JP2014012826A - Curable composition and cured product of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which can increase or improve the adhesiveness of a cured product thereof to a substrate without impairing excellent properties such as high refractive index.SOLUTION: A curable composition comprises at least a curable component comprising a polyfunctional curable compound (A) [for example, a (meth)acrylic compound having a fluorene skeleton, such as 9,9-bis((meth)acryloyloxyaryl) fluorenes, and 9,9-bis((meth)acryloyloxy(poly)alkoxyaryl) fluorenes] and a specific fluorene compound (B) having a hydrolytically condensable group. The curable component may further contain a monofunctional curable compound.

Description

  The present invention relates to a curable composition containing a fluorene compound having a hydrolytic condensable group and a cured product thereof.

  A curable component such as a heat or photo-curable resin forms a cured product on various substrates depending on the application. Therefore, such a curable component or cured product is required to have adhesion to the substrate, but depending on the combination of the curable component and the substrate, the adhesion may not be sufficient. For example, a cured product of a (meth) acrylic compound is widely used as an optical material, and has a high light-transmitting substrate [for example, an inorganic substrate (glass, etc.), an organic substrate (polyethylene terephthalate, polycarbonate, cellulose triacetate). Etc.), etc.], but generally has low adhesion to a substrate such as glass.

  In order to improve such adhesion, various techniques are being developed. For example, JP 2009-167244 A (Patent Document 1) discloses an active energy ray-curable glass containing a specific radical polymerizable compound (for example, di (meth) acrylic acid polyethoxylated hydrogenated bisphenol A). It is described that a silane coupling agent (such as γ- (meth) acryloxypropyltrimethoxysilane) can be used as a component for improving the adhesion of the adhesive composition.

  However, with such a silane coupling agent, depending on the type of the (meth) acrylic compound to be combined, there is a risk that properties such as the refractive index will be significantly reduced. In addition, sufficient compatibility and storage stability cannot be ensured, handling properties may be impaired, and good cured products may not be obtained. In addition, physical properties such as hardness and optical characteristics (refractive index, etc.) are insufficient, and there is a risk that the appearance may be impaired by bleeding out.

  On the other hand, it has high refractive index and heat resistance for hard coating or scratch resistance for optical materials such as optical overcoat agent, hard coat agent, antireflection film, spectacle lens, optical fiber, optical waveguide, and hologram. A polymerizable compound having a fluorene skeleton (in particular, a 9,9-bisarylfluorene skeleton) (for example, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene) There has been proposed a curable composition containing.

  However, the curable composition containing a polymerizable compound having such a fluorene skeleton also usually has insufficient adhesion to the substrate, and a cured product (cured film) cannot be formed on the substrate with high adhesion. There are many cases.

  In JP-A-2007-91870 (Patent Document 2), a specific polyfunctional (meth) acrylate having a fluorene skeleton and a hydrolytic condensable organosilicon compound having a polymerizable group (for example, γ- ( (Meth) acryloyloxypropyltrimethoxysilane and the like) and a photoacid generator, and a hydrolytic condensable organosilicon compound having no polymerizable group (for example, phenyltrimethoxysilane) ) Is disclosed. In this document, it is assumed that a hydrolyzable condensable organosilicon compound having a polymerizable group is polymerized with a polyfunctional (meth) acrylate and hydrolyzed and condensed (sol-gel reaction) to obtain a hybrid cured film. It is assumed that the hydrolytic condensable organosilicon compound having no functional group is hydrolyzed and condensed (sol-gel reaction) together with the hydrolytic condensable organosilicon compound having a polymerizable group. It is not assumed to be used as a component for improving. Moreover, when these components are used, there exists a possibility that the optical characteristics (refractive index etc.) derived from the specific polyfunctional (meth) acrylate which has a fluorene skeleton may be reduced. Furthermore, curing shrinkage is likely to occur.

  In JP 2009-256293 A (Patent Document 3) and JP 2009-269854 A (Patent Document 4), a 9,9-bisarylfluorene skeleton and a hydrolytic condensable silicon-containing group (such as an alkoxy group) are disclosed. ) Are disclosed.

  In these documents, it is assumed that the fluorene compound is used as a component (that is, a modifier for titanium alkoxides) for obtaining an organic-inorganic hybrid by a sol-gel reaction combined with titanium alkoxides, Similar to Patent Document 2, it is not assumed to be used as a component that improves adhesion to the substrate.

JP 2009-167244 A (claims, paragraph [0020], examples) JP 2007-91870 A (Claims, Examples) JP 2009-256293 A (Claims, Examples) JP 2009-269854 A (Claims, Examples)

  Therefore, the objective of this invention is providing the curable composition which can improve or improve the adhesiveness of the hardened | cured material with respect to a base material (especially inorganic base materials, such as a glass base material), and its hardened | cured material.

  Another object of the present invention is to provide a curable composition capable of improving or improving adhesion to a substrate without impairing excellent properties such as a high refractive index, and a cured product thereof.

  Still another object of the present invention is to provide a curable composition that is excellent in storage stability and capable of forming a cured product without curing shrinkage, and a cured product thereof.

  Another object of the present invention is to provide an additive for improving or improving the adhesion of a cured product to a substrate and a method for improving or improving the adhesion to a substrate using the additive.

  Still another object of the present invention is to provide an additive for improving or improving the adhesion of a cured product to a substrate without impairing the storage stability and compatibility with the curable component, and to use this additive as a basis. The object is to provide a method for improving or improving the adhesion to a material.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a fluorene compound having a hydrolytic condensable group is a polyfunctional curable compound (for example, a polyfunctional (meth) acrylic compound). It is possible to improve or improve the adhesion of the curable composition containing the curable component (or its cured product) to the base material, and such a fluorene compound is excellent in compatibility with the curable component and good. Even when combined with a curable component, it can form a cured product without impairing storage stability, while maintaining excellent properties such as high refractive index at a high level (or depending on the type of curable component, The inventors have found that properties such as refractive index can be improved or improved and a cured product can be formed, and the present invention has been completed.

  That is, the curable composition of the present invention comprises a curable component (curable resin, curable resin component) composed of a polyfunctional curable compound (A), and a fluorene compound having a hydrolytic condensable group ( B). The curable compound (A) may be a radical polymerizable compound such as a (meth) acrylic compound. The curable compound (A) may be a compound having a fluorene skeleton.

  Typically, the curable compound (A) may be a (meth) acrylic compound including a (meth) acrylic compound having a fluorene skeleton. In such a curable composition, the (meth) acrylic compound having a fluorene skeleton is a compound represented by the following formula (A1) [for example, 9,9-bis ((meth) acryloyloxyaryl) fluorenes, 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorenes and the like].

(In the formula, ring Z represents an aromatic hydrocarbon ring, R ¹ represents a substituent, R ² represents an alkylene group, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a substituent, and k represents An integer of 0 to 4, m is an integer of 0 or more, n is an integer of 0 or more, and p is an integer of 1 or more.)
The curable component further includes a monofunctional curable compound (for example, at least one monofunctional curable compound selected from aromatic (meth) acrylate and sulfur-containing (meth) acrylate). Also good. In such a curable composition, the ratio of the monofunctional curable compound may be, for example, about 10 to 600 parts by weight with respect to 100 parts by weight of the polyfunctional curable compound (A).

  In the curable composition of the present invention, the fluorene compound (B) may be, for example, a compound represented by the following formula (B1).

{Wherein X is a linking group, R ⁵ , R ⁶ and R ⁷ are the same or different and are a hydrogen atom, a hydroxyl group, a halogen atom, a group —OR ⁸ , wherein R ⁸ is a hydrocarbon group or a group -[(R ⁹ O) _a -R ¹⁰ ] (wherein R ⁹ represents a hydrocarbon group, R ¹⁰ represents a hydrocarbon group, a represents an integer of 1 or more) or a hydrocarbon group, , R ¹ , R ² , R ³ , R ⁴ , k, m, n, p are the same as above. However, at least one of R ⁵ , R ⁶ and R ⁷ is a hydrogen atom, a hydroxyl group, a halogen atom, or a group —OR ⁸ . }
In the above formula (B1), X may be a group containing a sulfur atom (linking group). Typically, in the formula (B1), X may be a group represented by the following formula.

—OCO—CHR ¹¹ —CH ₂ —S—X ^4a —
(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and X ^4a represents an alkylene group.)
The refractive index of the fluorene compound (B) may be 1.55 or more at 25 ° C. and 589 nm.

  In the curable composition of the present invention, the ratio of the fluorene compound (B) may be, for example, about 0.1 to 30 parts by weight with respect to 100 parts by weight of the curable component. Further, the molecular weight per hydrolytic condensable group contained in the fluorene compound (B) may be about 500 to 10,000 with respect to the total amount of the curable component and the fluorene compound (B).

  In the curable composition of the present invention, even if the fluorene compound (B) is combined with the curable component, a decrease in the refractive index can be suppressed as much as possible. For example, the refractive index (25 ° C., 589 nm) of the curable component can be reduced. n1, When the refractive index (25 ° C., 589 nm) of the curable composition is n2, the reduction rate of the refractive index represented by the formula [(n1−n2) / n1] × 100 (%) is 0.5%. It may be the following.

  The present invention includes a method for producing a cured product that imparts active energy to the curable composition and cures the curable composition. Moreover, the hardened | cured material (or hardened | cured material obtained by the said manufacturing method) which the said curable composition hardened | cured is also contained in this invention. Such a cured product may be formed on a substrate. Therefore, the present invention comprises a substrate [particularly, a substrate composed of a transparent inorganic material such as glass (transparent substrate, transparent inorganic substrate)] and the cured product formed on the substrate. The laminated body made is also included.

  Therefore, in this invention, in order to improve or improve the adhesiveness with respect to the base material (especially inorganic base materials, such as glass) of the hardened | cured material containing the curable component comprised by the polyfunctional curable compound (A). And an additive composed of a fluorene compound (B) having a hydrolytic condensable group. Moreover, the said additive is added or mixed with the curable composition containing the sclerosing | hardenable component comprised by the polyfunctional curable compound (A), and with respect to the base material of the hardened | cured material which the said curable composition hardened | cured A method for improving or improving adhesion is also included.

  In the curable composition of this invention, the adhesiveness of the hardened | cured material with respect to a base material (especially inorganic base materials, such as a glass base material) can be improved or improved. In addition, excellent properties such as high refractive index (for example, optical properties) are not impaired, and excellent properties of the curable composition or cured product can be maintained or maintained at a high level, depending on the type of curable component. Further, characteristics such as refractive index can be improved or improved. In particular, the difference in refractive index between a cured product and a glass substrate is usually large, but in the present invention, such a difference in refractive index can be made relatively small. Therefore, a cured product with reduced interference fringes (a substrate on which the cured product is formed) can also be obtained efficiently. In addition, the fluorene compound (B) may be easily transferred to the surface of the base material depending on the affinity depending on the type of the base material (for example, in the case of a glass base material). However, depending on the type of the curable component, the refractive index difference between the curable compound (A) and the fluorene compound (B) is relatively small, so the refractive index spread (variation, distribution) in the entire cured product is high. Can be suppressed.

  Moreover, the curable composition of this invention is excellent in storage stability, and its handleability is also favorable. In addition, such a curable composition can suppress (or prevent) curing shrinkage. Furthermore, the additive (adhesion improver or adhesion improver) of the present invention is useful as an additive for improving or improving the adhesion of the cured product to the substrate as described above. In particular, such an additive can improve or improve the adhesion of the cured product to the substrate without impairing the storage stability and compatibility with the curable component.

[Curable composition]
The curable composition (resin composition) of the present invention has a curable component (curable resin, curable resin component) composed of a polyfunctional curable compound (A) and a hydrolytic condensable group. A fluorene compound (B).

(Curable compound (A))
Examples of the polyfunctional curable compound (A) include a heat or photocurable resin (heat or photocurable compound) such as a radical polymerizable resin [or a radical polymerizable compound such as an unsaturated polyester resin or diallyl phthalate. Resin, vinyl ester resin, (meth) acrylic compound ((meth) acrylic resin, etc.), condensation resin [or condensation compound, such as phenol resin, amino resin (urea resin, melamine resin, etc.), furan resin , Epoxy resin (epoxy compound), episulfide resin (episulfide compound), polyurethane resin, silicone resin, polyimide resin, and the like]. The curable compounds may be used alone or in combination of two or more.

  Preferred curable compounds (A) include radically polymerizable compounds (polymerizable unsaturated bond-containing compounds), particularly (meth) acrylic compounds. In this invention, even if it is a sclerosing | hardenable component with few adhesiveness with respect to base materials (especially glass base material etc.) like a (meth) acrylic-type compound, the adhesiveness with respect to a base material can be improved.

As the (meth) acrylic compound (polyfunctional (meth) acrylic compound), for example, polyfunctional (meth) acrylate, for example, bifunctional (meth) acrylate {for example, alkylene glycol di (meth) acrylate [C _2-10 alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. Etc.], (poly) oxyalkylene glycol di (meth) acrylate [for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol Of (poly) oxy C _2-6 alkylene glycol di (meth) acrylate such as di (meth) acrylate and polytetramethylene glycol di (meth) acrylate], bisphenol A (or its C _2-3 alkylene oxide adduct) Di (meth) acrylate, bridged cyclic (meth) acrylate (eg, tricyclodecane dimethanol di (meth) acrylate, etc.), alkanetri to hexaol di (meth) acrylate [eg, glycerin di (meth) acrylate, trimethylol Etanji (meth) acrylates, C _3-10 alkane tri to Hekisaoruji (meth) acrylates such as trimethylolpropane di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate], etc. , Trifunctional or higher (meth) acrylate {e.g., polyhydric alcohols (or its C _2-3 alkylene oxide adducts) (meth) acrylate, for example, glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate polyol tri to hexa (meth) acrylate}, (poly) urethane (meth) acrylate, (poly) este (Meth) acrylate, epoxy (meth) acrylate. The (meth) acrylic compound also includes a (meth) acrylic compound having a fluorene skeleton as described later.

  The (meth) acrylic compounds may be used alone or in combination of two or more.

  A preferable curable compound (A) includes a curable compound having a fluorene skeleton. The curable compound having such a fluorene skeleton is excellent in affinity (or compatibility) with the fluorene compound (B), and a good cured product is easily obtained. Moreover, by having a fluorene skeleton in common, even if the fluorene compound (B) is combined with the curable compound (A), characteristics such as refractive index (such as optical characteristics) can be easily maintained at a high level.

Examples of the curable compound having a fluorene skeleton include the above-described heat or photocurable resins, for example, (meth) acrylic compounds (such as compounds represented by the formula (A1) described below), epoxy compounds {formulas described below ( In A1), a compound in which a (meth) acryloyl group (—CO—CR ³ ═CH ₂ ) is substituted with a glycidyl group, such as 9,9-bis (glycidyloxyphenyl) fluorene [for example, 9,9-bis (4 - glycidyloxyphenyl) fluorene, 9,9-bis (mono- or _{di-C 1-4} alkyl - glycidyl oxyphenyl) fluorene [9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, 9,9 - bis (4-glycidyloxy-3,5-dimethylphenyl) fluorene, etc.], 9,9-bis (mono- or _{di-C 6-10} ants Lu-glycidyloxyphenyl) fluorene [9,9-bis (4-glycidyloxy-3-phenylphenyl) fluorene and the like], 9,9-bis [di- or tri (glycidyloxy) phenyl] fluorene [for example, 9,9 -Bis [3,4-di (glycidyloxy) phenyl] fluorene, etc.], 9,9-bis (glycidyloxynaphthyl) fluorene [9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, etc.], 9 , 9-bis (glycidyloxy alkoxyphenyl) fluorene [e.g., 9,9-bis (4-glycidyloxy-ethoxyphenyl) fluorene such as 9,9-bis (glycidyloxy _{C 2-4} alkoxyphenyl) fluorene, etc.], etc.} Etc. The curable compounds having a fluorene skeleton may be used alone or in combination of two or more.

  Among these curable compounds, (meth) acrylic compounds having a fluorene skeleton are particularly preferable.

  A (meth) acrylic compound having a fluorene skeleton [or a fluorene compound having two or more (meth) acryloyl groups] has a fluorene skeleton together with a (meth) acryloyl group (or (meth) acryloyloxy group). Yes.

  Examples of such a fluorene skeleton include fluorene (fluorene skeleton having no substituent at the 9-position), 9-substituted fluorene (for example, 9-alkylfluorene, 9-monoarylfluorene, 9,9-bisarylfluorene, etc.). And fluorene having a hydrocarbon group. A typical fluorene skeleton is a 9,9-bisarylfluorene skeleton. Note that the fluorene skeleton may have a substituent in fluorene or a substituent substituted at the 9-position of fluorene.

  The substitution position (bonding position) of the (meth) acryloyl group (or a group containing the (meth) acryloyl group) is not particularly limited, and may be the fluorene skeleton itself or bonded to the substituent located at the 9th position of fluorene. You may do it.

  Typical (meth) acrylic compounds having a fluorene skeleton include 9,9-bisarylfluorenes having two or more polymerizable unsaturated bonds (particularly (meth) acryloyl groups), for example, the following formula (A1) And the like.

(In the formula, ring Z represents an aromatic hydrocarbon ring, R ¹ represents a substituent, R ² represents an alkylene group, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a substituent, and k represents An integer of 0 to 4, m is an integer of 0 or more, n is an integer of 0 or more, and p is an integer of 1 or more.)
In the above formula (A1), examples of the aromatic hydrocarbon ring represented by ring Z include a benzene ring and a condensed polycyclic arene (or condensed polycyclic aromatic hydrocarbon) ring. As the condensed polycyclic arene (or condensed polycyclic aromatic hydrocarbon) ring, for example, a condensed bicyclic arene ring (for example, a C _8-20 condensed bicyclic arene ring such as an indene ring or a naphthalene ring), Examples thereof include fused bicyclic to tetracyclic arene rings such as fused tricyclic arene rings (eg, anthracene ring). The two rings Z may be the same or different rings, and may usually be the same ring.

  A typical ring Z is a benzene ring or a naphthalene ring.

In the formula (A1), examples of the group R ¹ include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [eg, an alkyl group, an aryl group (C ₆ such as a phenyl group). Non-reactive substituents such as an _-10 aryl group), etc., and in particular, an alkyl group is often used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, such as _{C 1-12} alkyl group _{(e.g., C 1-8} alkyl groups, especially methyl groups, such as t- butyl group _{C 1- 4} alkyl group) and the like. In addition, when k is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

In the formula (A1), examples of the alkylene group represented by the group R ² include C _2-6 alkylene groups such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group, Is a C _2-4 alkylene group, more preferably a C _2-3 alkylene group. When m is 2 or more, the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group. In the two rings Z, the groups R ² may be the same or different, and may usually be the same.

The number (addition mole number) m of oxyalkylene groups (OR ² ) can be selected, for example, from a range of about 0 to 25 (for example, 0 to 20) according to the application and desired performance, and is usually 0 to 18 (For example, 0 to 15), preferably 0 to 12 (for example, 0 to 10), more preferably 0 to 8 (for example, 0 to 7), particularly 1 or more. Two m's may be the same or different.

  In the formula (A1), the total of two m is, for example, 0 to 30 (for example, 0 to 25), preferably 0 to 20 (for example, 0 to 18), more preferably 0 to 16 (for example, 0-14) may be sufficient and 2 or more may be sufficient especially.

  In the formula (A1), various properties (hardness, viscosity, refractive index, etc. in the cured product) vary depending on the sum of two m. Therefore, the sum of the two m values may be adjusted according to desired characteristics. For example, in the formula (A1), the sum of two m may be relatively small (for example, 2 to 6, preferably 2 to 5, more preferably 2 to 4, particularly about 2 to 3). Thus, when the sum of two m is made small, it is easy to obtain a hard cured product with a high refractive index and high heat resistance.

  On the other hand, in the formula (A1), the sum of two m is relatively large [for example, 6 or more (for example, 6.5 to 20), preferably 7 to 18 (for example, 7 to 16), and more preferably 8 to 14 (for example, 8.5 to 12), particularly 9 to 12 (for example, about 9.5 to 11.5)]. When the sum of the two m is increased in this way, it is easy to obtain a cured product having softness or flexibility while having a relatively high refractive index and heat resistance.

  The compound represented by the formula (A1) may be an aggregate of compounds having the same value of m, or an aggregate of compounds having different values of m. In the latter case, the value of m and the sum of the two m are average values (arithmetic average or arithmetic average).

In the formula (A1), the substitution number p of the group containing the group R ² (sometimes referred to as a (meth) acryloyl group-containing group) may be 1 or more, for example, 1 to 4, preferably 1 to 3, more preferably 1-2, especially 1. In addition, the substitution number p may be the same or different in each ring Z, and is usually the same in many cases. The substitution position of the (meth) acryloyl group-containing group is not particularly limited as long as it is substituted at an appropriate substitution position on ring Z. For example, when the ring Z is a benzene ring, the (meth) acryloyl group-containing group may be substituted at an appropriate position (particularly at least the 4th position) of the benzene ring, and the ring Z is condensed. When it is a polycyclic hydrocarbon ring, it may be substituted at least with a hydrocarbon ring different from the hydrocarbon ring bonded to the 9th position of the fluorene (for example, the 5th and 6th positions of the naphthalene ring).

The substituent R ⁴ substituted on the ring Z is usually a non-reactive substituent, for example, an alkyl group (for example, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, C _1-8 alkyl group etc.), cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group), aryl group (eg, phenyl group, tolyl group, xylyl group, naphthyl group etc.) _6-10 an aryl group), a hydrocarbon group such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group); an alkoxy group (methoxy group, _{C 1} such as ethoxy groups _-8 an alkoxy group), such as C _5-10 cycloalkyl group such as a cycloalkoxy group (hexyloxy group cyclohexylene), an aryloxy group (Fe _{C 6-10} aryloxy groups such as alkoxy groups), the radical -OR [expression such aralkyloxy groups _{(C 6-10} aryl _{-C 1-4} alkyl group such as a benzyl group), R is a hydrocarbon radical (Such as the hydrocarbon groups exemplified above). A group such as an alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group) —SR (wherein R is as defined above); an acyl group (such as a C _1-6 acyl group such as an acetyl group); Alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group; substituted amino group (for example, dimethyl) And a dialkylamino group such as an amino group).

Preferred group R ⁴ includes, for example, a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _{6 -10} aryl group), an aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group) and the like, and an alkoxy group (C _1-4 alkoxy group etc.). In particular, R ⁴ is preferably an alkyl group [C _1-4 alkyl group (especially methyl group) or the like], an aryl group [eg C _6-10 aryl group (especially phenyl group)] or the like.

In the same ring Z, when n is plural (2 or more), the groups R ⁴ may be different from each other or the same. In the two rings Z, the groups R ⁴ may be the same or different. Moreover, the preferable substitution number n can be selected according to the kind of the ring Z, for example, 0-8, Preferably it is 0-4 (for example, 0-3), More preferably, it may be 0-2. In different rings Z, the number of substitutions n may be the same or different from each other, and may usually be the same.

  Typical (meth) acrylic compounds having a fluorene skeleton (or a compound represented by the formula (A1)) include 9,9-bis ((meth) acryloyloxyaryl) fluorenes and 9,9-bis. ((Meth) acryloyloxy (poly) alkoxyaryl) fluorenes are included.

As 9,9-bis ((meth) acryloyloxyaryl) fluorenes, for example, 9,9-bis ((meth) acryloyloxyphenyl) fluorene [for example, 9,9-bis (4- (meth) acryloyloxy) Phenyl) fluorene and the like], 9,9-bis (alkyl- (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- (meth) acryloyloxy-3-methylphenyl) fluorene, 9,9-bis ( 9,9-bis (mono or diC _1-4 alkyl- (meth) acryloyloxyphenyl) fluorene etc.] such as 4- (meth) acryloyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis ( Aryl (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- (meth) acryloylo 9,9-bis (mono- or di-C _6-8 aryl- (meth) acryloyloxyphenyl) fluorene, etc.] such as xyl-3-phenylphenyl) fluorene, 9,9-bis (poly (meth) acryloyloxyphenyl) Fluorene {for example, 9,9-bis [2,4-di ((meth) acryloyloxy) phenyl] fluorene, 9,9-bis [3,4-di ((meth) acryloyloxy) phenyl] fluorene, 9,9-bis ((9,9-bis (di or tri (meth) acryloyloxyphenyl) fluorene} such as 9-bis [3,4,5-tri ((meth) acryloyloxy) phenyl] fluorene) (Meth) acryloyloxyphenyl) fluorenes (compound in which ring Z is a benzene ring and m is 0 in the formula (A1)); 9,9-bi Sus ((meth) acryloyloxynaphthyl) fluorene [eg 9,9-bis [6- (2- (meth) acryloyloxynaphthyl)] fluorene, 9,9-bis [1- (5- (meth) acryloyloxy) 9,9-bis ((meth) acryloyloxynaphthyl) fluorenes (compound in which ring Z is a naphthalene ring and m is 0 in the above formula (A1)), and the like.

The 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorenes correspond to the 9,9-bis ((meth) acryloyloxyaryl) fluorenes, and m is 1 in the formula (1). Compounds that are above, for example, 9,9-bis ((meth) acryloyloxyalkoxyphenyl) fluorene [eg 9,9-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) fluorene, etc. 9-bis ((meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene and the like], 9,9-bis ((meth) acryloyloxydialkoxyphenyl) fluorene (eg, 9,9-bis {4- [2- 9,9-bi, such as (2- (meth) acryloyloxyethoxy) ethoxy] phenyl} fluorene etc. Scan {[2- (2- (meth) acryloyloxy _{C 2-4 alkoxy) C 2-4} alkoxy] phenyl} fluorene), 9,9-bis (alkyl - (meth) acryloyloxy-alkoxyphenyl) fluorene [e.g., 9,9-bis (4- (2- (meth) acryloyloxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) -3,5-dimethyl 9,9-bis (mono- or di-C _1-4 alkyl (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene etc.] such as phenyl) fluorene, 9,9-bis (aryl- (meth) acryloyloxyalkoxyphenyl) ) Fluorene [9,9-bis (4- (2- (meth) acryloyloxyethoxy) -3-phenyl] 9,9-bis (mono- or di-C _6-8 aryl (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene etc.], 9,9-bis [di- or tri ((meth) acryloyloxy) Alkoxy) phenyl] fluorene [e.g., 9,9-bis [2,4-di (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3,4-di (2- (meth)) 9,9-bis [di or tri ((meth) acryloyl) such as acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3,4,5-tri (2- (meth) acryloyloxyethoxy) phenyl] fluorene oxy _{C 2-4} alkoxy) phenyl] fluorene] such as 9,9-bis ((meth) acryloyloxy (poly) Arukokishifu Nyl) fluorenes (compound in which the ring Z is a benzene ring and m is 1 or more in the above formula (A1)); 9,9-bis ((meth) acryloyloxyalkoxynaphthyl) fluorene [eg, 9,9-bis ( 9,9-bis ((meth) acryloyloxy (poly) alkoxynaphthyl) fluorenes such as (meth) acryloyloxy C _2-4 alkoxynaphthyl) fluorene etc.] (in the formula (A1), ring Z is a naphthalene ring, m Is a compound in which is 1 or more.

  The (meth) acrylic compounds having a fluorene skeleton may be used alone or in combination of two or more.

  As the (meth) acrylic compound having a fluorene skeleton, a commercially available product may be used, or one synthesized by a conventional method may be used.

  Also, (meth) acrylic compounds having a fluorene skeleton and other (meth) acrylic compounds ((meth) acrylic compounds not having a fluorene skeleton, (meth) other than (meth) acrylic compounds having a fluorene skeleton) (Acrylic compound). When combined, the ratio of the (meth) acrylic compound having a fluorene skeleton to the other (meth) acrylic compound is the former / the latter (molar ratio) = 99.9 / 0.1 / 1/99, preferably 99. 5 / 0.5 to 10/90 (for example, 99/1 to 30/70), more preferably 99/1 to 40/60 (for example, 98/2 to 50/50), particularly 95/5 to 60 / 40 (for example, 90/10 to 70/30), 95/5 to 10/90 (for example, 90/10 to 15/85, preferably 85/15 to 20/80, more preferably) May be about 80/20 to 25/75).

(Monofunctional curable compound)
The curable component may be composed of at least a polyfunctional curable compound, and may further include a non-polyfunctional curable compound, that is, a monofunctional curable compound. The monofunctional curable compound can be used, for example, for the purpose of adjusting curability, hardness and viscosity.

  Examples of the monofunctional curable compound include monofunctional compounds corresponding to the polyfunctional curable compound, such as a monofunctional radically polymerizable compound and a monofunctional epoxy compound (for example, 2-ethylhexyl). Alkyl glycidyl ethers such as glycidyl ether, glycidyl ethers such as aryl glycidyl ether such as phenyl glycidyl ether; alkene oxides such as octylene oxide, styrene oxide, 4-vinylcyclohexene monooxide, and the like. Monofunctional curable compounds may be used alone or in combination of two or more.

  In particular, when a radically polymerizable compound (particularly, a (meth) acrylic compound) is used as the polyfunctional curable compound, a monofunctional radically polymerizable compound can be preferably used. Monofunctional radically polymerizable compounds (monofunctional monomers) include (meth) acrylic monomers ((meth) acrylic compounds), non- (meth) acrylic monomers [for example, styrenic monomers (for example, styrene, α- Methyl styrene, vinyl toluene, etc.), vinyl ester monomers (for example, vinyl acetate, etc.), N-vinyl pyrrolidone, etc.]. The monofunctional monomer may usually contain at least a (meth) acrylic monomer.

  When a (meth) acrylic monomer and a non- (meth) acrylic monomer are used as the monofunctional monomer, the ratio of the non- (meth) acrylic monomer to the entire monofunctional monomer is 30% by weight or less, preferably It may be 20% by weight or less, more preferably 10% by weight or less, particularly 5% by weight or less.

Examples of monofunctional (meth) acrylic monomers include (meth) acrylic acid, (meth) acrylamide, N-substituted (meth) acrylamide (N, N-diC _1-4 such as N, N-dimethyl (meth) acrylamide). (Meth) acrylic acid ester (or (meth) acrylate) and the like are included in addition to alkyl (meth) acrylamide and the like. Monofunctional (meth) acrylates include aliphatic (meth) acrylates ((meth) acrylates having an aliphatic skeleton), aromatic (meth) acrylates ((meth) acrylates having an aromatic skeleton), sulfur-containing (meta) ) Acrylate and the like.

Monofunctional aliphatic (meth) acrylates include alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate , T-butyl (meth) acrylate, isobutyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) ) Acrylate, C _1-20 alkyl (meth) acrylate such as stearyl (meth) acrylate], alicyclic (meth) acrylate {e.g. cycloalkyl (meth) acrylate [e.g. (meth) acrylate (Meth) acrylic acid C _5-8 cycloalkyl such as cyclohexyl silylate; (meth) acrylic polycyclic cycloalkyl such as bornyl (meth) acrylate and isobornyl (meth) acrylate], bridged cyclic (meth) acrylate [For example, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate etc.], etc.}, haloalkyl (meth) acrylates (e.g., trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, halo _{C 1-10} alkyl, such as hexafluoroisopropyl (meth) acrylate (meth Acrylate), hydroxyalkyl (meth) acrylate (e.g., hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl _{C 2-10} alkyl (meth) acrylates such as hydroxybutyl (meth) acrylate), alkoxyalkyl (meth ) Acrylates (eg C _1-10 alkoxy C _1-10 alkyl (meth) acrylates such as methoxyethyl (meth) acrylate), polyalkylene glycol mono (meth) acrylates [eg di to tetraethylene glycol mono (meth) acrylates such as (poly) such as oxy _{C 2-6} alkylene glycol mono (meth) acrylate, aliphatic epoxy (meth) acrylate {e.g., 2-hydroxy-3-alkoxypropyl ( Data) acrylates [e.g., 2-hydroxy-3-butoxypropyl (meth) acrylate, 2-hydroxy-3-pentadecyloxy propyl (meth) 2-hydroxy _{-3-C 2-20} alkoxy-propyl, such as acrylates (meth) Acrylate] etc.} Mono (meth) acrylate of an aliphatic polyol having 3 or more hydroxyl groups in one molecule {eg aliphatic triol mono (meth) acrylate [eg glycerol mono (meth) acrylate, trimethylolethane mono (meth) acrylate, alkane triol mono (meth) acrylates such as trimethylolpropane mono (meth) acrylates (e.g., C _3-10 alkane triol mono (meth) acrylate), etc.], etc.}, aminoalkyl (meth) acrylates [For example, N, N- dimethylaminoethyl acrylate such as N- substituted aminoalkyl (meth) acrylate, etc.], glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate.

Examples of the monofunctional aromatic (meth) acrylate include aryl (meth) acrylate (for example, C _6-10 aryl (meth) acrylate such as phenyl (meth) acrylate), aralkyl (meth) acrylate (for example, benzyl) C _6-10 arylC _1-4 alkyl (meth) acrylate such as (meth) acrylate), aryloxyalkyl (meth) acrylate (for example, C _6-10 aryloxy C _1-10 such as phenoxyethyl (meth) acrylate) Alkyl (meth) acrylate), arylaryloxyalkyl (meth) acrylate (for example, C _6-10 aryl C _6-10 aryloxy C _1-10 alkyl such as 2- (o-phenylphenoxy) ethyl (meth) acrylate ( Meta) Acrelay ), Aryloxy (poly) alkoxyalkyl (meth) acrylates [for example, phenoxy _{C 6-10} aryloxy, such as ethoxyethyl (meth) acrylate _{(poly) C 2-4} alkoxy _{C 2-4} alkyl (meth) acrylate, Alkylaryloxy (poly) alkoxyalkyl (meth) acrylates [eg C _4-20 alkyl C _6-10 aryloxy (poly) C _2-4 alkoxy C ₂₋ such as nonylphenoxy (poly) ethoxyethyl (meth) acrylate) ₄ alkyl (meth) acrylate], arylaryloxy (poly) alkoxyalkyl (meth) acrylate [for example, C _6-10 aryl C _6-10 aryloxy (poly) such as phenylphenoxy (poly) ethoxyethyl (meth) acrylate) C _2-4 alkoxy _C2-4 alkyl (meth) acrylate], bisphenols or alkylene oxide adducts thereof (for example, C _2-4 alkylene oxide adducts such as ethylene oxide adduct, propylene oxide adduct (for example, 2 to 2). An adduct of about 10 alkylene oxides), the same applies hereinafter) mono (meth) acrylate, aromatic epoxy (meth) acrylate {for example, 2-hydroxy-3-aryloxypropyl (meth) acrylate [for example, 2 2-hydroxy-3-C _{6-10 aryloxypropyl} (meth) acrylate such as hydroxy-3-phenoxypropyl (meth) acrylate; 2-hydroxy-3- (2-phenylphenoxy) propyl (meth) acrylate and the like 2-hydroxy-3 -(C _6-10 aryl C _6-10 aryl) oxypropyl (meth) acrylate] and the like}, (meth) acrylate having a fluorene skeleton {for example, 9- (meth) acryloyloxyfluorene, 9- (meth) acryloyloxy 9- (meth) acryloyloxyfluorenes such as 9-alkylfluorene and 9- (meth) acryloyloxy-9-arylfluorene; 9- (meth) acryloyloxymethylfluorene such as 9- (meth) acryloyloxymethylfluorene 9- (meth) acryloyloxyphenyl-9-phenylfluorene [for example, 9- (4- (meth) acryloyloxyphenyl) -9-phenylfluorene, etc.], 9- (alkyl- (meth) acryloyloxyphenyl) -9-phenylfluoro [For example, 9- (4- (meth) acryloyloxy-3-methylphenyl) -9-phenylfluorene, 9- (4- (meth) acryloyloxy-3,5-dimethylphenyl) -9-phenylfluorene, etc. 9- (mono- or di-C _1-4 alkyl- (meth) acryloyloxyphenyl) -9-phenylfluorene], 9- (aryl- (meth) acryloyloxyphenyl) -9-phenylfluorene [e.g. 9- ( 9- (such as 9- (mono or di-C _6-10 aryl- (meth) acryloyloxyphenyl) -9-phenylfluorene] such as 4- (meth) acryloyloxy-3-phenylphenyl) -9-phenylfluorene (Meth) acryloyloxyphenyl-9-phenylfluorenes; 9- (meth) acryloyloxy Poly) alkoxy-phenyl-9-phenyl fluorene [e.g., 9- (4- (2- (meth) acryloyloxy ethoxy) phenyl) -9-phenyl-fluorene 9- (meth) acryloyloxy _{(poly) C 2-4} 9- (meth) acryloyloxy (poly) alkoxyphenyl-9-phenylfluorenes} such as alkoxyphenyl-9-phenylfluorene], arylthio (meth) acrylate, aralkylthio (meth) acrylate, arylthioalkyl (described later) And (meth) acrylate.

Examples of the sulfur-containing (meth) acrylate include alkylthio (meth) acrylate (for example, C _1-10 alkylthio (meth) acrylate such as methylthio (meth) acrylate), arylthio (meth) acrylate (for example, phenylthio (meth) acrylate) , Tolylthio (meth) acrylate, 2-naphthylthio (meth) acrylate, C _6-10 arylthio (meth) acrylate such as chlorophenylthio (meth) acrylate), aralkylthio (meth) acrylate (for example, benzylthio (meth) acrylate, etc.) _{C 6-10} and aryl _{C 1-4} alkylthio (meth) acrylate), arylthioalkyl (meth) acrylate (e.g., phenyl thio (meth) _{C 6-10,} such as acrylate Riruchio such _{C 2-10} alkyl (meth) acrylate), and the like. In addition, arylthio (meth) acrylate, aralkylthio (meth) acrylate, and arylthioalkyl (meth) acrylate can also be classified as aromatic (meth) acrylate.

  Monofunctional monomers may be used alone or in combination of two or more.

Among these monofunctional monomers, monofunctional (meth) acrylates are preferable, and among monofunctional (meth) acrylates, they may be used properly depending on the application. For example, among monofunctional monomers, from the viewpoint of improving handling properties, aliphatic (meth) acrylate [particularly branched alkyl (meth) acrylate (particularly branched C _3-10 alkyl such as isoamyl (meth) acrylate) ( (Meth) acrylates, preferably branched C _3-6 alkyl (meth) acrylates, alicyclic (meth) acrylates and the like] can be suitably used. In addition, from the viewpoint of balancing optical characteristics such as a high refractive index and excellent handling properties in a balanced manner, aromatic (meth) acrylates, sulfur-containing (meth) acrylates, and the like can be suitably used.

  The viscosity of the monofunctional monomer is not particularly limited, and may be selected from a range of about 200 mPa · s or less at 25 ° C., for example, 100 mPa · s or less (eg, 0.01 to 100 mPa · s), preferably May be 50 mPa · s or less (eg, 0.1 to 50 mPa · s), more preferably 30 mPa · s or less (eg, 0.3 to 30 mPa · s), particularly 20 mPa · s or less [eg, 0 0.01 to 20 mPa · s, preferably 0.05 to 10 mPa · s, more preferably 0.1 to 5 mPa · s (for example, 0.5 to 3 mPa · s).

  The refractive index of the monofunctional monomer may be, for example, 1.4 or more at 25 ° C. and 589 nm, for example, 1.4 to 1.65, preferably 1.41 to 1.62, Preferably, it may be about 1.42 to 1.6. In particular, the refractive index of the monofunctional monomer may be 1.5 or more, for example, 1.5 to 1.65, preferably 1.51 to 1.62, more preferably 1.515 to 1.5. It may be about 6, particularly 1.53 or more (for example, about 1.54 to 1.6, preferably about 1.55 to 1.59).

  In the case of using a monofunctional curable compound, the ratio of the monofunctional curable compound is, for example, 1 to 1000 mol (for example, 3 to 100 mol) with respect to 100 mol of the polyfunctional curable compound (A). 800 mol), preferably 5 to 700 mol (eg 8 to 600 mol), more preferably 10 to 500 mol (eg 15 to 300 mol), particularly 20 to 250 mol (eg 30 to 200 mol). There may be. The proportion of the monofunctional curable compound is, for example, 1 to 1000 parts by weight (for example, 3 to 900 parts by weight), preferably 5 with respect to 100 parts by weight of the polyfunctional curable compound (A). ~ 800 parts by weight (for example, 8 to 700 parts by weight), more preferably about 10 to 600 parts by weight (for example, 15 to 500 parts by weight), particularly about 20 to 400 parts by weight (for example, 30 to 300 parts by weight). May be.

  In the case where the curable component includes a compound having a fluorene skeleton as a polyfunctional curable compound (for example, a (meth) acrylic compound having a fluorene skeleton), the ratio of the compound having a fluorene skeleton to the entire curable component Is, for example, 10 mol% or more (for example, 15 to 100 mol%), preferably 20 mol% or more (for example, 25 to 100 mol%), more preferably 30 mol% or more (for example, 35 to 100 mol%). In particular, it may be 40 mol% or more (for example, 45 to 100 mol%). The ratio of the compound having a fluorene skeleton to the entire curable component is, for example, 15% by weight or more (for example, 20 to 100% by weight), preferably 25% by weight or more (for example, 30 to 100% by weight), and more preferably. May be 35% by weight or more (for example, 40 to 100% by weight), particularly 45% by weight or more (for example, 50 to 100% by weight).

(Fluorene compound (B))
In the fluorene compound (B), examples of the hydrolytic condensable group include a hydrogen atom, an alkoxy group, an aryloxy group, a halogen atom (such as a chlorine atom), and a hydroxyl group. The hydrolytic condensable groups may be used alone or in combination of two or more. The hydrolytic condensable group is usually directly bonded to a metal atom (for example, silicon, zirconium, titanium, etc.). In addition, the fluorene compound (B) should just have a hydrolytic condensable group of at least 1 [usually 2 or more (for example, 2-20, preferably 3-15, more preferably 4-12)]. .

  The fluorene compound (B) has a fluorene skeleton together with a hydrolytic condensable group. That is, the fluorene compound (B) is a compound in which a hydrolytic condensable group (or a group containing a hydrolytic condensable group) is bonded (or substituted) to the fluorene skeleton.

  Examples of such a fluorene skeleton include fluorene (fluorene skeleton having no substituent at the 9-position), 9-substituted fluorene (for example, 9-alkylfluorene, 9-monoarylfluorene, 9,9-bisarylfluorene, etc.). And fluorene having a hydrocarbon group. A typical fluorene skeleton is a 9,9-bisarylfluorene skeleton. Note that the fluorene skeleton may have a substituent in fluorene or a substituent substituted at the 9-position of fluorene.

  The substitution position (bonding position) of the hydrolytic condensable group (or the group containing the hydrolytic condensable group) with respect to the fluorene skeleton is not particularly limited, and may be the fluorene skeleton itself or a substitution located at the 9th position of the fluorene. It may be bonded to a group.

  Typical fluorene compounds (B) include 9,9-bisarylfluorenes having two or more hydrolytic condensable groups (for example, alkoxy groups), for example, compounds represented by the following formula (B1), etc. Is included.

{Wherein X is a linking group, R ⁵ , R ⁶ and R ⁷ are the same or different and are a hydrogen atom, a hydroxyl group, a halogen atom, a group —OR ⁸ , wherein R ⁸ is a hydrocarbon group or a group -[(R ⁹ O) _a -R ¹⁰ ] (wherein R ⁹ represents a hydrocarbon group, R ¹⁰ represents a hydrocarbon group, a represents an integer of 1 or more) or a hydrocarbon group, , R ¹ , R ² , R ³ , R ⁴ , k, m, n, p are the same as above. However, at least one of R ⁵ , R ⁶ and R ⁷ is a hydrogen atom, a hydroxyl group, a halogen atom, or a group —OR ⁸ . }
In the formula (B1), examples of the aromatic hydrocarbon ring Z include the rings (benzene ring, naphthalene ring, etc.) exemplified in the section of the formula (A1). The two rings Z may be the same or different rings, and may usually be the same ring.

In the formula (B1), examples of the substituent R ¹ include the groups (such as an alkyl group) exemplified in the section of the formula (A1). In addition, when k is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited, and the preferred substitution number k is 0 to 1, particularly 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

In the formula (B1), examples of the alkylene group R ² include the groups exemplified in the section of the formula (A1) (C _2-4 alkylene groups such as ethylene group and propylene group). When m is 2 or more, the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group. In the two rings Z, the groups R ² may be the same or different, and may usually be the same.

In the formula (B1), the number (number of added moles) m of the oxyalkylene group (OR ² ) and the total of the two can also be selected from the range exemplified in the section of the formula (A1). In particular, m and the sum of the two are relatively small values {e.g., m is 6 or less [e.g. 0-6 (e.g. 1-6), preferably 0-4 (e.g. 1-4), more preferably 0 to 3 (for example, 1 to 3), particularly 0 to 2 (for example, 1 to 2)], and the total of two m is 12 or less [for example, 0 to 12 (for example, 2 to 12), preferably 0 to 0 8 (for example, 2 to 8), more preferably 0 to 6 (for example, 2 to 6), particularly 0 to 4 (for example, 2 to 4)], etc.}. If m and the total of two m are made small, adhesiveness can be improved efficiently with a small amount, and the refractive index and the like are easily held at a high level.

  In the formula (B1), the linking group X may be a direct bond, but may usually be a group containing a hetero atom (nitrogen atom, oxygen atom, sulfur atom, etc.). Typically, the linking group X is selected from, for example, an ether group (—O—) (or oxygen atom), a thioether group (—S—) (or sulfur atom), and an imino group (—NH—). It may contain at least one group.

Typically, the compound represented by the formula (B1) is a compound represented by the following formula (B1-1) [that is, in the formula (B1), the linking group X is a group-[X ^1- X ² —X ³ —X ⁴ ] —.

(In the formula, X ¹ represents an ether bond-containing group, a thioether bond-containing group, or an imino bond-containing group, X ² represents a direct bond, or an alkylene group that may have a hydroxyl group, and X ³ represents A direct bond, an oxygen atom, a sulfur atom or an imino group, and X ⁴ represents a direct bond or an alkylene group, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , k, m, n and p are the same as above.)
In the above formula (B1-1), examples of the ether bond-containing group represented by X ¹ include an oxygen atom (or an ether group, —O—) and an ester group (—OCO— or —COO—). It is done. Examples of the thioether bond-containing group represented by X ¹ include a sulfur atom (or thioether group, -S-), a thioester group (-SCO- or -COS-), and the like. Examples of the imino bond-containing group represented by X ¹ include an imino group (—NH—), an amide group (—CONH— or —NHCO—), a urethane group (—OCONH— or —NHCOO—), and a thiourethane group. (-SCONH- or -NHCOS-), urea group (-NHCONH-) and the like can be mentioned.

In the formula (B1-1), examples of the alkylene group optionally having a hydroxyl group represented by X ² include an alkylene group [including an alkylidene group. For example, a C _1-10 alkylene group such as a methylene group, an ethylene group, a trimethylene group (or 1,3-propanediyl group), a tetramethylene group (1,4-butanediyl group), a pentamethylene group, a hexamethylene group, Is a C _2-6 alkylene group, more preferably a C _2-4 alkylene group], a hydroxyalkylene group [including a hydroxyalkylidene group, such as a 2-hydroxy-1,3-propanediyl group (—CH ₂ —CH ( OH) _-CH 2 -), 2- hydroxy-2,3-butanediyl group _{(-CH 2 -CH (OH) -CH} (CH 3) -) hydroxy _{C 2-10} alkylene group such as, preferably hydroxy _{C 2 -6} alkylene group, more preferably a hydroxy _C2-4 alkylene group, etc.].

Furthermore, in the formula (B1-1), the alkylene group represented by X ⁴ is the same group as the alkylene group represented by X ² , for example, a methylene group, an ethylene group, a trimethylene group (or 1, C _1-10 alkylene groups such as 3-propanediyl group), preferably C _2-6 alkylene groups, and more preferably C _2-4 alkylene groups.

These X ^{1 to} X ⁴ may be the same or different with respect to different rings Z, and may usually be the same.

In the formula (B1-1), typical combinations of X ^{1 to} X ⁴ are shown below.

(1) A combination in which X ¹ is an ether bond-containing group:
(1A) A combination in which X ¹ is an oxygen atom and X ^{2 to} X ⁴ are all direct bonds (1B) X ¹ is an oxygen atom, and X ² and X ³ are both direct bonds, and X ⁴ Is an alkylene group (eg, a C _2-6 alkylene group) (1C) X ¹ is an oxygen atom, X ² is a hydroxy alkylene group (eg, a hydroxy C _2-6 alkylene group), and X ³ is A combination wherein X ⁴ is an alkylene group (eg, a C _2-6 alkylene group) (1D) X ¹ is an ester group (—OCO—), and X ² is a hydroxyalkylene group (eg, hydroxy C _2-6 alkylene group), ^{X 3} is an oxygen atom, ^{X 4} is an alkylene group _{(e.g., C 2-6} combination (1E) ^{X 1} is an alkylene group) an ester group X ² is an alkylene group _{(e.g., C 2-6} alkylene group), ^{X 3} is a sulfur atom (-S-), ^{X 4} is an alkylene group _{(e.g., C 2-6} alkylene group) combination.

(2) A combination in which X ¹ is a thioether bond-containing group:
(2A) A combination in which X ¹ is a sulfur atom and X ^{2 to} X ⁴ are all direct bonds (2B) X ¹ is a sulfur atom, and both X ² and X ³ are direct bonds, and X ⁴ Is an alkylene group (eg, a C _2-6 alkylene group) (2C) X ¹ is a sulfur atom, X ² is a hydroxy alkylene group (eg, a hydroxy C _2-6 alkylene group), and X ³ is A combination in which X ⁴ is an alkylene group (for example, a C _2-6 alkylene group) (2D) X ¹ is a thioester group (—OCS— or —SCO—), and X ² and X ³ are either Is a direct bond, and X ⁴ is an alkylene group (for example, a C _2-6 alkylene group).

(3) A combination in which X ¹ is an imino bond-containing group:
(3A) X ¹ is an imino group (—NH—), X ² is a hydroxyalkylene group (for example, a hydroxy C _2-6 alkylene group), X ³ is an oxygen atom, and X ⁴ is an alkylene group ( For example, a combination (3B) X ¹ is an amide group (—NHCO—), X ² and X ³ are both direct bonds, and X ⁴ is an alkylene group (for example, C _2-6 alkylene group). _2-6 in combination an alkylene group) (3C) ^{X 1} is an amide group, ^{X 2} is an alkylene group _(e.g., a _{C 2-6} alkylene group), ^{X 3} is an imino group, ^{X 4} is alkylene group _{(e.g., C 2-6} alkylene group) combinations are (3D) ^{X 1} is a urethane group (-OCONH-), a bond directly both the ^{X 2} and ^{X 3, X 4} is an alkylene group (eg , _{C 2-6} alkylene group) is a combination (3E) ^{X 1} urea group, a direct bond both the ^{X 2} and ^{X 3, X 4} is an alkylene group _{(e.g., C 2-6} alkylene group) Is a combination.

Among these, in terms of refractive index and viscosity, in the formula (B1), a compound in which X is a group containing a sulfur atom (linking group) [for example, in the formula (B1-1), X ^{1 to} X ⁴ Or a combination of (1A), (2A), (2B), (2C) or (2D). In particular, in the present invention, a compound represented by the following formula (B1-2) [that is, X in the formula (B1) (or X ^{1 to} X ⁴ in the formula (B1-1)) is a group —OCO—CHR ¹¹ —. A compound that is CH ₂ —S—X ^4a —] may be preferably used.

(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, X ^4a represents an alkylene group, Y represents —SiR ⁵ R ⁶ R ⁷ , Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^6. , R ⁷ , k, m, n and p are the same as above.)
In the above formula (B1-2), as the alkylene group X ^4a , the alkylene group exemplified in the above section X ⁴ [for example, methylene group, ethylene group, propylene group, trimethylene group (or 1,3-propanediyl group) C _1-10 alkylene group such as, preferably C _2-6 alkylene group, more preferably C _2-4 alkylene group and the like].

In the formula (B1) (or (B1-1) or (B1-2)), at least one of R ⁵ , R ⁶ and R ⁷ is a hydrolytic condensable group, that is, a hydrogen atom, a hydroxyl group, a halogen Atom, group -OR ⁸ [wherein R ⁸ is a hydrocarbon group or group-[(R ⁹ O) _a -R ¹⁰ ] (wherein R ⁹ is a hydrocarbon group (a divalent hydrocarbon group); R ¹⁰ represents a hydrocarbon group, and a represents an integer of 1 or more. Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom. Of these halogen atoms, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

In the group —OR ⁸ , the hydrocarbon groups R ⁸ and R ¹⁰ include, for example, saturated aliphatic hydrocarbon groups [for example, alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc. C _1-10 alkyl group, preferably C _1-6 alkyl group, more preferably C _1-4 alkyl group, particularly C _1-2 alkyl group, etc., cycloalkyl group (cyclopentyl group, cyclohexyl group etc.) C _5-10 cycloalkyl group etc.)], unsaturated aliphatic hydrocarbon group [eg, alkenyl group (eg, C _2-6 alkenyl group such as vinyl group, allyl group, etc., preferably C _2-4 alkenyl group etc.) ), etc.], an aromatic hydrocarbon group [for example, an aryl group (e.g., C _6-10 aryl groups such as a phenyl group, preferably a phenyl group), Ala Etc. Kill group (such as _{C 6-10} aryl _{-C 1-4} alkyl group such as a benzyl group)], and the like. Of these hydrocarbon groups R ⁸ , an alkyl group is preferable, and a lower alkyl group (for example, a C _1-4 alkyl group such as a methyl group, an ethyl group, or a propyl group, particularly a C _1-2 alkyl group) is preferable. . In addition, as the group R ⁹ , divalent hydrocarbon groups corresponding to these hydrocarbon groups (monovalent hydrocarbon groups), for example, saturated aliphatic hydrocarbon groups [for example, alkylene groups (for example, ethylene groups, C _2-6 alkylene group such as propylene group, preferably C _2-4 alkylene group)] and the like. Moreover, a may be 1-4, for example, Preferably it is 1-2, More preferably, 1 may be sufficient. Preferred groups -O-[(R ⁹ O) _a -R ¹⁰ ] include C _1-4 alkoxy C _2-4 alkoxy groups such as 2-methoxyethoxy group and 2-ethoxyethoxy group (particularly C _1-2 Alkoxyethoxy group) and the like.

In R ⁵ , R ⁶ and R ⁷ , examples of the hydrocarbon group include the same hydrocarbon groups as described above. Of these hydrocarbon groups, an alkyl group, an aryl group, and the like are preferable, and an alkyl group (for example, a C _1-4 alkyl group such as a methyl group) is particularly preferable.

As described above, at least one of R ⁵ , R ^6, and R ⁷ is a hydrogen atom, a hydroxyl group, a halogen atom, or a group —OR ⁸ . Such a group is important in that it directly bonds to a silicon atom and imparts polymerizability (hydrolytic condensation property) or reactivity to the compound represented by the formula (B1). Among these, at least one of R ⁵ , R ⁶ and R ⁷ is a chlorine atom or an alkoxy group (that is, a group in which R ⁷ is an alkyl group, for example, a C _1-4 alkoxy group such as a methoxy group or an ethoxy group). Or an aryloxy group (that is, a group in which R ⁷ is an aryl group, for example, a C _6-10 aryloxy group such as a phenoxy group), particularly an alkoxy group (for example, C _1-4). An alkoxy group, preferably a _C1-2 alkoxy group).

In the formula (B1) (formula (B1-1) and formula (B1-2)), examples of the representative group —SiR ⁵ R ⁶ R ⁷ include a dialkylalkoxysilyl group (for example, a dimethylmethoxysilyl group, dimethyl _{C 1-4} alkyl _{-C 1-4} alkoxysilyl group such as ethoxy silyl group), diaryl alkoxysilyl group (e.g., diphenyl methoxy silyl groups, di _{C 6-10} aryl _-C such diphenyl ethoxy silyl group _{1- 4} alkoxysilyl groups), alkylarylalkoxysilyl groups (for example, C _1-4 alkyl-C _6-10 aryl-C _1-4 alkoxysilyl groups such as methylphenylmethoxysilyl group), R ⁵ , R ⁶ and R one of the ^7, hydrogen atom, a hydroxyl group, a halogen atom or a silyl a group -OR ⁸ ; Alkyldialkoxysilyl group (e.g., methyl dimethoxy silyl group, C _1-4 alkyl such as methyl diethoxy silyl group, an ethyl dimethoxy silyl group, ethyl diethoxy silyl group - di C _1-4 alkoxysilyl group), aryldi Two of R ⁵ , R ⁶ and R ⁷ such as an alkoxysilyl group (for example, a C _6-10 aryl-diC _1-4 alkoxysilyl group such as phenyldimethoxysilyl group, phenyldiethoxysilyl group) are hydrogen atoms , A hydroxyl group, a halogen atom, or a silyl group that is —OR ⁸ ; a trialkoxysilyl group (for example, a tri-C _1-4 alkoxy such as a trimethoxysilyl group, a triethoxysilyl group, a trimesyl group, and an ethyldiethoxysilyl group) Silyl group), dialkoxyaryloxysilyl group (for example, di Butoxy phenoxy di _{C 1-4} alkoxy _{-C 6-10} aryloxy silyl group such as a silyl group), triaryl oxy silyl group (e.g., tri _{C 6-10} aryloxy silyl group such as tri-phenoxy silyl group), trihalosilyl group A silyl group in which all of R ⁵ , R ⁶ and R ⁷ such as (for example, a trichlorosilyl group) are a hydrogen atom, a hydroxyl group, a halogen atom, or a group —OR ⁸ is included.

Among these, a silyl group in which at least one of R ⁵ , R ⁶ and R ⁷ is an alkoxy group, for example, a dialkylalkoxysilyl group (for example, a diC _1-4 alkyl-C _1-4 alkoxysilyl group, particularly di _{C 1-4} alkyl _{-C 1-2} alkoxysilyl group), an alkyl dialkoxy silyl groups _{(e.g., C 1-4} alkyl - di _{C 1-4} alkoxysilyl group, in particular _{C 1-4} alkyl - di _{C 1- 2} alkoxysilyl groups) and trialkoxysilyl groups (for example, tri-C _1-4 alkoxysilyl groups, especially tri-C _1-2 alkoxysilyl groups) are preferable, and trialkoxysilyl groups are particularly preferable.

In the formula (B1), the substitution number p of a group (sometimes referred to as a hydrolytic condensable silicon-containing group) containing a group —SiR ⁵ R ⁶ R ⁷ may be 1 or more, for example, 1 to 4 , Preferably 1 to 3, more preferably 1 to 2, especially 1. In addition, the substitution number p may be the same or different in each ring Z, and is usually the same in many cases. In addition, the substitution position of the hydrolytic condensable group is the same as the substitution position similar to the (meth) acryloyl group in the formula (A1).

In the formula (B1), examples of the substituent R ⁴ substituted on the ring Z include the groups exemplified in the section of the formula (A1) {an alkyl group [C _1-4 alkyl group (especially a methyl group)], an aryl group [ For example, a _C6-10 aryl group (especially phenyl group etc.)] etc.] are mentioned, and a preferable aspect etc. are the same.

In the same ring Z, when n is plural (2 or more), the groups R ⁴ may be different from each other or the same. In the two rings Z, the groups R ⁴ may be the same or different. Moreover, the preferable substitution number n can be selected according to the kind of the ring Z, for example, 0-8, Preferably it is 0-4 (for example, 0-3), More preferably, it may be 0-2. In different rings Z, the number of substitutions n may be the same or different from each other, and may usually be the same.

  The fluorene compound (B) may be used alone or in combination of two or more.

  The molecular weight per hydrolytic condensable group (for example, alkoxy group) of the fluorene compound (B) can be selected from a range of about 50 to 2000 (for example, 55 to 1500), for example, 60 to 1000 (for example, 65 to 800), more preferably 70 to 500 (for example, 75 to 400), particularly 80 to 300 (for example, 90 to 250), and usually about 100 to 220 (for example, 110 to 200).

  The refractive index of the fluorene compound (B) can be selected from a range of about 1.45 or more (for example, 1.47 to 1.75) at 25 ° C. and 589 nm, for example, 1.5 or more (for example, 1.52). 1.7), preferably 1.53 or more (for example, 1.535 to 1.68), more preferably 1.54 or more (for example, 1.545 to 1.66), usually 1.53 to 1. About 65 (for example, 1.54 to 1.63, for example) may be sufficient.

  The refractive index difference (or the absolute value of the difference) between the curable component and the fluorene compound (B) is 0.20 or less (for example, 0.01 to 0.18), preferably 0.15 at 25 ° C. and 589 nm. It may be about (for example, 0.02 to 0.14) or less, more preferably about 0.10 or less (for example, 0.03 to 0.09). In particular, when the curable compound (A) is composed of a curable compound having a fluorene skeleton (for example, a compound represented by the formula (A1)), the refractive index difference between the curable component and the fluorene compound (B). (Or the absolute value of the difference) is 0.10 or less (for example, 0.01 to 0.095), preferably 0.09 or less (for example, 0.015 to 0.085) at 25 ° C. and 589 nm, Preferably, it may be about 0.08 or less (for example, 0.02 to 0.075), particularly about 0.07 or less (for example, 0.03 to 0.07).

  The fluorene compound (B) may be a commercially available product, and was synthesized by a conventional method (a method described in JP 2009-256293 A, a method described in JP 2009-269854 A, or the like). A thing may be used. For example, the compound represented by the formula (B1-2) reacts the compound represented by the following formula (b1) with the compound represented by the following formula (b2) (Michael addition type reaction or enethiol reaction). ).

(In the formula, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹¹ , k, m, n, p, and X ^4a are the same as described above.)
In the curable composition of the present invention, the ratio of the fluorene compound (B) is from about 0.01 to 50 parts by weight (for example, 0.05 to 40 parts by weight) with respect to 100 parts by weight of the curable component. For example, 0.1 to 30 parts by weight (for example, 0.15 to 25 parts by weight), preferably 0.2 to 20 parts by weight, and more preferably 0.3 to 15 parts by weight (for example, 0.5 ˜12 parts by weight), usually about 0.1 to 15 parts by weight. In particular, in the present invention, the proportion of the compound (B) having a fluorene skeleton is small [for example, 15 parts by weight or less (for example, 0.05 to 13 parts by weight of the fluorene compound (B) with respect to 100 parts by weight of the curable component). ), Preferably 10 parts by weight or less (for example, 0.1 to 8 parts by weight), more preferably 7 parts by weight or less (for example, 0.3 to 6 parts by weight), particularly 5 parts by weight or less (for example, 1 to 4 parts). Part by weight)].

  In the curable composition of the present invention, the molecular weight per hydrolytic condensable group (alkoxy group, etc.) contained in the fluorene compound (B) is based on the total amount of the curable component and the fluorene compound (B). 200 to 30000 (eg 250 to 25000), preferably 300 to 20000 (eg 350 to 18000), more preferably 400 to 15000 (eg 450 to 12000), particularly 500 to 10,000, You may adjust the ratio of a fluorene compound (B) so that it may become about 400-8000 (for example, 600-6000).

  Furthermore, in the curable composition of the present invention, when the curable compound (A) includes a compound having a fluorene skeleton, the ratio of the compound having a fluorene skeleton as the curable compound (A) and the fluorene compound (B) is: For example, 15 mol% or more (for example, 20 to 100 mol%), preferably 25 mol% or more (for example, 30 to 100 mol%), more preferably 35, based on the entire curable component and fluorene compound (B). It may be at least mol% (for example, 40 to 100 mol%), particularly at least 45 mol% (for example, 50 to 100 mol%). The ratio of the compound having a fluorene skeleton to the entire curable component is, for example, 20% by weight or more (for example, 25 to 100% by weight), preferably 30% by weight or more (for example, 35 to 100% by weight), and more preferably. May be 40% by weight or more (eg 45 to 100% by weight), in particular 50% by weight or more (eg 55 to 100% by weight).

(Polymerization initiator, curing agent)
The curable composition may further contain a curing agent, a curing accelerator, a polymerization initiator, and the like depending on the type (curing form) of the curable component. For example, when the curable composition is composed of an epoxy compound or the like, a general-purpose epoxy resin curing agent or curing accelerator may be included.

  In particular, when the curable component is composed of a radical polymerizable compound, the curable composition may contain a polymerization initiator (radical polymerization initiator) as necessary. Such a polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photo radical generator). A preferred polymerization initiator is a photopolymerization initiator.

  Examples of the photopolymerization initiator or photo radical generator include benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether); acetophenones (acetophenone, p- Dimethylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-phenyl-2-hydroxy-acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc .; propiophenones (p-dimethylaminopropiophenone, -Hydroxy-2-methyl-propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.); butyrylphenones [1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy 2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propane- 1-one etc.]; aminoacetophenones [2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2-methyl 1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino- 2-methyl-1- (4-methylphenyl) propan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1- (4 -Methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Dimethylaminophenyl) -butan-1-one etc.]; ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal etc.); thioxanthenes ( (Thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, etc.); anthraquinones (2-ethylanthraquinone, 1-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc.); ) Xanthones (thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone); acridines (1,3-bis- (9-acridinyl) propane, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, etc.); triazines (2,4,6-tris (trichloromethyl) -s-triazine, 2- ( 4-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, etc.); sulfides (benzyl diphenyl sulfide, etc.); acylphosphine oxides ( 2,4,6-trimethylbenzoyldiphenylphosphine oxide); titanocene photopolymerization initiators; oxime esters and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  In addition, a photoinitiator can be obtained as a commercial item, for example, a brand name "Irgacure" "Darocur" (Ciba Japan Co., Ltd. product), a brand name "Syracure" (made by Union Carbide), etc.

  Examples of thermal polymerization initiators include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxide (such as lauroyl peroxide), and dialoyl peroxide (benzoyl peroxide). Oxide, benzoyl toluyl peroxide, toluyl peroxide, etc.)], peracid esters (percarboxylic acid alkyl esters such as t-butyl peracetate, t-butyl peroxyoctate, t-butyl peroxybenzoate, etc.), Organic peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyro) Nitrile) 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc.], azoamide compound {2,2′-azobis {2-methyl -N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compounds {2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, etc.}, azoalkane compounds [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis (4-cyano) Azo compounds, etc.], and azo compounds having an oxime skeleton [2,2′-azobis (2-methylpropionamidooxime, etc.)]. You may use a thermal-polymerization initiator individually or in combination of 2 or more types.

  The ratio of the polymerization initiator (particularly the photopolymerizable initiator) is, for example, 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 0.1 to 100 parts by weight of the curable component. About 7-10 weight part (for example, 1-7 weight part) may be sufficient.

  In addition, you may combine a photoinitiator with a photosensitizer. Examples of the photosensitizer include conventional components such as tertiary amines [for example, trialkylamine, trialkanolamine (such as triethanolamine), ethyl N, N-dimethylaminobenzoate, N, N-dimethyl. Dialkylaminobenzoic acid alkyl esters such as amyl aminobenzoic acid, bis (dialkylamino) benzophenones such as 4,4-bis (dimethylamino) benzophenone (Michler's ketone), 4,4′-diethylaminobenzophenone], triphenylphosphine, etc. Examples include phosphine, toluidines such as N, N-dimethyltoluidine, anthracene such as 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. It is done. The photosensitizers may be used alone or in combination of two or more.

  The amount of the photosensitizer used is, for example, 0.1 to 150 parts by weight, preferably 1 to 100 parts by weight, more preferably 5 to 75 parts by weight (particularly 10 parts by weight) with respect to 100 parts by weight of the photopolymerization initiator. (About 50 parts by weight).

(Other ingredients)
The curable composition of the present invention further comprises a catalyst for promoting the hydrolysis condensation reaction (hydrolysis condensation catalyst such as an acid catalyst and a base catalyst, a photoacid generator, etc.), a conventional additive [for example, , Pigments, colorants, thickeners, sensitizers, antifoaming agents, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, light stabilizers, etc.), ultraviolet rays Other components such as an absorbent, a plasticizer, a surfactant, a filler, an antistatic agent, etc.] may be included. These other components may be used alone or in combination of two or more.

  The curable composition may contain a hydrolytic condensable compound (for example, a general-purpose silane coupling agent) other than the fluorene compound (B) as long as there is no actual harm. It is preferable that such other hydrolytic condensable compounds are not substantially contained.

  Such a curable composition of this invention can be prepared by mixing each component.

[Cured product]
The curable composition (resin composition) of the present invention is easily cured by applying active energy (active energy rays). Therefore, the curable composition of the present invention is useful for forming a cured product using thermal energy and / or light energy (particularly, light energy) as active energy. Among the curable compositions of the present invention, when the curable component is a radical polymerization component, it is often excellent in photocurability and may be cured by applying at least light energy (light irradiation). Good. The fluorene compound (B) seems to hydrolyze and condense with moisture in the air, etc., and depending on the type of base material, it seems to react with a functional group present on the surface of the base material. When the affinity between the fluorene compound (B) and the substrate is relatively high (for example, an inorganic substrate such as a glass substrate), the fluorene compound (B) is near the surface of the substrate or at the interface with the substrate. It may be easier to move nearby. In the present invention, even in such a case, the refractive index difference between the fluorene compound (B) and the substrate is relatively small (further, the refraction between the curable compound (A) and the fluorene compound (B). Since the difference in rate is relatively small and the ratio of the fluorene compound (B) is small), the spread (variation) of the refractive index in the entire cured product can be suppressed.

  The cured product may have a three-dimensional structure, and in particular, may be a cured film. The cured film may be a film pattern (particularly a thin film pattern). The cured film can be formed by applying the resin composition on a base material (or on a substrate), drying if necessary, and then exposing to heating or actinic rays, and the film pattern can be formed on the base material or the substrate. It can be formed by selectively exposing the film with actinic light and developing the resulting latent image pattern.

  The material of the base material or the substrate can be selected depending on the application, and inorganic materials [for example, metals (aluminum, copper, etc.), ceramics (zirconium oxide, titanium oxide, etc.), transparent inorganic materials (glass, quartz, magnesium fluoride, Calcium fluoride, etc.)], organic materials {eg, resins [eg, cyclic olefin resins, styrene resins, (meth) acrylic resins (polymethyl methacrylate, etc.), acrylonitrile resins, polyester resins, polyamides] Resin, polycarbonate resin, cellulose ester (such as triacetyl cellulose)], wood, etc.}. In particular, since the curable composition of the present invention is an inorganic substrate (a substrate formed of an inorganic material) and has excellent adhesion, it may be suitably formed on an inorganic substrate.

  Moreover, since the curable composition of the present invention has a high refractive index and high transparency, it is suitable for optical applications. Among these substrates, a transparent substrate or a transparent film can be coated to be transparent. Substrate or transparent film {for example, transparent inorganic substrate (for example, glass substrate or glass substrate), transparent organic substrate [for example, cyclic olefin resin, styrene resin, (meth) acrylic resin (polymethacrylic acid] Methyl, etc.), acrylonitrile resins, polyester resins, polyamide resins, polycarbonate resins, substrates or films formed of cellulose esters (triacetyl cellulose, etc.), etc.] Good. In particular, when a cured product is formed on a transparent inorganic substrate such as a glass substrate (a substrate formed of glass), the laminate has a high adhesion and a relatively small refractive index difference between the substrate and the cured product. Can be obtained efficiently.

  The thickness of the base material can be selected according to the use and is not particularly limited. The thickness of the film-like or plate-like base material is, for example, 1 μm to 10 mm (for example, 5 to 7000 μm), preferably 10 to 5000 μm, Preferably, it may be about 30 to 3000 μm (for example, 50 to 1000 μm).

  The coating method is not particularly limited. For example, flow coating method, spin coating method, spray coating method, screen printing method, casting method, bar coating method, curtain coating method, roll coating method, gravure coating method, dipping method, slit method. It may be.

  After apply | coating a curable composition, you may dry (for example, dry at about 40-150 degreeC). Although the thickness of a coating film changes with uses, it can select from the range of about 0.01-1000 micrometers, for example, 1-500 micrometers, Preferably it is 5-400 micrometers, More preferably, it may be about 10-300 micrometers.

  The curable composition is usually liquid or solid (or highly viscous liquid) at normal temperature, but the solid curable composition is melted by heating or dissolved in a solvent to form a coating film. Can be formed.

  When the coating film is cured by heating, the heating temperature may be, for example, 60 to 200 ° C. (for example, 80 to 180 ° C.), preferably about 100 to 150 ° C. In addition, when comprising a sclerosing | hardenable component with a radically polymerizable component, hardened | cured material can also be obtained by irradiation of actinic light, without heating.

In the exposure step, the entire surface may be exposed depending on the application, or a patterned latent image may be formed by selective exposure using a photomask or the like. For exposure, radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, etc. can be used, and usually ultraviolet rays are often used. As the light source, for example, in the case of ultraviolet rays, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, a laser light source (light source such as helium-cadmium laser or excimer laser), etc. Can be used. Irradiation light amount (irradiation energy) varies depending on the thickness of the coating film, for example, be selected from 50~10000mJ / cm ² in the range of about, 75~5000mJ / cm ^2, more preferably 100~3000mJ / cm ² (e.g., 100 to 2000 mJ / cm ² ).

  If necessary, heat treatment (after-cure or post-bake, etc.) may be performed before exposure, with exposure, or after exposure. The heating temperature may be, for example, 60 to 200 ° C, preferably 65 to 150 ° C, more preferably about 70 to 120 ° C.

  When a pattern-like latent image is formed, a developed coating pattern can be formed by developing the latent image pattern. Developers include water, alkaline aqueous solutions (eg, tetramethylammonium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc.), acidic aqueous solutions, hydrophilic solvents (eg, alcohols such as methanol, ethanol, isopropanol, Ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves, cellosolve acetates, etc.), and mixtures thereof. The development can be performed using immersion, washing, spraying or spray development.

  As described above, a cured product (cured film or the like) is obtained. Such a cured product is excellent in various properties. In particular, in the present invention, a cured product having excellent optical properties (high refractive index, high transparency, etc.), high heat resistance, etc. can be efficiently obtained by constituting the curable component with a compound having a fluorene skeleton. be able to. For example, the refractive index of the curable composition (or cured product) of the present invention can be selected from a range of about 1.50 or more (for example, 1.51 to 1.75) at 25 ° C. and 589 nm. Or more (for example, 1.525 to 1.7), preferably 1.53 or more (for example, 1.535 to 1.68), more preferably 1.54 or more (for example, 1.545 to 1.65), In particular, it may be about 1.55 or more (for example, 1.555 to 1.64). In particular, in the present invention, the refractive index at 25 ° C. and 589 nm of the curable composition (or cured product) is 1.56 or more (for example, 1.57 to 1.7), preferably 1.58 or more (for example, 1.59 to 1.68), more preferably 1.6 or more (for example, 1.605 to 1.65).

  In the present invention, as described later, by combining the curable component and the fluorene compound (B), it is possible to suppress the decrease in the refractive index as much as possible, and depending on the type of the curable component, the refractive index can be further increased. You can also For example, the refractive index (25 ° C., 589 nm) of the curable component (or cured product thereof) constituting the curable composition of the present invention is n1, and the refractive index (25 ° C., cured product thereof) of the curable composition (or cured product thereof). 589 nm) is n2, the refractive index difference represented by n1-n2 (or its absolute value) is 0.02 or less (for example, 0 to 0.015), preferably 0.01 or less (for example, 0 0.0001 to 0.08), more preferably 0.07 or less (for example, 0.0003 to 0.06), and particularly 0.05 or less (for example, 0.0005 to 0.03).

  Moreover, the decreasing rate (or the absolute value thereof) of the refractive index represented by the formula [(n1-n2) / n1] × 100 (%) is, for example, 0.5% or less (for example, 0 to 0.45%). ), Preferably 0.4% or less (for example, 0.01 to 0.35%), more preferably 0.3% or less (for example, 0.02 to 0.25), particularly 0.2% or less (for example, 0.03-0.15%).

  The glass transition temperature of the hardened | cured material of this invention is not specifically limited, For example, 50-300 degreeC, Preferably it is 70-280 degreeC, More preferably, about 80-250 degreeC may be sufficient. In particular, in the present invention, a cured product having excellent heat resistance can also be obtained. The glass transition temperature (Tg) of such a cured product is, for example, 150 ° C. or higher (for example, 155 to 300 ° C.), preferably 160. Or higher (for example, 165 to 280 ° C.), more preferably 170 ° C. or higher (for example, 175 to 270 ° C.), particularly 180 ° C. or higher (for example, 185 to 260 ° C.), and usually 160 to 290 ° C. (For example, about 165 to 280 ° C, preferably 170 to 270 ° C, more preferably 175 to 260 ° C).

  As described above, in the cured product of the present invention, the base material is maintained or imparted with excellent characteristics by combining a curable component (particularly, a curable compound having a fluorene skeleton) and a fluorene compound (B). Adhesion to (in particular, a transparent inorganic substrate such as glass) can be improved or improved. In other words, it can be said that the fluorene compound (B) acts or functions as an additive for improving or improving the adhesion of the cured product containing the curable component to the substrate. Therefore, the present invention includes such an additive and a method for improving or improving the adhesion to the substrate using the additive.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples, the various components (and their abbreviations) used are as follows.

BPEFA: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd.)
BPF-11EOA: Diacrylate of an adduct obtained by adding 11 mol of ethylene oxide to 1 mol of 9,9-bis (4-hydroxyphenyl) fluorene {in the above formula (A1), the total of oxyalkylene groups (m + m ) Is 11, compound synthesized in Synthesis Example 2}
BNFPOA: Diacrylate {9,9-bis [6- (2- (meth) acryloyloxypropoxy) -2-naphthyl] fluorene of propylene oxide adduct of 9,9-bis (6-hydroxy-2-naphthyl) fluorene A diacrylate having a main component, synthesized by the same method as in Example 2 of JP2009-173648}
BREFA: 9,9-bis [2,4-di (2-acryloyloxyethoxy) phenyl] fluorene (synthesized in Synthesis Example 1)
PETA: Pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd., trade name “M305”)
POA: Phenoxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., “Light acrylate PO-A”)
BzA: benzyl acrylate (“FA-BZA” manufactured by Hitachi Chemical Co., Ltd., refractive index (25 ° C., 589 nm) 1.515)
OPP: o-phenylphenol monoethoxy acrylate [or 2- (o-phenylphenoxy) ethyl acrylate, manufactured by Nippon Kayaku Co., Ltd., viscosity (25 ° C.) 163 mPa · s, refractive index (25 ° C., 589 nm) 1.577 ]
BPEF-MS: fluorene compound having a hydrolytic condensable group represented by the following formula (molecular weight: 939.29, synthesized in the same manner as in Example 1 of JP-A-2009-269854, refraction at 25 ° C. and 589 nm 1.55)

Reactive siloxane A: “Dynasylan 1146” (amino / alkyl group-containing oligomeric reactive siloxane) manufactured by EVONIC INDUSTRIES
Reactive siloxane B: “Dynasylan 6490” (vinyl group-containing oligomeric reactive siloxane) manufactured by EVONIC INDUSTRIES
Reactive siloxane C: “Dynasylan 6598” (vinyl / alkyl group-containing oligomeric reactive siloxane) manufactured by EVONIC INDUSTRIES
γ-methacryloxypropyltrimethoxysilane: “Dynasylan MEMO” manufactured by EVONIC INDUSTRIES
Initiator (photopolymerization initiator): “IRGACURE 184” manufactured by Ciba Japan Co., Ltd.

(Synthesis Example 1)
36 g (about 0.2 mol) of 9-fluorenone, 159 g (about 0.8 mol) of 1,3-bis (2-hydroxyethoxy) benzene, 0.7 ml of β-mercaptopropionic acid, and 60 g of 1,4-dioxane It put into the reactor and 5 ml of 98% sulfuric acid was dripped at 60 degreeC heating state. After completion of the reaction, extraction was performed by adding 200 ml of toluene and 100 ml of water. Excess sulfuric acid was removed by performing the same operation three times. After concentration of the solvent, recrystallization in toluene was repeated to obtain the desired product [ie, 9,9-bis [2,4-di (2-hydroxyethoxy) phenyl] fluorene]. The obtained compound was analyzed by high performance liquid chromatography. The purity was 98%.

  40 g (0.06 mol) of the obtained compound, 43 g (0.6 mol) of acrylic acid, 1 g of paratoluenesulfonic acid aqueous solution, 0.01 g of methoquinone and 100 mL of toluene were put into a reactor equipped with a Dean-Stark trap and refluxed with toluene. The esterification reaction was carried out for 5 hours below. Water generated during the esterification reaction was removed by a Dean-Stark trap to obtain 9,9-bis [2,4-di (2-acryloyloxyethoxy) phenyl] fluorene (BREFA).

(Synthesis Example 2)
BPF-11EOA was synthesized as follows. 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEF) 1 in the same manner as in Example 1 of JP-A-2001-139651 The reaction was carried out using 10 moles of ethylene oxide (EO) per mole. From the hydroxyl value of the obtained product, a compound in which 11.0 mol of EO is added to 1 mol of BPEF, that is, 5.1 mol of 9,9- (4-hydroxy) phenylfluorene (BPF). It was found to be a compound to which 0 mol of EO was added (hereinafter referred to as BPF-11EO).

  Then, using the obtained BPF-11EO, acrylated in the same manner as in Synthesis Example 1 to obtain BPF-11EOA.

(Examples 1-11 and Comparative Examples 1-10)
The components shown in the table were thoroughly mixed in propylene glycol monomethyl ether acetate (PGMEA) in a shaker heated to 60 ° C. in the proportions (parts by weight) shown in the table to prepare a resin composition (curable composition). did. The resin composition was a PGMEA solution containing 50% by weight of the components shown in the table. The prepared resin composition was applied to one side of various substrates [glass substrate (“Eagle XG” manufactured by Matsunami Glass Industrial Co., Ltd., thickness 500 μm), polyethylene terephthalate (PET) film (“A4300” manufactured by Toyobo Co. Ltd., thickness 100 μm)], and a high-pressure mercury lamp. Were irradiated with ultraviolet rays having an integrated light amount of 500 mJ / cm ² and further heated (post-baked) at 80 ° C. for 30 minutes to obtain a cured product (thickness of about 20 μm). In the examples, bleed out was not confirmed after coating and curing.

  In Example 9, 60 parts by weight of BPEFA and 62 parts by weight of PETA were used as the curable compound (A) (BPEFA / PETA (molar ratio) = 35/65).

  Various characteristics of the obtained resin composition and cured product were measured or evaluated.

(Compatibility and storage stability)
The prepared resin composition was allowed to stand at room temperature for one week and visually observed, and the compatibility (storage stability) of the resin composition was evaluated according to the following criteria.

○: No change compared to immediately after preparation ×: Precipitation or gelation.

(Refractive index)
Using a multi-wavelength Abbe refractometer (manufactured by Atago Co., Ltd., DR-M2 <using circulating thermostatic water bath 60-C3>), the refractive index of the curable composition at 589 nm was measured while maintaining a temperature of 25C.

(viscosity)
Using a TV-22 viscometer (cone plate type, “TVE-22L” manufactured by Toki Sangyo Co., Ltd.), the viscosity of the curable composition at 25 ° C. (viscosity before being diluted with PGMEA) is measured viscosity. Measurement was performed at 1 to 20 rpm (selected according to viscosity) with a corresponding optional rotor (01: 1 ° 34 × R24, 07: 3 ° × R7.7).

(Adhesion to glass substrate)
The adhesion of the cured product was evaluated according to the following criteria.

○: After the cured film is cut into a grid, the cured film does not peel off from the glass substrate. ×: After the cured film is cut into a grid, the cured film peels off from the glass substrate.

(Curing shrinkage)
The presence or absence of cure shrinkage was evaluated according to the following criteria.

○: The area of the cured film does not change before and after curing. ×: The area of the cured film changes greatly before and after curing.

  The results are shown in the table.

(Example 12)
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that 100 parts by weight of BREFA was used instead of 100 parts by weight of BPEFA. In the resin composition, compatibility and storage stability were good (evaluation ○) as in Example 1. Further, the refractive index of the resin composition was 1.557, and the refractive index reduction amount was 0.000.

(Example 13)
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that 100 parts by weight of BNFPOA was used instead of 100 parts by weight of BPEFA. In the resin composition, compatibility and storage stability were good (evaluation ○) as in Example 1. Further, the refractive index of the resin composition was 1.606, and the amount of decrease in the refractive index was -0.001.

The curable composition of the present invention includes, for example, an ink material, a light emitting material (for example, a light emitting material for organic EL), an organic semiconductor, a graphitization precursor, a gas separation membrane (for example, a CO ₂ gas separation membrane), OCA (Optical adhesive layer), adhesives, coating agents (for example, optical overcoat agents such as LED (light emitting diode) element coating agents or hard coating agents), lenses [pickup lenses (eg, DVD (digital versatile) Pickup lens for disc), microlens (for example, microlens for liquid crystal projector), spectacle lens, etc.], polarizing film (for example, polarizing film for liquid crystal display), composite sheet, brightness enhancement film, prism sheet, Antireflection film (or antireflection film such as an antireflection film for display device), LCD panel film, flexible substrate film, display film [eg, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (field emission display) ), NED (nano-emissive display), cathode ray tube, electronic paper display (especially thin display) film (protective film, etc.)], color filter [eg, lens filter, display color filter, etc.], liquid crystal display Resist for devices [eg, photoresist for TFT array etching, pigment dispersion type photoresist, protective film, etc.], interlayer insulating film, solder resist, fuel cell film, optical fiber, optical waveguide, hologram It can be suitably used etc.. In particular, since the curable composition of the present invention has a high refractive index, it can be suitably used for optical material applications. Examples of the shape of the optical material include a film or sheet shape, a plate shape, a lens shape, and a tubular shape.

Claims (19)

  A curable composition comprising a curable component composed of a polyfunctional curable compound (A) and a fluorene compound (B) having a hydrolytic condensable group.   The curable composition according to claim 1, wherein the curable compound (A) is a (meth) acrylic compound.   The curable composition according to claim 1 or 2, wherein the curable compound (A) is a (meth) acrylic compound containing a (meth) acrylic compound having a fluorene skeleton. The curable composition according to any one of claims 1 to 3, wherein the curable compound (A) is a (meth) acrylic compound containing a compound represented by the following formula (A1).

(In the formula, ring Z represents an aromatic hydrocarbon ring, R ¹ represents a substituent, R ² represents an alkylene group, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a substituent, and k represents An integer of 0 to 4, m is an integer of 0 or more, n is an integer of 0 or more, and p is an integer of 1 or more.)   The curable composition according to any one of claims 1 to 4, wherein the curable component further contains a monofunctional curable compound.   The curable composition according to any one of claims 1 to 5, wherein the curable component further comprises at least one monofunctional curable compound selected from aromatic (meth) acrylate and sulfur-containing (meth) acrylate. object.   The curable composition according to claim 5 or 6, wherein the proportion of the monofunctional curable compound is 10 to 600 parts by weight with respect to 100 parts by weight of the polyfunctional curable compound (A). The curable composition according to any one of claims 1 to 7, wherein the fluorene compound (B) is a compound represented by the following formula (B1).

{Wherein X is a linking group, R ⁵ , R ⁶ and R ⁷ are the same or different and are a hydrogen atom, a hydroxyl group, a halogen atom, a group —OR ⁸ , wherein R ⁸ is a hydrocarbon group or a group -[(R ⁹ O) _a -R ¹⁰ ] (wherein R ⁹ represents a hydrocarbon group, R ¹⁰ represents a hydrocarbon group, a represents an integer of 1 or more) or a hydrocarbon group, , R ¹ , R ² , R ³ , R ⁴ , k, m, n, p are the same as above. However, at least one of R ⁵ , R ⁶ and R ⁷ is a hydrogen atom, a hydroxyl group, a halogen atom, or a group —OR ⁸ . }   The curable composition according to claim 8, wherein in the formula (B1), X is a group containing a sulfur atom. The curable composition according to claim 8 or 9, wherein in the formula (B1), X is a group represented by the following formula.
—OCO—CHR ¹¹ —CH ₂ —S—X ^4a —
(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and X ^4a represents an alkylene group.)   The curable composition according to any one of claims 1 to 10, wherein the fluorene compound (B) has a refractive index of 1.55 or more at 25 ° C and 589 nm.   The ratio of a fluorene compound (B) is 0.1-30 weight part with respect to 100 weight part of sclerosing | hardenable components, The curable composition in any one of Claims 1-11.   The molecular weight per hydrolyzable condensable group contained in the fluorene compound (B) is 500 to 10,000 with respect to the total amount of the curable component and the fluorene compound (B). Curable composition.   When the refractive index (25 ° C., 589 nm) of the curable component is n1, and the refractive index (25 ° C., 589 nm) of the curable composition is n2, the formula [(n1-n2) / n1] × 100 (%) The curable composition according to any one of claims 1 to 13, which has a refractive index reduction rate of 0.5% or less.   The manufacturing method of the hardened | cured material which provides active energy to the curable composition in any one of Claims 1-14, and is made to harden | cure.   Hardened | cured material which the curable composition of Claim 15 hardened | cured.   The laminated body comprised by the base material comprised with the transparent inorganic material, and the hardened | cured material of Claim 16 formed on this base material.   A fluorene compound having a hydrolytic condensable group, which is an additive for improving or improving the adhesion of a cured product containing a curable component composed of a polyfunctional curable compound (A) to a substrate. B) additive.   The additive of Claim 18 is added or mixed with the curable composition containing the curable component comprised by the polyfunctional curable compound (A), The group of the hardened | cured material which the said curable composition hardened | cured A method for improving or improving adhesion to a material.