JP6007136B2 - Curable composition and cured product thereof - Google Patents

Description

  The present invention relates to a curable composition containing a fluorene compound having a polymerizable unsaturated bond and a cured product thereof.

  Optical curable resin (epoxy acrylate, polyester acrylate, polyurethane acrylate, etc.), photo curable monomer, etc. for optical material applications such as optical overcoat agent, hard coat agent, antireflection film, lens, optical fiber, optical waveguide, hologram, etc. Components having a polymerizable group such as (polyfunctional acrylate and the like) are known.

  A compound having a 9,9-bisphenylfluorene skeleton such as bisphenolfluorene (BPF) is known to have excellent functions such as a high refractive index and high heat resistance. Photopolymerizable resin made from a compound having such a fluorene skeleton [for example, 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene, 9,9-bis [4- (2- (meth) acryloyl) An attempt has been made to obtain a cured product having characteristics such as a high refractive index using (meth) acrylate having a fluorene skeleton such as oxyethoxy) phenyl] fluorene.

  For example, JP-A-4-325508 (Patent Document 1) discloses a copolymer of a radically polymerizable composition mainly composed of 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene. A plastic lens material having a refractive index of 1.60 or more is disclosed.

  However, although such a bifunctional (meth) acrylate [di (meth) acrylate] has a high refractive index, it has been difficult to obtain a cured product having sufficient hardness.

On the other hand, a tetra- or higher functional (meth) acrylate having a 9,9-bisphenylfluorene skeleton is also known. For example, WO2005 / 033061 (Patent Document 2) discloses a tetraacrylate of a C _2-4 alkylene oxide adduct of 9,9-bis (3,4-dihydroxyphenyl) fluorene. In the examples, it is described that a cured product having a high refractive index was obtained using such a tetraacrylate. This document also describes such tetra (meth) acrylates and monofunctional monomers [for example, (meth) acrylic monomers such as alkyl (meth) acrylates] and bifunctional or polyfunctional (meta) ) Acrylate [for example, alkylene glycol di (meth) acrylate, trifunctional or polyfunctional (meth) acrylate etc. of polyhydric alcohol (or its C _2-3 alkylene oxide adduct), etc.] in combination with the polymerizable composition It is described that it may be formed. In addition, this literature does not make any study on the hardness (hardness) of the cured product.

JP-A-4-325508 (Claims) WO2005 / 033061 (Claims, paragraphs [0083] to [0087], Examples)

  Accordingly, an object of the present invention is to provide a curable composition capable of achieving both a high refractive index and a high hardness and a cured product thereof.

  Another object of the present invention is to provide a curable composition capable of efficiently suppressing curing shrinkage and a cured product thereof.

  Still another object of the present invention is to provide a curable composition capable of forming a cured product (cured film) having excellent adhesion to a substrate and a cured product thereof.

  The present inventors investigated the physical properties of a cured product of a tetrafunctional or higher functional (meth) acrylate having a fluorene skeleton. The effect of improving the refractive index as compared with the functional (meth) acrylate cannot be confirmed, or rather, a cured product having a low refractive index can be obtained. It has been found that it is difficult to obtain a cured product satisfying a high refractive index and a high hardness even in combination with a bifunctional or polyfunctional (meth) acrylate as disclosed.

  Under such circumstances, as a result of intensive studies to achieve the above-mentioned problems, the present inventors have conducted fluorene having 2 or less (1 or 2) polymerizable unsaturated bonds (for example, (meth) acryloyloxy groups). When a compound and a fluorene compound having three or more polymerizable unsaturated bonds (for example, (meth) acryloyloxy group) are combined, surprisingly, each has a high refractive index and high hardness that are not compatible with each other. The present inventors have found that a cured product can be obtained and completed the present invention.

  That is, the curable composition of the present invention includes a fluorene compound (A) having two or less polymerizable unsaturated bonds (for example, a fluorene compound having two (meth) acryloyl groups) and three or more polymerizations. And a fluorene compound (B) having a polymerizable unsaturated bond (for example, a fluorene compound having 4 or more (meth) acryloyl groups).

  In the composition of the present invention, the fluorene compound (A) includes, for example, 9,9-bis ((meth) acryloyloxyaryl) fluorenes and 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorene. The fluorene compound (B) may be 9,9-bis (poly (meth) acryloyloxyaryl) fluorenes and 9,9-bis [poly ((meth) acryloyl). It may be at least one selected from oxy (poly) alkoxy) aryl] fluorenes.

  In the composition of the present invention, the fluorene compound (B) contains 9,9-bis (2,4-di (meth) acryloyloxyphenyl) fluorenes and 9,9-bis [2,4-di (( It may be at least one selected from (meth) acryloyloxy (poly) alkoxy) phenyl] fluorenes, in particular, 9,9-bis [2,4-di ((meth) acryloyloxy (poly) alkoxy) Phenyl] fluorenes may be used.

  In the composition, the ratio of the fluorene compound (A) to the fluorene compound (B) is, for example, the former / the latter (weight ratio) = 5/95 to 95/5 (for example, 10/90 to 90/10). It may be.

In a typical composition of the present invention, the fluorene compound (A) contains 9,9-bis ((meth) acryloyloxymono to hexa C _2-4 alkoxyphenyl) fluorene [for example, 9,9-bis (( meth) acryloyloxy mono- to tetra _{C 2-4} alkoxyphenyl) fluorene, 9,9-bis [mono- or di - ((meth) acryloyloxy mono- to hexa _{C 2-4} alkoxy) phenyl] fluorene {e.g., 9, 9-bis [mono or dialkyl-((meth) acryloyloxymono to tetra _C2-4alkoxy ) phenyl] fluorene}, 9,9-bis [mono or diaryl-((meth) acryloyloxymono to hexa _{C2- 4} alkoxy) phenyl] fluorene {e.g., 9,9-bis [mono or diaryl - (( Data) acryloyloxy mono- to tetra _{C 2-4} alkoxy) phenyl] fluorene}, and 9,9-bis ((meth) acryloyloxy mono- to hexa _{C 2-4} alkoxy naphthyl) fluorene [e.g., 9,9-bis ( (meth) acryloyloxy mono- to tetra C _2-4 alkoxy naphthyl) is at least one selected from fluorene,
Fluorene compound (B) is 9,9-bis [2,4-di ((meth) acryloyloxy mono- to hexa _{C 2-4} alkoxy) phenyl] fluorene {e.g., 9,9-bis [2,4-di ((Meth) acryloyloxymono to tetra _C2-4alkoxy ) phenyl] fluorene},
A composition in which the ratio of the fluorene compound (A) to the fluorene compound (B) is about the former / the latter (weight ratio) = 20/80 to 80/20 is included.

  The composition of the present invention further comprises a non-fluorene-based monofunctional monomer (C) [for example, at least one monofunctional (meth) acrylate selected from aromatic (meth) acrylate and sulfur-containing (meth) acrylate ] May be included. The proportion of such a non-fluorene monofunctional monomer (C) may be, for example, about 1 to 100 parts by weight with respect to 100 parts by weight of the total amount of the fluorene compound (A) and the fluorene compound (B). .

  The present invention also includes a method for producing a cured product obtained by imparting active energy to the curable composition and curing the cured product, and a cured product obtained by the production method (a cured product obtained by curing the curable composition). Such a cured product has high hardness and excellent optical characteristics. For example, in the cured product, the refractive index at 25 ° C. and 589 nm may be 1.58 or more (for example, 1.59 or more, preferably 1.6 or more), and the thickness is 10 μm (cured product having a thickness of 10 μm). The pencil hardness may be H or higher.

  In the present invention, a cured product having a high refractive index and high hardness can be obtained. Moreover, in the composition of this invention, there is little coloring and a highly transparent hardened | cured material can be obtained. Furthermore, the cured product of the present invention is excellent in adhesion to the substrate. In particular, in the present invention, even a thin film can form a cured product having such excellent characteristics, so that it is extremely practical as an optical material. Moreover, in this invention, although it contains the fluorene compound which has a 3 or more polymerizable unsaturated bond, hardening shrinkage | contraction can be suppressed. In addition, the cured product has excellent adhesion to the substrate. Therefore, in this invention, while being excellent in the adhesiveness with respect to a board | substrate, the cured | curing material (cured film) with small curl can be obtained efficiently. Furthermore, the curable composition of this invention is excellent also in storage stability, and can obtain the cured | curing material which has the above outstanding characteristics efficiently.

[Curable composition]
The curable composition (resin composition) of the present invention comprises, as a polymerization component (radical polymerization component, radical polymerizable component), a fluorene compound (A) having 2 or less polymerizable unsaturated bonds, and 3 or more A fluorene compound (B) having a polymerizable unsaturated bond.

(Fluorene compound (A))
In the fluorene compound (A) having a polymerizable unsaturated bond (or the polymerizable unsaturated compound (A) having a fluorene skeleton), the polymerizable unsaturated bond (polymerizable unsaturated group) may be a carbon-carbon unsaturated bond. (Carbon-carbon unsaturated group). Such a polymerizable unsaturated bond only needs to have a carbon-carbon unsaturated bond, and specific examples thereof include an alkenyl group (for example, a vinyl group) and a (meth) acryloyl group. The fluorene compound having a polymerizable unsaturated bond may have a polymerizable unsaturated group alone or in combination of two or more. A typical fluorene compound is a fluorene compound having a (meth) acryloyl group (or (meth) acryloyloxy group).

  In the fluorene compound (A), the number of polymerizable unsaturated bonds may be 2 or less (that is, 1 or 2). Preferred fluorene compounds (A) include fluorene compounds having two polymerizable unsaturated bonds (for example, (meth) acryloyl groups).

  Therefore, the fluorene compound (A) may be composed of at least a fluorene compound (bifunctional fluorene compound) having two polymerizable unsaturated bonds. In other words, the fluorene compound may be composed of only a fluorene compound having two polymerizable unsaturated bonds, and a fluorene compound having two polymerizable unsaturated bonds as a main component has one polymerizable unsaturated bond. It may contain a fluorene compound (monofunctional fluorene compound). In the latter case, the ratio of the fluorene compound having two polymerizable unsaturated bonds to the whole fluorene compound is 40 mol% or more (for example, 50 to 99.9 mol%), preferably 60 mol% or more ( For example, it may be 65 to 99.7 mol%), more preferably 70 mol% or more (for example, 80 to 99.5 mol%), particularly 85 mol% or more (for example, 90 to 99 mol%).

  The fluorene compound (A) has a fluorene skeleton together with a polymerizable unsaturated bond. That is, the fluorene compound (A) is a compound in which a polymerizable unsaturated bond (or a group containing a polymerizable unsaturated bond) 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 polymerizable unsaturated bond (or group containing a polymerizable unsaturated bond) 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 include 9,9-bisarylfluorenes having 2 or less (especially 2) polymerizable unsaturated bonds (especially (meth) acryloyl groups), such as those represented by the following formula (A1). And the like.

(Wherein ring ^{Z a} represents an aromatic hydrocarbon ^{ring, R 1a} represents a ^{substituent, R 2a} is an alkylene ^{group, R 3a} represents a hydrogen atom or a methyl ^{group, R 4a} represents a substituent K1 is an integer of 0 to 4, m1 is an integer of 0 or more, and n1 is an integer of 0 or more.)
In the above formula (A1), the aromatic hydrocarbon ring represented by ring Z ^a, benzene ring, condensed polycyclic arenes (or condensed polycyclic aromatic hydrocarbon) such as rings. 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). Incidentally, two rings Z ^a may be the same or different rings, may be generally the same ring.

Representative ring Z ^a is a benzene ring, a naphthalene ring, particularly, a naphthalene ring is preferable from the viewpoint of high refractive index.

In the formula (A1), examples of the group R ^1a 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 k1 is plural (2 or more), the groups R ^1a may be different from each other or the same. Further, the groups R ^1a substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ^1a to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k1 is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the substitution number k1 may be the same or different from each other.

In the formula (A1), examples of the alkylene group represented by the group R ^2a 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. In particular, radicals R ^2a from the viewpoint of solvent solubility branched alkylene groups such as a propylene group (e.g., C _3-4 alkylene group) fluorene compound of the (e.g., a fluorene compound ring Z ^a is a naphthalene ring) suitable You may use for. When m1 is 2 or more, the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group. Further, in the two rings Z ^a, also radicals R ^2a may be the same or different, may be a conventional same.

The number (average number of added moles) m1 of the oxyalkylene group (OR ^2a ) can be selected from a range of about 0 to 15 (for example, 0 to 12), for example, 0 to 10 (for example, 0 to 8), preferably 0-6 (for example, 1-6), More preferably, 0-4 (for example, 1-4) may be sufficient. In particular, m1 may be 1 or more (for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1). Such a compound having m1 of 1 or more can be suitably used from the viewpoints of handling properties such as solvent solubility, skin irritation, and improvement of brittleness in a cured product. Incidentally, substituents which m1 is in a different ring Z ^a, may be the same or different. Further, in the two rings ^{Z a,} to the sum of the oxyalkylene groups (m1 × 2, m1 + m1) is 0-30 (e.g., 2-24) can be selected from the range of about, for example, 0 to 16 (e.g., 2 14), preferably 0 to 12 (eg 2 to 10), more preferably 0 to 8 (eg 0 to 6), in particular 0 to 4 (eg 2 to 4).

In the formula (A1), the substitution position of the group containing the group R ^2a (sometimes referred to as a (meth) acryloyl group-containing group) is not particularly limited, and the substitution position at the ring Z ^a is substituted. It only has to be. For example, (meth) acryloyl group-containing group, when the ring Z ^a is a benzene ring, a suitable position 2-6 position of the benzene ring (in particular, 4-position) may be substituted on the ring Z ^a is When it is a condensed polycyclic hydrocarbon ring, it may be substituted with a hydrocarbon ring different from the hydrocarbon ring bonded to the 9th position of fluorene (for example, the 5th and 6th positions of the naphthalene ring).

The substituent R ^4a substituting the ring Z ^a, typically, non-reactive substituent, e.g., an alkyl group (e.g., methyl group, ethyl group, propyl group, C _1-12 alkyl groups such as isopropyl group, butyl group , Preferably C _1-8 alkyl group), cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group), aryl group (for example, phenyl group, tolyl group, xylyl group, naphthyl group, etc.) Hydrocarbon groups such as C _6-10 aryl groups), aralkyl groups (C _6-10 aryl-C _1-4 alkyl groups such as benzyl and phenethyl groups); alkoxy groups (C such as methoxy groups and ethoxy groups) _1-8 alkoxy groups), cycloalkoxy groups (C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryloxy groups (such as Groups such as C _6-10 aryloxy groups such as phenoxy groups), aralkyloxy groups (C _6-10 aryl-C _1-4 alkyloxy groups such as benzyloxy groups), etc. —OR ⁵ [wherein R ⁵ is carbonized; A hydrogen group (such as the hydrocarbon group exemplified above) is shown. A group such as an alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group) —SR ⁵ (wherein R ⁵ 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); nitro group; cyano group; substituted amino group (for example, And a dialkylamino group such as a dimethylamino group).

Preferred group R ^4a 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 ^4a is preferably an alkyl group [C _1-4 alkyl group (particularly a methyl group)], an aryl group [eg C _6-10 aryl group (particularly a phenyl group)], or the like.

Note that in the same ring Z ^a, when n1 is plural (2 or more), groups R ^4a may be different from each other, it may be identical. Further, in the two rings Z ^a, group R ^4a may be the same or different. Further, it preferred substituents which n1 can be selected according to the kind of ring ^{Z a,} for example, 0-8, preferably 0-4 (e.g., 0-3), more preferably may be 0-2. In particular, when the ring Za is ^a benzene ring, the substitution number n1 may be 1 to 3, preferably about 1 to 2. Note that in a different ring Z ^a, few substitutions n1, which may be the same or different, may be a conventional same.

  Representative fluorene compounds (A) (or the compounds represented by the formula (A1)) include 9,9-bis ((meth) acryloyloxyaryl) fluorenes and 9,9-bis ((meth) acryloyl). Oxy (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 ((meth) acryloyloxyphenyl) such as 9,9-bis (mono or di C _6-8 aryl- (meth) acryloyloxyphenyl) fluorene etc.] such as xyl-3-phenylphenyl) fluorene Fluorenes (compound in which the ring Za is ^a benzene ring and m1 is 0 in the formula (A1)); 9,9-bis ((meth) acryloyloxynaphthyl) fluorene [for example, 9,9-bis (6- ( 9,9-bis ((meth) acryloyloxynaphthyl) fluorenes such as (meth) acryloyloxy-2-naphthyl) fluorene, 9,9-bis (5- (meth) acryloyloxy-1-naphthyl) fluorene, etc.] A compound in which the ring Za is ^a naphthalene ring and m1 is 0) in the formula (A1).

The 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorenes correspond to the 9,9-bis ((meth) acryloyloxyaryl) fluorenes, and m1 is 1 in the formula (A1). More than (for example, 1-6, preferably 1-4, more preferably 1-2) compounds such as 9,9-bis ((meth) acryloyloxy (poly) alkoxyphenyl) fluorene {for example 9, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) phenyl] fluorene, 9,9-bis {4- 9,9-bis ((meth) acryloyl such as [2- (2- (meth) acryloyloxyethoxy) ethoxy] phenyl} fluorene Okishimono to hexa _{C 2-4} alkoxyphenyl) fluorene, preferably 9,9-bis ((meth) acryloyloxy mono- to tetra _{C 2-4} alkoxyphenyl) fluorene, and more preferably 9,9-bis ((meth) acryloyl Oxymono or di- _C2-4 alkoxyphenyl) fluorene}, 9,9-bis (alkyl- (meth) acryloyloxy (poly) alkoxyphenyl) fluorene {e.g., 9,9-bis [4- (2- (meta ) Acryloyloxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) -3-methylphenyl] fluorene, 9,9-bis {4- [2- (2- (Meth) acryloyloxyethoxy) ethoxy] -3-methylphenyl} full 9,9-bis [mono or dialkyl-((meth) acryloyloxy mono to hexa) such as len, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) -3,5-dimethylphenyl] fluorene C _2-4 alkoxy) phenyl] fluorene, preferably 9,9-bis [mono or dialkyl-((meth) acryloyloxymono to tetra C _2-4 alkoxy) phenyl] fluorene, more preferably 9,9-bis [ Mono or di C _1-4 alkyl-((meth) acryloyloxy mono or di C _2-4 alkoxy) phenyl] fluorene}, 9,9-bis (aryl- (meth) acryloyloxy (poly) alkoxyphenyl) fluorene { For example, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) -3-fur Nylphenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) -3-phenylphenyl] fluorene, 9,9-bis {4- [2- (2- (meth) acryloyloxyethoxy) ) ethoxy] -3-phenyl-phenyl} fluorene 9,9-bis [mono or diaryl - ((meth) acryloyloxy mono- to hexa _{C 2-4} alkoxy) phenyl] fluorene, preferably 9,9-bis [mono Or diaryl-((meth) acryloyloxymono to tetra _C2-4alkoxy ) phenyl] fluorene, more preferably 9,9-bis [mono or _diC6-10 aryl-((meth) acryloyloxymono or diC _2-4 alkoxy) phenyl] fluorene} etc. 9,9-bis ((meth) acrylo Yloxy (poly) alkoxyphenyl) fluorenes [Ring ^{Z a} in the formula (A1) is a benzene ring, m1 is 1 or more (e.g., 1-6, preferably 1-4, more preferably 1-2) Compound 9,9-bis ((meth) acryloyloxy (poly) alkoxynaphthyl) fluorene {e.g., 9,9-bis [6- (2- (meth) acryloyloxyethoxy) -2-naphthyl] fluorene, 9, 9-bis [5- (2- (meth) acryloyloxyethoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2- (meth) acryloyloxypropoxy) -2-naphthyl] fluorene, 9, 9,9-bis ((meth) such as 9-bis {6- [2- (2- (2- (meth) acryloyloxyethoxy) ethoxy] -2-naphthyl} fluorene Methacryloyloxy mono- to hexa _{C 2-4} alkoxy naphthyl) fluorene, preferably 9,9-bis ((meth) acryloyloxy mono- to tetra _{C 2-4} alkoxy naphthyl) fluorene, and more preferably 9,9-bis (( meth) acryloyloxy mono- or _{di-C 2-4} alkoxy-naphthyl) fluorene} etc. 9,9-bis ((meth) acryloyloxy (poly) alkoxy naphthyl) ring ^{Z a} naphthalene ring in fluorenes [formula (A1) , M1 is 1 or more (for example, 1 to 6, preferably 1 to 4, more preferably 1 to 2)] and the like.

Preferred fluorene compounds (A) include 9,9-bis ((meth) acryloyloxyphenyl) fluorenes (or a compound in which ring Za is ^a benzene ring and m1 is 0 in the formula (A1)), 9,9 -Bis ((meth) acryloyloxynaphthyl) fluorenes (or a compound in which the ring Za is ^a naphthalene ring and m1 is 0 in the formula (A1)), 9,9-bis ((meth) acryloyloxy (poly) alkoxy Phenyl) fluorenes (or a compound in which the ring Za is ^a benzene ring and m1 is 1 or more in the formula (A1)), 9,9-bis ((meth) acryloyloxy (poly) alkoxynaphthyl) fluorenes (or the above) In the formula (A1), a compound in which ring Za is ^a naphthalene ring and m1 is 1 or more is included.

Particularly preferred fluorene compounds (A) include 9,9-bis ((meth) acryloyloxy (poly) alkoxyphenyl) fluorenes [for example, 9,9-bis ((meth) acryloyloxy mono to octa C _2-4 alkoxyphenyl) fluorene, preferably 9,9-bis ((meth) acryloyloxy mono- to tetra _{C 2-4} alkoxyphenyl) fluorene such as 9,9-bis ((meth) acryloyloxy (poly) alkoxyphenyl) fluorene; 9,9-bis [mono- or di - ((meth) acryloyloxy mono- to octa _{C 2-4} alkoxy) phenyl] fluorene, preferably 9,9-bis [mono- or di - ((meth) acryloyloxy mono- to tetra 9 such as C _2-4 alkoxy) phenyl] fluorene , 9-bis (alkyl- (meth) acryloyloxy (poly) alkoxyphenyl) fluorene; 9,9-bis [mono or diaryl-((meth) acryloyloxymono to octa C _2-4 alkoxy) phenyl] fluorene, preferably 9,9-bis [mono- or diaryl-((meth) acryloyloxymono to tetra _C2-4alkoxy ) phenyl] fluorene and other 9,9-bis (aryl- (meth) acryloyloxy (poly) alkoxyphenyl) Fluorene, etc.], 9,9-bis ((meth) acryloyloxy (poly) alkoxynaphthyl) fluorenes [eg, 9,9-bis ((meth) acryloyloxymono to octa C _2-4 alkoxynaphthyl) fluorene, preferably Is 9,9-bis ((meth) acryloylio) Etc. Shimono to tetra C _2-4 alkoxy naphthyl) fluorene such as 9,9-bis ((meth) acryloyloxy (poly) alkoxy naphthyl) fluorene.

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

  In addition, a commercial item may be used for a fluorene compound (A), and what was synthesize | combined by the conventional method may be used.

(Fluorene compound (B))
In the fluorene compound (B) having three or more polymerizable unsaturated bonds (or the polymerizable unsaturated compound (B) having a fluorene skeleton), as the polymerizable unsaturated bond (polymerizable unsaturated group), the fluorene can be used. The groups exemplified in the section of compound (A) can be mentioned, and a typical fluorene compound (B) is a fluorene compound having a (meth) acryloyl group (or (meth) acryloyloxy group).

  In the fluorene compound (B), the number of polymerizable unsaturated bonds may be 3 or more (for example, 3 to 10, preferably 4 to 8, more preferably 4 to 6, particularly 4). Preferred fluorene compounds include fluorene compounds having 4 or more polymerizable unsaturated bonds (for example, (meth) acryloyl groups).

  The fluorene compound (B) has a fluorene skeleton together with a polymerizable unsaturated bond. That is, the fluorene compound (B) is a compound in which a polymerizable unsaturated bond (or a group containing a polymerizable unsaturated bond) is bonded (or substituted) to the fluorene skeleton. Examples of such a fluorene skeleton include the fluorene skeleton exemplified in the section of the fluorene compound (A), and may be a 9,9-bisarylfluorene skeleton typically. Note that the fluorene skeleton may have a substituent in fluorene or a substituent substituted at the 9-position of fluorene.

  In addition, the substitution position (bonding position) of the polymerizable unsaturated bond (or a group containing a polymerizable unsaturated bond) with respect to the fluorene skeleton is not particularly limited, and may be the fluorene skeleton itself or the 9th position of fluorene. May be bonded to the substituent.

  Representative fluorene compounds (B) are represented by 9,9-bisarylfluorenes having 4 or more polymerizable unsaturated bonds (particularly (meth) acryloyl groups), for example, the following formula (B1): Compounds and the like.

(Wherein ring ^{Z b} represents an aromatic hydrocarbon ^{ring, R 1b} represents a ^{substituent, R 2b} represents an alkylene ^{group, R 3b} is a hydrogen atom or a methyl ^{group, R 4b} represents a substituent K2 is an integer of 0 to 4, m2 is an integer of 0 or more, n2 is an integer of 0 or more, and p is an integer of 2 or more.)
In the above formula (B1), the aromatic hydrocarbon ring represented by ring Z ^b, ring illustrated by ring Z ^a in the formula (A1) can be exemplified. Representative ring Z ^b is a benzene ring, a naphthalene ring, in particular, a benzene ring is preferred. Incidentally, two rings Z ^b may be the same or different rings, may be generally the same ring.

In the formula (B1), examples of the group R ^1b include the groups exemplified for the group R ^1a in the formula (A1). In addition, when k2 is plural (2 or more), the groups R ^1b may be different from each other or the same. Further, the groups R ^1b substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ^1b to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k2 is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the substitution number k2 may be the same or different from each other.

In the formula (B1), examples of the alkylene group represented by the group R ^2b include the alkylene groups exemplified by the group R ^2a (such as C _2-4 alkylene group). The group R ^2b may be a branched alkylene group (eg, a C _3-4 alkylene group) as in the case of the group R ^2a . When m2 is 2 or more, the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group. Further, in the two rings Z ^b, also radicals R ^2b are the same or different, may be a conventional same.

The number of oxyalkylene groups (OR ^2b ) (average added mole number) m2 is the same range as in the case of the oxyalkylene group (O ^2a ) [eg 0 to 10 (eg 0 to 8), preferably 0 to 0]. 6 (for example, 1 to 6), more preferably 0 to 4 (for example, 1 to 4)]. In particular, m2 may be 1 or more (for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2). Incidentally, substitution number m2, in different rings Z ^b, may be the same or different. Further, in the two rings ^{Z b,} the sum of the oxyalkylene groups (m2 × 2 × p, m2 × p + m2 × p) is 0 to 40 (e.g., 4 to 36) can be selected from the range of about, for example, 0 32 (for example, 4 to 28), preferably 0 to 24 (for example, 2 to 20), more preferably 0 to 16 (for example, 0 to 12), particularly 0 to 8 (for example, 4 to 8), Also good.

In the formula (B1), the substitution number p of the group containing the group R ^2b (sometimes referred to as a (meth) acryloyl group-containing group) may be 2 or more (for example, 2 to 6). -4, preferably 2-3, more preferably 2. In addition, the number p of substitutions may be the same or different in each ring Z ^b and is usually the same in many cases.

In the above formula (B1), the substitution position of (meth) acryloyl group-containing group is not particularly limited, as long as the replaced with appropriate substitution position of ring Z ^b. For example, the (meth) acryloyl group-containing group has an appropriate position (for example, the 3 and 4 positions, the 2 and 4 positions, etc.) of the benzene ring when the ring Z ^b is a benzene ring and p is 2. In particular, it may be substituted at positions 2 and 4. In particular, a compound substituted at the 2- and 4-positions can be suitably used from the viewpoint of easily suppressing or preventing coloring in the cured product.

Examples of the substituent R ^4b substituted on the ring Z ^b include the same groups as those exemplified for the substituent R ^4a . Note that in the same ring Z ^b, if n2 is plural (2 or more), groups R ^4b may be different from each other, it may be identical. Further, in the two rings Z ^b, groups R ^4b may be the same or different. Further, preferred substituents which n2 can be selected according to the kind of ring ^{Z b,} for example, 0-8, preferably 0-4 (e.g., 0-3), more preferably may be 0-2 . In particular, when the ring Za is ^a benzene ring, the substitution number n2 may be 0 to 2, preferably 0 to 1, and more preferably about 0. Note that in different rings Z ^b, several substitutions n2 may be the same or different, may be a conventional same.

  Representative fluorene compounds (B) (or the compounds represented by the formula (B1)) include 9,9-bis (poly (meth) acryloyloxyaryl) fluorenes, 9,9-bis (poly (meta ) Acryloyloxy (poly) alkoxyaryl) fluorenes.

The 9,9-bis (poly (meth) acryloyloxyaryl) fluorenes include, for example, 9,9-bis (di to tetra (meth) acryloyloxyphenyl) fluorene [for example, 9,9-bis (2,4 -Di (meth) acryloyloxyphenyl) fluorene, 9,9-bis (3,4-di (meth) acryloyloxyphenyl) fluorene, 9,9-bis (3,4,5-tri (meth) acryloyloxyphenyl) ) 9,9-bis (di or tri (meth) acryloyloxyphenyl) fluorene such as fluorene, preferably 9,9-bis (di (meth) acryloyloxyphenyl) fluorene, more preferably 9,9-bis (2 , 4-di (meth) acryloyloxyphenyl) fluorene] and the like 9,9-bis (poly (meth) acrylo Oxy phenyl) fluorenes [In the formula (B1) Ring ^{Z b} is a benzene ring, m2 is 0, p is 2 or more (e.g., 2-4, preferably 2-3, further compounds preferably 2)] ; corresponding thereto to 9,9-bis (poly (meth) acryloyloxy naphthyl) fluorenes (ring ^{Z b} in the formula (B1) is a naphthalene ring, compounds m2 is 0, p is 2 or more), and the like It is done.

The 9,9-bis [poly ((meth) acryloyloxy (poly) alkoxy) aryl] fluorenes correspond to the 9,9-bis (poly (meth) acryloyloxyaryl) fluorenes and are represented by the formula (B1) In which m2 is 1 or more (for example, 1-6, preferably 1-4, more preferably 1-2), such as 9,9-bis [di to tetra ((meth) acryloyloxy (poly) alkoxy ) Phenyl] fluorene {eg, 9,9-bis [2,4-di (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3,4-di (2- (meth) acryloyl) Oxyethoxy) phenyl] fluorene, 9,9-bis [2,4-di (2- (meth) acryloyloxypropoxy) phenyl] fluorene, 9,9 Bis {2,4-di [2- (2- (meth) acryloyloxyethoxy) ethoxy] phenyl} fluorene, 9,9-bis [3,4,5-di (2- (meth) acryloyloxyethoxy) phenyl ] 9,9 bis fluorene [di- or tri ((meth) acryloyloxy mono- to hexa _{C 2-4} alkoxy) phenyl] fluorene, preferably 9,9-bis [di or tri ((meth) acryloyloxy mono or tetra _{C 2-4} alkoxy) phenyl] fluorene, more preferably 9,9-bis [di ((meth) acryloyloxy mono- or _{di-C 2-4} alkoxy) phenyl] fluorene, in particular 9,9-bis [2, 4-di ((meth) acryloyloxy mono- or _{di-C 2-4} alkoxy) phenyl] fluorene such as 9,9-bis [poly ( Meth) acryloyloxy (poly) alkoxy) phenyl] fluorenes [Ring ^{Z b} in the formula (B1) is a benzene ring, m2 is 1 or more (e.g., 1-6, preferably 1-4, more preferably 1-2 ), P is 2 or more (for example, 2 to 4, preferably 2 to 3, more preferably 2)]; 9,9-bis [poly ((meth) acryloyloxy (poly) alkoxy) corresponding thereto ) naphthyl] ring ^{Z b} is a naphthalene ring in fluorenes [formula (B1), m @ 2 is 1 or more (e.g., 1-6, preferably 1-4, more preferably 1 to 2), p is 2 or more (e.g. , 2-4, preferably 2-3, and more preferably 2).

Preferred fluorene compound (B), 9,9-bis (poly (meth) acryloyloxy phenyl) fluorenes [or the formula (B1) Ring ^{Z b} is a benzene ring, m2 is 0, p is 2 or more (e.g. , 2-4, preferably 2-3, more preferably 2)], 9,9-bis [poly ((meth) acryloyloxy (poly) alkoxy) phenyl] fluorenes [or the above formula (B1) ring ^{Z b} naphthalene ring in, m2 is 1 or more (e.g., 1-6, preferably 1-4, more preferably 1 to 2), p is 2 or more (e.g., 2-4, preferably 2-3, More preferably, the compound is 2).

Particularly preferred fluorene compounds (B) include 9,9-bis [poly ((meth) acryloyloxy (poly) alkoxy) phenyl] fluorenes {for example, 9,9-bis [di- or tri ((meth) acryloyloxy). mono- to octa _{C 2-4} alkoxy) phenyl] fluorene, preferably include 9,9-bis [di or tri ((meth) acryloyloxy mono- to tetra _{C 2-4} alkoxy) phenyl] fluorene, etc.}.

In addition, 9,9-bis (2,4-di (meth) acryloyloxyphenyl) fluorenes [eg, 9,9-bis (2,4-di (meth) acryloyloxyphenyl) fluorene], 9,9 -Bis [2,4-di ((meth) acryloyloxy (poly) alkoxy) phenyl] fluorenes {e.g. 9,9-bis [2,4-di ((meth) acryloyloxymono to octa _C2-4 Alkoxy) phenyl] fluorene, preferably 9,9-bis [2,4-di ((meth) acryloyloxymono to tetra C _2-4alkoxy ) phenyl] fluorene, etc.}, among which 9,9-bis [ 2,4-di ((meth) acryloyloxy (poly) alkoxy) phenyl] fluorenes are preferred.

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

  As the fluorene compound (B), a commercially available product may be used, and a conventional method [for example, 9-fluorenone and a polyhydric phenol (such as catechol) or an alkylene oxide adduct thereof in the presence of an acid catalyst may be used. You may use what was synthesize | combined by the method (the method of patent document 2 etc.), etc. which make the corresponding polyol obtain, react, and react a (meth) acrylic acid component with this polyol.

  For example, 9,9-bis (2,4-di (meth) acryloyloxyphenyl) fluorenes are present in the presence of acid catalysts (eg, sulfuric acid) and thiols (eg, mercaptoalkanoic acids such as mercaptopropionic acid). , 9-fluorenones and resorcinols are reacted with polyols [ie, 9,9-bis (2,4-dihydroxyphenyl) fluorenes] and (meth) acrylic acid components (for example, (meth) acrylic) It can be obtained by reacting acid, (meth) acrylic acid halide, etc.). In addition, 9,9-bis [2,4-di ((meth) acryloyloxyalkoxy) phenyl] fluorenes are similarly produced in the presence of an acid catalyst and thiols in the presence of 9-fluorenones and 1,3-bis ( Obtained by reacting a (meth) acrylic acid component with polyols [ie, 9,9-bis [2,4-di (hydroxyalkoxy) phenyl] fluorenes] obtained by reacting with hydroxyalkoxy) benzenes. It is done.

  In addition, the fluorene compound (B) obtained by synthesis may contain impurities (for example, (meth) acrylate of a multimerized polyol, etc.) derived from raw materials. For example, as described above, the fluorene compound (B) can be obtained by reacting the corresponding polyol with a (meth) acrylic acid component, and this polyol contains impurities such as a multimerized polyol. When a polyol containing such impurities is used, impurities other than the fluorene compound (B) are also contained in the (meth) acrylate as a product. In addition, when such impurities are obtained 9,9-bis (2,4-dihydroxyphenyl) fluorenes and 9,9-bis [2,4-di (hydroxyalkoxy) phenyl] fluorenes, It is easy to generate (by-product) relatively much.

  The amount of such impurities is preferably relatively small. For example, the ratio of the fluorene compound (B) and the fluorene compound (B) to the total amount of impurities (or the purity of the fluorene compound (B)) is 80% or more (for example, 85 to 100%), preferably 90% or more (for example, 93 to 100%), and more preferably 95% or more (for example, 97 to 100%). Such a ratio or purity can be determined by measuring purity (area ratio) by high performance liquid chromatography (HPLC), GPC measurement, or the like. The amount of impurities can be efficiently reduced by purifying a polyol as a precursor with which the (meth) acrylic acid component is reacted.

(Non-fluorene monofunctional monomer (C))
The composition of the present invention may contain only the fluorene compound (A) and the fluorene compound (B) as a polymerization component, but if necessary, it further contains a non-fluorene monofunctional monomer (having a fluorene skeleton). (Monofunctional monomer) (C) which does not. Examples of the non-fluorene monofunctional monomer (C) include monomers having one polymerizable unsaturated bond or polymerizable group [eg, alkenyl group (vinyl group, allyl group, etc.), (meth) acryloyl group]. It is done. Such a non-fluorene-based monofunctional monomer can be used for the purpose of adjusting curability, hardness and viscosity, for example, and the monofunctional monomer is mainly used for adjusting the viscosity and curability.

  Monofunctional monomers (non-fluorene-based monofunctional monomers) include (meth) acrylic monomers, non- (meth) acrylic monomers [for example, styrene-based monomers (for example, styrene, α-methylstyrene, vinyltoluene, etc.), vinyl esters Type monomers (for example, vinyl acetate, etc., N-vinylpyrrolidone, 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]}, arylthio (meth) acrylate, aralkylthio (meth) acrylate, arylthioa described below Examples include rualkyl (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, aromatic (meth) acrylates, sulfur-containing (meth) acrylates, and the like can be suitably used from the viewpoint of achieving a balance between high refractive index and excellent handling properties. Among these, phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate, C _6-10 aryl-C _1-4 alkyl (meth) acrylates such as benzyl (meth) acrylate, phenylthioethyl ( Phenylthio C _1-4 alkyl (meth) acrylates such as (meth) acrylate may 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 (for example, 0.01 to 100 mPa · s). , Preferably 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 0.01 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 a refractive index of 589 nm, for example, 1.4 to 1.65, preferably 1.41 to 1.62. More 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).

(Non-fluorene polyfunctional monomer (D))
The composition of the present invention uses a non-fluorene-based polyfunctional monomer (polyfunctional monomer having no fluorene skeleton) as long as the effect of the present invention is not impaired for the purpose of improving the hard coat property. May be. The polyfunctional monomer has at least two polymerizable unsaturated bonds or polymerizable groups [for example, alkenyl group (vinyl group, allyl group, etc.), (meth) acryloyl group] (for example, 2 to 8, preferably 2). ~ 6, more preferably 2-4). In the polyfunctional monomer, the polymerizable groups may be the same or different groups.

Examples of such a multifunctional monomer (non-fluorene-based multifunctional monomer) include a multifunctional (meth) acrylic monomer {for example, a bifunctional (meth) acrylate {for example, an alkylene glycol di (meth) acrylate [ C _2-10 alkylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 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 Rudi (meth) acrylate, (poly) oxy C _2-6 alkylene glycol di (meth) acrylate etc. such as 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) acrylate, 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 polyfunctional (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, dipenta Polyol tri to hexa (meth) acrylate} such as erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate}, multifunctional non- (meth) acrylic monomers (for example, , Divinylbenzene) and the like. Usually, the polyfunctional monomer may be composed at least of a polyfunctional (meth) acrylate. Polyfunctional monomers may be used alone or in combination of two or more.

(Ratio of each component constituting the polymerization component)
In the composition of the present invention, the ratio of the fluorene compound (A) and the fluorene compound (B) can be selected, for example, from the range of the former / the latter (weight ratio) = 1/99 to 99/1. 95/5, preferably 10/90 to 90/10 (for example, 15/85 to 85/15), more preferably about 20/80 to 80/20 (for example, 25/75 to 75/25) Also good.

  The ratio of the fluorene compound (A) to the fluorene compound (B) can be selected from the range of the former / the latter (molar ratio) = 1/99 to 99/1, for example, preferably 5/95 to 95/5. May be about 10/90 to 90/10 (for example, 15/85 to 85/15), more preferably about 20/80 to 80/20 (for example, 25/75 to 75/25).

  In addition, the ratio of the total amount of the fluorene compound (A) and the fluorene compound (B) is 30% by weight or more (for example, 40 to 100% by weight), preferably 50% with respect to the entire polymerization components constituting the composition of the present invention. It may be 70% by weight or more (for example, 60 to 100% by weight), more preferably 70% by weight or more (for example, 75 to 100% by weight), and particularly 80% by weight or more. Further, the ratio of the total amount of the fluorene compound (A) and the fluorene compound (B) is 20 mol% or more (for example, 30 to 100 mol%), preferably with respect to the entire polymerization components constituting the composition of the present invention. It may be 40 mol% or more (for example, 50 to 100 mol%), more preferably 60 mol% or more (for example, 65 to 100 mol%), particularly 70 mol% or more.

  When the composition of the present invention contains a non-fluorene-based monofunctional monomer (C), the proportion of the non-fluorene-based monomer (C) is 100 parts by weight based on the total amount of the fluorene compound (A) and the fluorene compound (B). 0.1 to 200 parts by weight (for example, 0.3 to 170 parts by weight), for example, 0.5 to 150 parts by weight (for example, 0.7 to 120 parts by weight), preferably 1 To 100 parts by weight (for example, 2 to 80 parts by weight), more preferably about 3 to 70 parts by weight (for example, 4 to 50 parts by weight), particularly about 5 to 40 parts by weight (for example, 7 to 30 parts by weight). May be.

  Moreover, the ratio of a non-fluorene-type monomer (C) is from the range of about 0.5-500 mol (for example, 1-400 mol) with respect to 100 mol of total amounts of a fluorene compound (A) and a fluorene compound (B). For example, 3 to 300 mol (eg 5 to 250 mol), preferably 10 to 200 mol (eg 15 to 180 mol), more preferably 20 to 150 mol (eg 25 to 120 mol), in particular About 30-100 mol may be sufficient.

  The proportion of the non-fluorene-based monofunctional monomer (C) can be selected from a range of about 0.3 to 400 parts by weight (for example, 0.5 to 350 parts by weight) with respect to 100 parts by weight of the fluorene compound (A). For example, 1 to 300 parts by weight (for example, 1.5 to 250 parts by weight), preferably 2 to 200 parts by weight (for example, 4 to 150 parts by weight), more preferably 5 to 120 parts by weight (for example, 8 to 100 parts by weight), particularly about 10 to 80 parts by weight (for example, 15 to 60 parts by weight).

  Moreover, the ratio of a non-fluorene type monofunctional monomer (C) can be selected from the range of about 1-1000 mol (for example, 2-800 mol) with respect to 100 mol of fluorene compounds (A). 600 mol (for example, 10 to 500 mol), preferably 20 to 400 mol (for example, 30 to 350 mol), more preferably 40 to 300 mol (for example, 50 to 250 mol), particularly about 60 to 200 mol. May be.

  In addition, the ratio of a non-fluorene type monofunctional monomer (C) is 70 weight% or less (for example, 0.1-60 weight%) with respect to the whole polymerization component, Preferably it is 50 weight% or less (for example, 1- 1). 40% by weight), more preferably 30% by weight or less (eg 2 to 25% by weight), in particular 20% by weight or less (eg 3 to 18% by weight). Moreover, the ratio of a non-fluorene type monofunctional monomer (C) is 80 mol% or less (for example, 0.5-70 mol%) with respect to the whole polymerization component, Preferably it is 60 mol% or less (for example, 1- 1). 50 mol%), more preferably 40 mol% or less (for example, 2 to 35 mol%).

  When the composition of the present invention contains a non-fluorene polyfunctional monomer (D), the proportion of the non-fluorene polyfunctional monomer (D) is 100 parts by weight of the total amount of the fluorene compound (A) and the fluorene compound (B). Can be selected from a range of about 0.1 to 100 parts by weight (for example, 0.2 to 80 parts by weight), for example, 0.3 to 50 parts by weight (for example, 0.5 to 40 parts by weight), Preferably it may be 0.7-30 weight part (for example, 0.8-20 weight part), More preferably, about 1-15 weight part may be sufficient.

  Moreover, the ratio of a non-fluorene type polyfunctional monomer (D) is 0.1-200 mol (for example, 0.3-150 mol) with respect to 100 mol of total amounts of a fluorene compound (A) and a fluorene compound (B). For example, 0.5 to 100 mol (eg 0.7 to 80 mol), preferably 1 to 50 mol (eg 1.5 to 40 mol), more preferably 2 to 30 mol. It may be about a mole.

  In addition, the ratio of a non-fluorene type polyfunctional monomer (D) is 50 weight% or less (for example, 0.05 to 40 weight%) with respect to the whole polymerization component, Preferably it is 40 weight% or less (for example, 0.8. 1 to 30% by weight), more preferably 25% by weight or less (for example, 0.5 to 20% by weight), particularly 15% by weight or less (for example, 1 to 10% by weight). Moreover, the ratio of a non-fluorene type polyfunctional monomer (D) is 70 mol% or less (for example, 0.1-60 mol%) with respect to the whole polymerization component, Preferably it is 50 mol% or less (for example, 0.8. 2 to 40 mol%), more preferably 35 mol% or less (for example, 0.5 to 30 mol%), particularly 20 mol% or less (for example, 1 to 15 mol%).

(Polymerization initiator)
The composition of the present invention may further contain a 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 photopolymerization initiator) is determined based on the polymerization components (for example, the total amount of the fluorene compound (A) and the fluorene compound (B), the fluorene compound (A), the fluorene compound (B), and the non-fluorene compound. For example, 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight (for example, 2 to 7 parts) per 100 parts by weight of the total amount of the functional monomer (C). Part by weight).

  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 to 100 parts by weight) with respect to 100 parts by weight of the photopolymerization initiator. 50 parts by weight).

(Other additives)
The curable composition of the present invention further contains conventional additives such as a solvent, a thermal polymerization inhibitor (hydroquinone, hydroquinone monoethyl ether, etc.), an antifoaming agent, a coating property improver, a thickener, a lubricant, and a stabilizer. (Antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, surfactants, dissolution accelerators, colorants, fillers, antistatic agents, silane coupling agents, leveling agents, dispersants, dispersion aids Etc. may be included. The additives may be used alone or in combination of two or more.

  Examples of the solvent include alcohols (alkyl alcohols such as ethanol, propanol, and isopropanol, glycols such as ethylene glycol and propylene glycol), hydrocarbons (aliphatic hydrocarbons such as hexane, and alicyclic rings such as cyclohexane). Formula hydrocarbons, aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, etc.), ethers (chain ethers such as dimethyl ether, diethyl ether, dioxane, tetrahydrofuran, etc.) Cyclic ethers), esters (methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl butyrate, etc.), ketones (acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrole) Cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), carbitols (methylcarbitol, ethylcarbitol, butylcarbitol, etc.), propylene glycol monoalkyl ethers (propylene glycol monomethyl ether, propylene glycol mono) Ethyl ether, propylene glycol mono n-butyl ether, etc.), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide etc.), Organic solvents such as sulfoxides (such as dimethyl sulfoxide) and nitriles (such as acetonitrile and benzonitrile) That. The solvent can be used alone or as a mixed solvent.

  A mixture comprising a combination of the fluorene compound (A) and the fluorene compound (B) has a rigid fluorene skeleton, and is relatively excellent in solvent solubility, so that a composition containing a solvent (coating composition) can be easily obtained. Can be formed.

  In the composition containing the solvent, the proportion of the polymerization component (or solid content) is 1 to 90% by weight (for example, 3 to 85% by weight), preferably 5 to 80% by weight (for example, 10 to 75% by weight). ), More preferably about 15 to 70% by weight (for example, 20 to 65% by weight).

  The curable composition of the present invention can be used in solid or liquid form at normal temperature (for example, about 20 to 25 ° C.). In particular, the curable composition of the present invention may be in a liquid form (for example, a composition containing a solvent).

  In addition, such a curable composition of this invention can be prepared by mixing each component.

[Cured product]
The curable composition of this invention hardens | cures easily by providing active energy (active energy ray). Therefore, the curable resin 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. The curable composition of the present invention is often excellent in photocurability and may be cured by applying at least light energy (light irradiation). The cured product may have a three-dimensional structure and is usually a cured film in many cases. The cured film may be a film pattern (particularly a thin film pattern). The cured film can be formed by applying the resin composition to a base material or a substrate and drying it if necessary, and then heating or exposing to an actinic ray. Then, it can be formed by selectively exposing and developing the generated latent image pattern.

  The base material or the substrate can be selected according to the use, and may be a porous material such as wood, a metal such as aluminum or copper, a ceramic such as glass or quartz, a plastic such as polyester, polymethyl methacrylate, or polycarbonate. . The curable composition of the present invention is relatively excellent in adhesion to a substrate, has a high refractive index and high transparency, and is suitable for optical applications. Among these substrates, a transparent substrate or a transparent film is suitable. You may utilize as a laminated body with a transparent base material or a transparent film by coating on top. As the transparent film, for example, it is excellent in transparency and has excellent adhesion to the curable composition. For example, cyclic olefin resin, styrene resin, (meth) acrylic resin (polymethyl methacrylate, etc.), acrylonitrile type, etc. A transparent film composed of a resin, a polyester-based resin (polyethylene terephthalate, etc.), a polyamide-based resin, a cellulose ester (triacetylcellulose, etc.) is preferable. The thickness of a transparent film can be selected according to a use, for example, 1-1000 micrometers, Preferably it is 10-500 micrometers, More preferably, about 30-300 micrometers may be sufficient.

  The application method is not particularly limited, and can be appropriately selected depending on the form (solid or liquid) of the curable composition, but in the case of a liquid composition, for example, a flow coating method, a spin coating method, or a spray coating method. , Screen printing method, casting method, bar coating method, curtain coating method, roll coating method, gravure coating method, dipping method, slit method and the like.

  After apply | coating a curable composition, you may dry (for example, dry at about 40-150 degreeC). The (pre-curing and post-curing thickness) of the coating varies depending on the application, but can be selected from a range of about 0.01 to 1000 μm, for example, 0.1 to 500 μm, preferably 0.5 to 300 μm, and more preferably 1 It may be about ~ 200 μm. In particular, in the present invention, even a relatively thin film (thin film) has high hardness. The thickness of such a thin film is, for example, 100 μm or less [for example, 0.1 to 100 μm (for example, 0.2 to 80 μm)], preferably 50 μm or less [for example, 0.3 to 50 μm (for example, 0.5 to 40 μm)], more preferably 30 μm or less [eg 1 to 30 μm (eg 2 to 25 μm)], in particular 20 μm or less (eg 3 to 15 μm).

  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. Since the curable composition of this invention is excellent in photopolymerizability, it can also obtain hardened | cured material 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, about 60 to 200 ° C, preferably about 100 to 150 ° 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 has properties such as high hardness, high heat resistance, and excellent optical properties (high transparency, high refractive index, etc.). For example, the refractive index of the cured product of the present invention can be selected from a range of about 1.55 or more (for example, 1.56 to 1.75) at 25 ° C. and 589 nm, and 1.57 or more (for example, 1.58). 1.7), preferably 1.59 or more (for example, 1.595 to 1.68), more preferably about 1.6 or more (for example, 1.605 to 1.65).

  Further, the pencil hardness of the cured product may be, for example, HB or more (for example, HB to 8H), preferably H or more (for example, H to 5H), more preferably 2H or more (for example, 2H to 4H). It can also be 3H or more. In particular, in the present invention, even a thin film having a relatively small thickness (for example, 50 μm or less, preferably 30 μm or less), such a cured film having a high hardness can be obtained. Therefore, the pencil hardness may be a pencil hardness at a thickness of 10 μm.

  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.)
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}
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 (1), the total of oxyalkylene groups (m1 + m1 ) Is 11, compound synthesized in Synthesis Example}
BREFA: 9,9-bis [2,4-di (2-acryloyloxyethoxy) phenyl] fluorene (synthesized in synthesis example)
BZA: benzyl acrylate (“FA-BZA” manufactured by Hitachi Chemical Co., Ltd., refractive index (25 ° C., 589 nm) 1.515)
DPHA: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA-2C”)
DPHA-40H: 8-functional urethane acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “DPHA-2C”, reaction product of DPHA and hexamethylene diisocyanate)
M305: Pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd., trade name “M305”)
Photopolymerization initiator: “IRGACURE 184” manufactured by Ciba Japan.

(Synthesis example)
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 placed in 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 is removed by a Dean-Stark trap, and tetraacrylate {ie, 9,9-bis [2,4-di (2-acryloyloxyethoxy) phenyl] fluorene represented by the following formula: BREFA} was obtained.

  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 (a compound having a total (average value) of m1 + m1 of 11 in the formula (1), hereinafter referred to as BPF-11EO).

  The obtained BPF-11EO and acrylic acid were reacted in the same manner as BREFA to obtain BPF-11EOA (diacrylate of BPF-11EO).

(Examples 1-9, Comparative Examples 1-2 and Reference Examples 1-8)
The components shown in Table 1, 3 parts by weight of a photopolymerization initiator, and 100 parts by weight of a solvent (propylene glycol monomethyl ether acetate) were sufficiently mixed in a shaker to prepare a resin composition. The prepared resin composition is applied to one side of a polyethylene terephthalate (PET) film (Toyobo Co., Ltd. “A4300”), film thickness of 100 μm, and irradiated with an ultraviolet ray with an integrated light quantity of 500 mJ / cm ² using a carbon arc ultraviolet ray irradiator. Thus, a cured product (cured film) having a predetermined size was obtained.

  Various characteristics of the obtained resin composition and cured product were measured or evaluated. In addition, as for the thickness of hardened | cured material (or coating film), pencil hardness was 10 micrometers or 100 micrometers, and other than that was 20-25 micrometers.

(Refractive index)
Using a multi-wavelength Abbe refractometer (manufactured by Atago, DR-M2 <using circulating thermostatic bath 60-C3>), the refractive index before and after curing at 589 nm was measured while maintaining a temperature of 25 ° C.

(Pencil hardness)
It measured based on JIS5600-5-4. In other words, the cured film was placed on a pencil hardness meter (“HEIDON-14” manufactured by Shinto Kagaku Co., Ltd.), and various pencils were pressed at a 45 degree angle while applying a weight of 750 g, and cured at a speed of 1 mm / second. The pencil hardness was measured by moving on the film and visually confirming the presence or absence of scratches on the cured film.

(Adhesion)
It measured based on JIS K5600-5-6. That is, after creating a cured film on a PET film and making 100 grid cuts in a grid pattern with a specified cutting tool, the tape was peeled after applying the tape, and the number of squares that were not peeled off It was measured.

(Curing shrinkage (curl))
A cured film of 6 cm × 6 cm was formed on the PET film, and the average of the heights of the four corners of the cured film measured on a flat desk was measured and evaluated as follows.

○: Less than 14 mm Δ: 14-17 mm
X: More than 17 mm or two corners come into contact and become cylindrical.

(Storage stability)
About the storage stability of a resin composition, after mix | blending a composition, it was left still at normal temperature for 1 week, the state of the composition was observed visually, and the following references | standards evaluated.

○: No change from the state one week ago ×: Precipitation or gelation.

(Coloring)
Visual evaluation was performed according to the following criteria.

○: No coloring or little coloring ×: Colored.

  The results are shown in the table.

The resin composition (or cured product thereof) 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, CO ₂ gas separation). Film, etc.), coating agents (for example, optical overcoat agents such as coating agents for LED (light emitting diode) elements or hard coating agents, etc.), lenses [pickup lenses (for example, DVD (digital versatile disc) pickups) Lens, etc.), microlens (eg, microlens for liquid crystal projector), spectacle lens, etc.], polarizing film (eg, polarizing film for liquid crystal display), composite sheet, brightness enhancement film, prism sheet, antireflection film (or Anti-reflection film (for example, anti-reflection film for display device), touch panel film 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), OLED (organic EL display), cathode ray tube, electronic paper and other displays (particularly thin displays) films (filters, protective films, etc.), color filters [eg, lens filters, displays Color filters, etc.], resists for liquid crystal display devices [for example, TFT array etching photoresists, pigment-dispersed photoresists, protective films, etc.], interlayer insulating films, solder resists, fuel cell films, optical films, etc. Iba, the optical waveguide can be suitably used, such as a hologram. In particular, the resin composition of the present invention 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 (12)

A curable composition comprising a fluorene compound (A) having two or less polymerizable unsaturated bonds and a fluorene compound (B) having three or more polymerizable unsaturated bonds ,
The fluorene compound (A) is at least one selected from 9,9-bis ((meth) acryloyloxyaryl) fluorenes and 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorenes And
The fluorene compound (B) is selected from 9,9-bis (poly (meth) acryloyloxyaryl) fluorenes and 9,9-bis [poly ((meth) acryloyloxy (poly) alkoxy) aryl] fluorenes. And at least one curable composition . Off fluorene compound (B) The curable composition according to claim 1, wherein the fluorene compound having four or more (meth) acryloyl groups. The fluorene compound (B) is 9,9-bis (2,4-di (meth) acryloyloxyphenyl) fluorenes and 9,9-bis [2,4-di ((meth) acryloyloxy (poly) alkoxy). The curable composition according to claim 1 or 2, which is at least one selected from phenyl] fluorenes. The curable composition according to any one of claims 1 to 3 , wherein the fluorene compound (B) is 9,9-bis [2,4-di ((meth) acryloyloxy (poly) alkoxy) phenyl] fluorenes. . Fluorene compound (A) and the fluorene compound ratio of (B) is the former / the latter (weight ratio) = 5/95 to 95/5 in which claim 1 curable composition according to any one of the 4. Fluorene compound (A), 9,9-bis ((meth) acryloyloxy mono- to hexa _{C 2-4} alkoxyphenyl) fluorene, 9,9-bis [mono- or di - ((meth) acryloyloxy mono- to hexa C _2-4 alkoxy) phenyl] fluorene, 9,9-bis [mono or diaryl - ((meth) acryloyloxy mono- to hexa _{C 2-4} alkoxy) phenyl] fluorene, and 9,9-bis ((meth) acryloyloxy Mono to hexa C _2-4 alkoxynaphthyl) fluorene,
Fluorene compound (B) is 9,9-bis [2,4-di ((meth) acryloyloxy mono- to hexa _{C 2-4} alkoxy) phenyl] fluorene,
Fluorene compound (A) and the fluorene compound ratio of (B) is the former / the latter (weight ratio) = 20/80 to 80/20 in which the curable composition according to any one of claims 1-5. Furthermore, the curable composition in any one of Claims 1-6 containing a non-fluorene type monofunctional monomer (C). The curable composition according to claim 7, wherein the non-fluorene-based monofunctional monomer (C) includes at least one monofunctional (meth) acrylate selected from aromatic (meth) acrylate and sulfur-containing (meth) acrylate. object. The curable composition according to claim 7 or 8 , wherein the proportion of the non-fluorene monofunctional monomer (C) is 1 to 100 parts by weight with respect to 100 parts by weight of the total amount of the fluorene compound (A) and the fluorene compound (B). object. The method according to claim 1 cured product is cured by applying an active energy curable composition according to any one of 9. Hardened | cured material of the curable composition in any one of Claims 1-9 . The cured product according to claim 11 , wherein the refractive index at 25 ° C. and 589 nm is 1.58 or more, and the pencil hardness at a thickness of 10 μm is H or more.