyl) ether, synthesized by Synthesis Example 2 described later BNFG: 9,9- Bis (6-glycidyloxy-2-naphthyl) fluorene, synthesized according to Synthesis Example 1 of JP2012-102228A BPFG: 9,9-bis (4-glycidyloxyphenyl) fluorene, JP2012-102228 Synthetic 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 acid imide, "SIN-11" manufactured by Sanpo Chemical Laboratory Co., Ltd.
(solvent)
Cyclohexanone: Made by Nacalai Tesque Co., Ltd.

[Synthesis Example 1]
9,9-Bis (6-hydroxy-2-naphthyl) fluorene (BNF, manufactured by 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. 3-Chloromethyl-3-methyloxetane (58.8 g, 487 mmol) was added dropwise to this solution at 60 ° C., and after completion of the addition, the temperature was raised to 80 ° C. for 5 hours, and the temperature was further raised 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 carried out three times. Then, washing with 300 g of water was carried out 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)) was analyzed. )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-115 as a photopolymerization initiator were stirred and uniformly mixed. The obtained mixed solution was spin-coated on a silicon substrate at 2000 rpm for 20 seconds, prebaked on a hot plate at 60 ° C. for 2 minutes to remove the solvent, and a thin film having a film thickness of 0.5 to 2.0 μm was removed. Was formed. ^{The obtained thin film was irradiated with visible light having a wavelength of 405 nm at 1600 mJ / cm 2} 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 a mixed solution of 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-115 was 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 a mixed solution of 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 was used. .. The obtained cured product had a refractive index of 1.6817 and an insolubilization rate of 64%.

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

(In the formula, n1 + n2 indicates 11 on average).

[Example 4]
Curing in the same manner as in Example 1 except that a mixed solution of BPEF-9EO-O 60.3 parts by weight, BNFG 6.7 parts by weight, PMPS 33 parts by weight, cyclohexanone 360 parts by weight and SIN-115 parts by weight was used. The thing was prepared. The obtained cured product had a refractive index of 1.6698 and an insolubilization rate of 71%.

[Comparative Example 1]
An attempt was made to prepare a cured product 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-115 was used. The cured product could not be formed probably 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-115 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-115 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-115 was used without adding PMPS. The obtained cured product had a refractive index of 1.6684 and an insolubilization rate of 70%.

The results obtained in Examples and Comparative Examples are shown in Table 1.

As is clear from Table 1, the refractive index of the examples was higher than that of the comparative examples. Further, in Examples, although a bifunctional cationically polymerizable compound was used as in Comparative Example 1, a surprisingly high insolubilization rate was exhibited and the contrast was also good. Further, in the examples, the flexibility was also excellent as compared with Comparative Example 2, and a high insolubilization rate and flexibility could be achieved at the same time.

The curable composition of the present invention and the cured product thereof are a paint, an electric wire coating material, a sealing material and an insulating material for electronic devices, a printed wiring board, a protective film, a photoresist, a printing plate making material, an ink, an adhesive, and an adhesive material. , Optical thin film (high refractive index layer of antireflection film such as liquid crystal display, reflector, etc.) can be suitably used.

Claims (10)

A curable composition containing a cationically polymerizable compound and polysilane, wherein the cationically polymerizable compound has the following formula (1).
(In the formula, Ar ¹ and Ar ² are arene rings, Z ¹ and Z ² are naphthalene rings, respectively, R ^1a and R ^1b and R ^{2a and R 2b} are substituents, and R ^3a and R ^3b are linear, respectively. Alternatively, the branched chain alkylene groups, R ^4a and R ^4b , are hydrogen atoms or substituents, respectively, and k1 and k2, m1 and m2, and n1 and n2 are integers of 0 or more, respectively.)
A curable composition containing the first cationically polymerizable compound represented by. In formula (1), Ar ¹ and Ar ² are C _6-10 arene rings, R ^3a and R ^3b are linear or branched C _2-6 alkylene groups, respectively, and R ^{4a and R 4b} are hydrogen atoms, respectively. Alternatively, _{the curable composition according to claim 1, wherein the C 1-6} alkyl group, k1 and k2 are integers of 0 to 4, m1 and m2 are integers of 0 to 6, respectively, and n1 and n2 are integers of 0 to 20, respectively. Stuff. In formula (1), Ar ¹ and Ar ² are benzene rings, R ^3a and R ^3b are linear or branched C _2-4 alkylene groups, and R ^4a and R ^4b are C _1-4 alkyl groups, respectively. The curable composition according to claim 1 or 2, wherein k1 and k2 are integers of 0 to 2, m1 and m2 are integers of 0 to 2, respectively, and n1 and n2 are integers of 0 to 8, respectively. The cationically polymerizable compound further contains the following formula (2).
(In the formula, Ar ³ and Ar ⁴ and Z ³ and Z ⁴ are arene rings, R ^5a and R ^5b and R ^{6a and R 6b} are substituents, respectively, and R ^7a and R ^7b are linear or branched chains, respectively. The alkylene group, R ^8a and R ^8b are hydrogen atoms or methyl groups, respectively, p1 and p2, q1 and q2 and r1 and r2 are integers of 0 or more, respectively, and s1 and s2 are integers of 1 to 4).
The curable composition according to any one of claims 1 to 3, which comprises a second cationically polymerizable compound represented by. In formula (2), Ar ³ and Ar ⁴ are C _6-10 arene rings, Z ³ and Z ⁴ are C _6-12 arene rings, and R ^7a and R ^{7 b} are linear or branched C _{2-. 6. The} fourth aspect of claim 4, wherein the alkylene group, p1 and p2 are integers of 0 to 4, q1 and q2 are integers of 0 to 6, respectively, r1 and r2 are integers of 0 to 20, respectively, and s1 and s2 are 1 or 2. Curable composition. The curable composition according to claim 4 or 5, wherein the ratio of the first cationically polymerizable compound to the second cationically 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 comprises a chain _{polyC 1-6} alkyl C 6-14 arylsilane. The curable composition according to any one of claims 1 to 7, wherein the ratio of the cationically polymerizable compound to polysilane is the former / the latter (weight ratio) = 90/10 to 20/80. A cured product obtained by curing the curable composition according to any one of claims 1 to 8. The cured product according to claim 9, wherein the refractive index at a temperature of 25 ° C. and a wavelength of 589 nm is 1.65 to 1.75.