JP6734840B2 - Resin composition and optical lens - Google Patents

Description

The present invention relates to a resin composition containing a cyclic olefin resin and a compound having a 9,9-bisarylfluorene skeleton (hereinafter sometimes referred to as a fluorene compound) and useful as an optical lens.

Since the cyclic olefin resin has excellent properties such as high transparency, high heat resistance, and low birefringence, it is an optical material, for example, an imaging lens (or an optical lens included in a mobile communication device such as a mobile phone or a smartphone). ) Is used.

In recent years, as mobile phones and smartphone terminals have become thinner and more multifunctional, the size of the imaging lens mounted on the imaging device has been reduced in order to secure a space for mounting components and elements. ing. In addition, along with the miniaturization, along with the increase in the number of pixels of image pickup devices such as sensors using charge-coupled devices (CCD sensors) and sensors using complementary metal oxide semiconductors (CMOS sensors), the resolution of image pickup lenses will also increase. Is required. Such an imaging lens is compact and has high imaging performance and correction of various aberrations within the constraints of cost. Therefore, it is possible to make various efforts to select the lens configuration, shape and material by making full use of optical design. Has been done. The optical design of the imaging lens unit is performed by inputting the data of the refractive index of the lens material at a plurality of wavelengths into the calculation software and repeating the adjustment while automatically calculating it according to the algorithm. However, since the resin (or material) that can be used for the optical lens is limited, the degree of freedom in design is limited, and there is a limit to highly effective or various designs. That is, the unit of the imaging lens is composed of a plurality of lenses having different Abbe numbers and refractive indexes, and therefore, generally, one or more lenses having a large Abbe number and a medium refractive index are provided. (For example, 2 to 4 lenses made of cyclic olefin resin having an Abbe number of 56 to 57 and a refractive index of 1.51 to 1.54), a lens having a small Abbe number and a large refractive index is used. It is configured by combining a plurality of lenses (for example, one or two lenses made of fluorene resin having an Abbe number of 22 to 27 and a refractive index of 1.61 to 1.64). If there is a material in the intermediate region between the high Abbe number and the low Abbe number (Abbe number is about 28 to 55), the degree of freedom in design is improved and optimization can be expected. Regarding thermosetting resins and glass, although there are materials with an Abbe number in the middle range, glass is expensive and thermosetting resins have low lens productivity, so they are used for optical lenses such as mobile phones and smartphones. not being used.

On the other hand, a resin composition in which a compound having a fluorene skeleton or a resin containing a fluorene component is added to a thermoplastic resin is disclosed. For example, in JP-A-2005-162785 (Patent Document 1) or JP-A-2011-8017 (Patent Document 2), a resin (particularly, an aromatic ring-containing resin) has a 9,9-bisarylfluorene skeleton. It is described that the compound can be added to increase the refractive index of the resin or decrease the birefringence. Further, in these documents, an olefin resin or a cyclic olefin resin is also exemplified as a resin, and it is also described that it can be used for applications such as an optical lens.

Further, in JP-A-2014-205734 (Patent Document 3), by adding a compound having a 9,9-bisarylfluorene skeleton to a resin having a relatively small Abbe number (particularly, an aromatic ring-containing resin), It is described that the Abbe number of the resin can be increased. In this document, a cyclic olefin resin is also exemplified as the resin, and it is also described that an optical lens, an optical film or the like may be formed. In the examples, a specific fluorene compound (for example, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) or the like) was added to the polycarbonate resin or polyethylene naphthalate, and the Abbe number was adjusted. Making it big. However, the ratio of the Abbe number to the added amount of the fluorene compound was small, and the adjustment was not sufficient as an Abbe adjusting agent. In addition, in Examples of these Patent Documents 1 to 3, there is no specific description regarding the cyclic olefin resin.

Further, JP-A-2013-194186 (Patent Document 4) discloses a resin composition containing an alicyclic polyester containing a 9,9-bisarylfluorene compound as a diol component and a polycycloolefin (cyclic olefin resin). It is described that a retardation film is formed of an object. In this document, in order to improve the compatibility (miscibility) with the polycycloolefin, the polyester is formed with a fluorene compound containing an alicyclic diol component. However, this document does not describe the adjustment of the Abbe number.

Further, JP-A-2014-218660 (Patent Document 5) describes a resin composition containing a cyclic olefin copolymer and a compound having a 9,9-bisarylfluorene skeleton. This document describes that the mechanical strength (for example, tensile strength) of the cyclic olefin copolymer can be improved, and that the Abbe number is also reduced. In the examples of this document, 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene (BCF) was added to a cyclic olefin copolymer "Arton4531F" or "APEL5014DP" to obtain a resin composition. ing. Although it is described that the latter resin composition has a reduced Abbe number, the degree of reduction of the Abbe number is small with respect to the amount of BCF added. The present inventors produced these resin compositions, and in the latter resin composition, although the miscibility (compatibility) between the resin and BCF was low, it seemed to have transparency, It has been found that the resin composition may become cloudy when subjected to treatments such as hot pressing and molding, and the Abbe number cannot be measured in some cases. It was also found that these resin compositions have insufficient heat resistance (glass transition temperature). Therefore, it was found that it cannot be used for applications such as optical lenses.

JP, 2005-162785, A (claim, [0015] [0059] [0079], an example) JP, 2011-8017, A (claim, [0017] [0082], an example). JP, 2014-205734, A (claim, [0087] [0126], an example) JP, 2013-194186, A (claim, [0015] [0025], an example) JP, 2014-218660, A (claim, [0028] [0029] [0034], an example).

Therefore, an object of the present invention is to effectively reduce the Abbe number of a cyclic olefin-based resin even when the content of a fluorene compound is small, and adjust it to an Abbe number in an intermediate region (for example, an Abbe number of about 28 to 55). Another object of the present invention is to provide a resin composition that can be used and is useful for applications such as optical lenses.

Another object of the present invention is to provide a resin composition having high transparency and high heat resistance (glass transition temperature) even when a relatively large amount of a fluorene compound is contained.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a compound having a predetermined 9,9-bisarylfluorene skeleton (sometimes referred to as a fluorene compound) with respect to a cyclic olefin resin having a functional group. Is added or mixed in the form of a monomer, even if the content of the fluorene compound is small, the Abbe number of the cyclic olefin-based resin can be effectively reduced to an intermediate region, even if the Abbe number of the intermediate region is adjusted. It was found that a resin composition having high heat resistance (glass transition temperature) can be obtained, and the present invention was completed.

That is, the resin composition of the present invention contains a cyclic olefin resin having a functional group and a compound having a 9,9-bisarylfluorene skeleton having a polar substituent. The cyclic olefin-based resin may be a resin including a norbornene skeleton, and for example, the cyclic olefin-based resin may be a resin including at least a structural unit represented by the following formula (1).

(In the formula, the group R ¹ represents a hydrogen atom or an alkyl group, the group R ² represents a hydrogen atom, an alkyl group or an aryl group, and the group W represents a carboxyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, A hydroxyalkylcarbonyl group, a glycidyloxycarbonyl group, a cyano group or an amide group is shown, and q is 0 or 1.)
In the formula (1), the group R ¹ is a hydrogen atom or a methyl group, the group R ² is a hydrogen atom, the group W is a carboxyl group, a C _1-2 alkoxy-carbonyl group, a cyano group or an amide group, and q is 0. May be. The glass transition temperature of the cyclic olefin resin may be about 140 to 250°C.

Further, the compound having the 9,9-bisarylfluorene skeleton may be a compound represented by the following formula (2).

[Wherein, ring Z is an arene ring, R ³ is a halogen atom, a cyano group, an alkyl group, an aryl group, a carboxyl group or an alkoxycarbonyl group, and R ⁴ is a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group. , Cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, alkylcarbonyl group, nitro group, cyano group, amino group or substituted amino group Or R ⁴ of two rings Z may be bonded to each other to form a direct bond or an alkylene group to form a hydrocarbon ring with an adjacent carbon atom, and the group X is a group —[ (OR ⁵ ) _n1- Y ¹ ] (In the formula, the substituent Y ¹ is a hydroxyl group, a mercapto group, a glycidyloxy group or a (meth)acryloyloxy group, R ⁵ is an alkylene group, and n 1 is 0 or an integer of 1 or more. . shown) or a group _- in ^{_{[(CH 2) n2 -Y 2}} ] ( wherein the substituents ^{Y 2} is a carboxyl group, an alkoxycarbonyl group, an amino group or a substituted amino group, n2 and is 0 or an integer of 1 or more , K is an integer of 0 to 4, m is 0 or an integer of 1 or more, and p is an integer of 1 or more. ]
In the above formula (2), when the group X is [(OR ⁵ ) _n1- Y ¹ ], the substituent Y ¹ is a hydroxyl group or a glycidyloxy group, the ring Z is a benzene ring, a naphthalene ring or a biphenyl ring (particularly a naphthalene ring). ), R ³ is a C _1-4 alkyl group, k is 0 or 1, R ⁴ is a C _1-4 alkyl group, C _1-4 alkoxy group, m is 0 or 1, and R ⁵ is a C _2-4 alkylene group. , N1 may be an integer of 0 to 2, and p may be 1 or 2.

Specifically, the compound represented by the above formula (2) includes 9,9-bis(mono- or dihydroxy C _6-12 aryl)fluorene, 9,9-bis(C _6-12 aryl-hydroxy C _{6-). 12} aryl)fluorene, 9,9-bis(mono or di C _1-4 alkyl-hydroxy C _6-12 aryl)fluorene, 9,9-bis(mono or dihydroxy (poly) C _2-4 alkoxy C _6-12 Aryl)fluorene, 9,9-bis(C _6-12 aryl-hydroxy(poly)C _2-4 alkoxy C _6-12 aryl)fluorene, 9,9-bis[mono or di C _1-4 alkyl-hydroxy( Poly)C _2-4 alkoxy C _6-12 aryl]fluorene, 9,9-bis(mono- or diglycidyloxy C _6-12 aryl)fluorene, 9,9-bis(C _6-12 aryl-glycidyloxy C _{6 -12} aryl)fluorene, 9,9-bis(mono or di C _1-4 alkyl-glycidyloxy C _6-12 aryl)fluorene, 9,9-bis(mono or diglycidyloxy(poly)C _2-4 alkoxy C _6-12 aryl)fluorene, 9,9-bis(C _6-12 aryl-hydroxy(poly)C _2-4 alkoxy C _6-12 aryl)fluorene, 9,9-bis[mono or di C _1-4 alkyl - Gurijishiruokishi _{(poly) C 2-4} alkoxy _{C 6-12} aryl] it may contain at least one selected from fluorene. In particular, the compound represented by the formula (2) may be 9,9-bis(mono- or dihydroxy(poly)C _2-4 alkoxynaphthyl)fluorene.

The ratio of the cyclic olefin-based resin to the compound having the 9,9-bisarylfluorene skeleton may be about the former/the latter (weight ratio)=99/1 to 30/70. Further, in the resin composition, the Abbe number calculated from the refractive index with respect to the spectra of C-line, D-line and F-line is 28 to 55 and/or the refractive index at a wavelength of 589 nm is about 1.51 to 1.60. Good.

The present invention also includes a molded body and an optical lens formed of the resin composition.

In addition, in this specification, a "(meth)acryloyloxy group" means an acryloyloxy group and a methacryloyloxy group.

The resin composition of the present invention can effectively reduce the Abbe number of the cyclic olefin resin, probably because the cyclic olefin resin has a predetermined functional group, and can easily adjust the Abbe number of the intermediate region. Moreover, since the cyclic olefin-based resin has a polycyclic structure having the functional group, it has high heat resistance (glass transition temperature) and can maintain heat resistance even when a fluorene compound is added. Therefore, the Abbe number and heat resistance (high glass transition temperature) of the intermediate region can be compatible. Furthermore, because of the high compatibility of both, even if the proportion of the fluorene compound is large, it can be mixed uniformly without clouding, has high transparency, and can significantly reduce the Abbe number. Such a resin composition can widen the degree of freedom in designing lenses and the like and is useful for applications such as optical materials (for example, optical lenses).

The resin composition of the present invention contains a cyclic olefin resin having a functional group, and a compound having a 9,9-bisarylfluorene skeleton having a polar substituent (sometimes referred to as a fluorene compound).

[Cyclic olefin resin]
The cyclic olefin resin has a functional group (A). The cyclic olefin resin is a resin containing at least a cyclic olefin having an ethylenic double bond in the ring as a polymerization component (for example, a homopolymer of a cyclic olefin, a copolymer of a cyclic olefin and a copolymerizable monomer). May be The functional group (A) may be contained in the cyclic olefin and/or the copolymerizable monomer, and preferably at least in the cyclic olefin.

The cyclic olefin having the functional group (A) may be a monocyclic olefin, but is usually a polycyclic olefin (for example, a bi- to tetra-cyclic olefin etc.) in many cases. The polycyclic olefin is an unsaturated compound having a functional group (A) and a carbon-carbon unsaturated double bond, and a cyclic di- or triene (eg, cyclopentadiene, dicyclohexyl) optionally containing a substituent (C). It can be prepared by utilizing a Diels-Alder reaction with a pentadiene or the like.

Examples of the unsaturated compound include compounds having a carboxyl group (eg, unsaturated mono- or dicarboxylic acid [eg (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid, etc.]], alkoxycarbonyl Compounds having a group [for example, alkyl (meth)acrylate (for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, and the like (meth)) C _1-6 alkyl acrylate, preferably C _1-4 alkyl (meth)acrylate, etc., unsaturated dicarboxylic acid alkyl ester (eg, itaconic acid C _1-4 alkyl ester such as itaconic acid methyl ester, dimethyl maleate) Maleic acid di-C _1-4 alkyl ester such as ester) and the like], a compound having a cycloalkyloxycarbonyl group [eg, cycloalkyl (meth)acrylate (eg, (meth)acrylic acid such as cyclohexyl (meth)acrylate) Acid (C _5-8 cycloalkyl etc.)], a compound having an aryloxycarbonyl group [eg C _6-10 aryl (meth)acrylate such as phenyl (meth)acrylate], a compound having a hydroxyl group [eg , Hydroxyalkyl (meth)acrylate (for example, hydroxy C _2-4 alkyl (meth)acrylate such as hydroxyethyl (meth)acrylate), and the like, compounds having an alkoxy group [for example, methoxy (meth)acrylate] C _2-4 alkoxy C _2-4 alkyl (meth)acrylate such as ethyl], a compound having a mercapto group (for example, a compound corresponding to the compound having the hydroxyl group), a compound having a glycidyl group (for example, Examples thereof include glycidyl (meth)acrylate, a compound having an amide group (eg, (meth)acrylamide), a compound having a cyano group (eg, (meth)acrylonitrile), and the like. These unsaturated compounds may be used alone or in combination of two or more. Among these unsaturated compounds, compounds having a carboxyl group, a C _1-2 alkoxy-carbonyl group, a cyano group or an amide group are preferable.

As the substituent (C) of the cyclic olefin, for example, a halogen atom (fluorine atom, chlorine atom, bromide atom, iodine atom, etc.), alkyl group (C _1-6 alkyl group such as methyl group, ethyl group, etc., preferably C _1-4 alkyl group, etc., cycloalkyl group (for example, C _5-10 cycloalkyl group such as cyclohexyl group), aryl group (for example, C _6-10 aryl group such as phenyl group), aralkyl group (benzyl group) , C _6-10 aryl-C _1-4 alkyl groups such as phenethyl group) and the like. The cyclic olefin may contain a single or two or more kinds of substituents (C).

Among the cyclic olefins having a functional group (A), examples of the bicyclic olefins (bicycloalkenes) include cyclic olefins in which at least the functional group (A) is substituted on 2-norbornene, 2,5-norbornadiene or the like ( For example, 5-C _1-4 alkyl-5 such as 5-carboxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-ethoxycarbonyl-2-norbornene and 5-methyl-5-carboxy-2-norbornene. -5-C _1-4 alkyl-5-C _1-2 alkoxy-, such as carboxy-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-methyl-5-ethoxycarbonyl-2-norbornene Carbonyl-2-norbornene, 5-methyl-5-cyclohexyloxycarbonyl-2-norbornene and the like 5-C _1-4 alkyl-5-C _5-10 cycloalkoxy-carbonyl-2-norbornene, 5-hydroxyethoxycarbonyl- 5-Hydroxy linear or branched C _2-3 alkoxy-carbonyl-2-norbornene such as 2-norbornene, 5-cyano-2-norbornene, 5-amido-2-norbornene, 5,6-dicarboxy- 2-norbornene, 5,6-diC _1-2 alkoxy-carbonyl-2-norbornene such as 5,6-dimethoxycarbonyl-2-norbornene, 6-phenyl-5-carboxy-2-norbornene, etc.) and the like can be exemplified. ..

As the tricyclic olefins (tricycloalkenes) having the functional group (A), for example, tricyclo[5.2.1.0 ^2,6 ]decane-3-ene is substituted with at least the functional group (A). the cyclic olefin (e.g., 8-hydroxy - tricyclo [5.2.1.0 ^{2, 6]} decane-3-ene, 9-hydroxy - tricyclo [5.2.1.0 ^{2, 6]} decane-3 ene, 8-methoxy - tricyclo [5.2.1.0 ^{2, 6]} _{decane-3-8-C 1-4} alkoxy such as ene - tricyclo [5.2.1.0 ^{2, 6]} decane -3 9-C _1-4 alkoxy-tricyclo[5.2.1.0 ^2,6 ]decane-, such as -ene, 9-methoxy-tricyclo[5.2.1.0 ^2,6 ]decane-3-ene. 3-ene, 8-cyano - tricyclo [5.2.1.0 ^{2, 6]} decane-3-ene, 9-cyano - tricyclo [5.2.1.0 ^{2, 6]} decane-3-ene) Can be exemplified.

Examples of the tetracyclic olefins (tetracycloalkenes) having the functional group (A) include tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene and the like) at least a functional group (A) is substituted with a cyclic olefin (for example, 8-carboxy-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-ethoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 8-C _1-2 alkoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .7 such as 1 ^7,10 ]dodec-3-ene. 1 ^7,10 ]dodec-3-ene, 8-methyl-8-carboxy-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10] _{dodeca-3-8-C 1-4} alkyl-8-carboxy such as ene - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ]dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-methyl-8-ethoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10] _{dodeca-3-8-C 1-4} alkyl _{-8-C 1-2} alkoxy such as ene - carbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ]dodec-3-ene, 8-methyl-8-cyclohexyloxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10] _{dodeca-3-8-C 1-4} alkyl _{-8-C 5-8} cycloalkoxy such as ene - carbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ]dodec-3-ene, 8-hydroxyethoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene such as 8-hydroxy straight-chain or branched-chain _{C 2-3} alkoxycarbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ]dodec-3-ene, 8-cyano-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-amido-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8,9-dicarboxy-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8,9-dimethoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene such as _{8,9-di-C 1-2} alkoxy - carbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ]dodec-3-ene, 8-phenyl-9-carboxy-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene and the like} and the like. These cyclic olefins may be used alone or in combination of two or more. Among these cyclic olefins, cyclic olefins containing a norbornene skeleton (particularly bicyclic olefins, tetracyclic olefins, etc.) are preferable from the viewpoint of heat resistance.

The cyclic olefin having a functional group (A) is a cyclic olefin having no functional group (A) (for example, a monocyclic olefin such as cycloheptene, 2-norbornene, tetracyclo[4.4.0.1 ^2,5 . ^1-7,10 ]-3-didecene and other ^{di- to} tetracyclic olefins) and the like.

In a cyclic olefin resin (for example, a copolymer of a cyclic olefin having a functional group (A) and a cyclic olefin having no functional group (A)), a cyclic olefin having a functional group (A) and a functional group ( The ratio with the cyclic olefin not having A) is, for example, former/latter (molar ratio)=50/50 to 100/0 (for example, 60/40 to 95/5), preferably 70/30 to 100/. 0 (for example, 75/25 to 90/10), more preferably 80/20 to 100/0 (for example, 85/15 to 95/5), particularly 90/10 to 100/0 (for example, 95/5). It may be about 100/0). If the proportion of the cyclic olefin having the functional group (A) is too small, the Abbe number may not be effectively reduced.

Specific examples of the cyclic olefin-based resin include resins (homopolymers or copolymers) containing at least a structural unit represented by the following formula (1).

(In the formula, the group R ¹ represents a hydrogen atom or an alkyl group, the group R ² represents a hydrogen atom, an alkyl group or an aryl group, and the group W represents a carboxyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, A hydroxyalkylcarbonyl group, a glycidyloxycarbonyl group, a cyano group or an amide group is shown, and q is 0 or 1.)
Examples of the alkyl group of the substituents R ¹ and R ² include a C _1-4 alkyl group such as a methyl group and an ethyl group. Examples of the aryl group of the substituent R ² include a phenyl group and the like. R ¹ is preferably a hydrogen atom or a methyl group, and R ² is preferably a hydrogen atom.

Examples of the alkoxycarbonyl group in the group W include a linear or branched C _1-6 alkoxy-carbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group, and a linear or branched chain is preferable. A _C1-4 alkoxy- carbonyl group etc. are mentioned. In addition, since the glass transition temperature of the alkoxycarbonyl group is often higher as the carbon number is shorter, a C _1-2 alkoxy-carbonyl group is particularly preferable.

Examples of the cycloalkyloxycarbonyl group include C _5-8 cycloalkyloxy-carbonyl groups such as cyclohexyloxy-carbonyl group.

Examples of the aryloxycarbonyl group include a C _6-10 aryloxy-carbonyl group such as a phenoxycarbonyl group.

Examples of the hydroxyalkylcarbonyl group include a hydroxy linear or branched C _2-4 alkyl-carbonyl group such as a 2-hydroxyethylcarbonyl group and a 2-hydroxypropylcarbonyl group.

Among the groups W, a carboxyl group, a C _1-2 alkoxycarbonyl group, a cyano group, an amide group and the like are preferable from the viewpoint of heat resistance (glass transition temperature). Note that q is 0 or 1, and is usually 0 in many cases.

The cyclic olefin-based resin may be a homopolymer, but usually may be a copolymer with a copolymerizable monomer.

Examples of the copolymerizable monomer include a chain olefin [alkene (eg, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 2-methyl-1-pentene. , 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1 -Hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and other C _2-12 alkenes) and the like], etc., and preferably α-olefins (eg, ethylene, propylene, It may be C _2-10 α-olefins such as 1-butene, 1-pentene, 1-hexene, preferably C _2-6 α-olefins, especially ethylene. The copolymerizable monomer may have a functional group (A), and, for example, a compound similar to the unsaturated compounds exemplified above (for example, (meth)acrylic acid, methyl (meth)acrylate). , (C _1-2 alkyl (meth)acrylate such as ethyl (meth)acrylate).

Among these copolymerizable monomers, C _2-6 α-olefins, (meth)acrylic acid, C _1-2 alkyl (meth)acrylate and the like are preferable.

In the cyclic olefin resin (for example, a copolymer of the copolymerizable monomer and the cyclic olefin), the ratio of the cyclic olefin is, for example, 20 to 99 mol% (for example, 25 to 90 mol %), preferably May be about 30 to 95 mol% (for example, 35 to 90 mol%), more preferably about 40 to 90 mol% (for example, 50 to 80 mol%), for example, 30 to 70 mol%, preferably It may be about 40 to 60 mol% (for example, 45 to 55 mol%). If the proportion of the cyclic olefin is too low, the miscibility (or affinity) with the fluorene compound may decrease, the Abbe number may not be effectively reduced, and the heat resistance (glass transition temperature) may decrease. ..

Further, the copolymer is a resin having a constitutional unit represented by the above formula (1) and a chain alkylene (for example, corresponding to C _2-6 alkene such as ethylene, propylene, butylene) unit. May be. For example, it may be a copolymer having a structural unit represented by the following formula (1a).

(R and s represent the repeating number of each structural unit and represent an integer of 1 or more. The ratio of r and s is r/s=90/10 to 10/90 (molar ratio). W, R ¹ , R ² and q are the same as above.)
The copolymer having the structural unit represented by the formula (1a) may be an alternating copolymer, a random copolymer, a block copolymer or the like.

In many cases, the heat resistance (glass transition temperature) of the cyclic olefin-based resin is improved when the ratio of the cyclic olefin having the functional group (A) is increased. The glass transition temperature of the cyclic olefin-based resin can be selected from the range of about 120 to 250° C. when measured according to JIS K7121, and is, for example, 140 to 250° C., preferably 150 to 220° C., and more preferably 160. The temperature may be about -200°C (for example, 160-180°C). The glass transition temperature of the cyclic olefin-based resin may be, for example, 120 to 180°C, preferably 130 to 180°C, more preferably 140 to 170°C. If the proportion of the cyclic olefin having the functional group (A) is too low, the miscibility (or affinity) with the fluorene compound may decrease, the heat resistance (glass transition temperature) may decrease, and the Abbe number may be effective. There is a risk that it will not be possible to reduce the amount. Depending on the type of resin, it may not be detected below the decomposition temperature. The glass transition temperature can be measured by using a differential scanning calorimeter or the like.

The weight average molecular weight (polystyrene conversion) of the cyclic olefin resin is, for example, 10,000 to 200,000 (e.g., 20,000 to 190000), preferably 30,000 to 170000 (e.g., 40,000 to) when measured by gel permeation chromatography (GPC). It is about 150,000, and more preferably about 40,000 to 130,000 (eg, 50,000 to 130,000) If the molecular weight is too large, the melt viscosity will be high, and the productivity and processability of the optical material may be lowered. Mechanical strength is reduced.

As such a cyclic olefin resin, a commercially available product (for example, "ARTON F4520" manufactured by JSR Corporation) may be used. Incidentally, "ARTONF4520" as the functional group (A), a carboxyl group, tetracyclic olefins having an alkoxycarbonyl group from such a methoxycarbonyl group or an ethoxycarbonyl group (tetracyclo ^[4.4.0.1 2, 5 .1 ^7,10 ]-3-dodecene) is a resin obtained by hydrogenation reaction of a ring-opening polymer. "APEL5014DP" manufactured by Mitsui Chemicals, Inc. is an addition polymer of a bicyclic olefin (2-norbornene) having no functional group and ethylene.

The cyclic olefin resin is produced by a conventional method [for example, addition polymerization, ring-opening polymerization (ring-opening metathesis polymerization, etc.), the ring-opening polymerization (ring-opening metathesis polymerization, etc.), followed by hydrogenation catalyst ( For example, a method of hydrogenating using a palladium catalyst, a palladium catalyst supported on alumina, a ruthenium catalyst, etc.) may be used.

The cyclic olefin resin has a relatively high Abbe number. In the present invention, without introducing an alicyclic structure into the additive component, by adding a fluorene compound in the form of a monomer to a cyclic olefin resin having a relatively high Abbe number, the Abbe number of the cyclic olefin resin is increased. It can be effectively reduced.

[Fluorene compound]
The fluorene compound has a 9,9-bisarylfluorene skeleton and a polar substituent (B). It is estimated that the combination of the polar substituent (B) and the functional group (A) improves the compatibility (or miscibility) between the fluorene compound and the cyclic olefin resin, and the Abbe number can be effectively reduced.

Specific examples of the fluorene compound include compounds represented by the following formula (2).

[Wherein, ring Z is an arene ring, R ³ is a halogen atom, a cyano group, an alkyl group, an aryl group, a carboxyl group or an alkoxycarbonyl group, and R ⁴ is a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group. , Cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, alkylcarbonyl group, nitro group, cyano group, amino group or substituted amino group Or R ⁴ of two rings Z may be bonded to each other to form a direct bond or an alkylene group to form a hydrocarbon ring with an adjacent carbon atom, and the group X is a group —[ (OR ⁵ ) _n1- Y ¹ ] (In the formula, the substituent Y ¹ is a hydroxyl group, a mercapto group, a glycidyloxy group or a (meth)acryloyloxy group, R ⁵ is an alkylene group, and n 1 is 0 or an integer of 1 or more. . shown) or ^{_{- [(CH 2) n2 -Y}} 2] ( wherein the substituents ^{Y 2} represents a carboxyl group, an alkoxycarbonyl group, an amino group or a substituted amino group, n2 and is 0 or an integer of 1 or more ,), k is an integer of 0 to 4, m is 0 or an integer of 1 or more, and p is an integer of 1 or more. ]
In the formula (2), examples of the arene ring represented by the ring Z include a monocyclic arene ring such as a benzene ring and a polycyclic arene ring, and the polycyclic arene ring includes a condensed polycyclic ring. The arene ring (condensed polycyclic hydrocarbon ring), the ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring) and the like are included.

Examples of the fused polycyclic arene ring include a fused bicyclic arene (eg, fused bicyclic C _10-16 arene such as naphthalene) ring, a fused tricyclic arene (eg, anthracene, phenanthrene, etc.) ring, and the like. Examples include fused bi- to tetracyclic arene rings. Examples of preferable fused polycyclic arene ring include fused C _10-14 polycyclic arene ring such as naphthalene ring and anthracene ring, and naphthalene ring is particularly preferable.

The ring-collecting arene ring includes a biarene ring, for example, a biphenyl ring, a binaphthyl ring, a biC _6-12 arene ring such as a phenylnaphthalene ring (1-phenylnaphthalene ring, 2-phenylnaphthalene ring, etc.), a terarene ring, for example, An example is a ter C _6-12 arene ring such as a terphenylene ring. Preferred ring-assembled arene rings include biC _6-10 arene rings, especially biphenyl rings. The two rings Z may be the same or different rings.

In the formula (2), examples of the group R ³ include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a cyano group, an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group). Group, C _1-6 alkyl group such as t-butyl group), aryl group (C _6-10 aryl group such as phenyl group), carboxyl group, alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.) C _1-6 alkoxy-carbonyl group, preferably C _1-4 alkoxy-carbonyl group) and the like. The group R ³ may be the polar substituent (B), and examples of the polar substituent (B) include a carboxyl group and an alkoxycarbonyl group (for example, C _1-6 such as methoxycarbonyl group). Alkoxy-carbonyl groups, preferably C _1-4 alkoxy-carbonyl groups, etc.) and the like. In particular, the group R ³ may be a polar substituent (B) such as a carboxyl group, an alkyl group or the like. The substitution number k is an integer of 0 to 4 (for example, 0 to 3), preferably an integer of 0 to 2 (for example, 0 or 1). The substitution numbers k may be the same or different from each other, and when k is 2 or more, the types of the substituents R ³ may be the same or different from each other, and the two benzene rings of the fluorene ring are substituted. The types of the substituents R ³ may be the same or different. The substitution position of the substituent R ³ is not particularly limited and may be, for example, the 2-position to the 7-position (2-position, 3-position and/or 7-position) of the fluorene ring.

Among these rings Z, a polycyclic arene ring is preferable, and a naphthalene ring is particularly preferable, from the viewpoint of excellent balance of heat resistance and optical properties.

In the above formula (2), the group R ⁴ is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, s A linear or branched C _1-10 alkyl group such as -butyl group and t-butyl group, preferably a linear or branched C _1-6 alkyl group), a cycloalkyl group (cyclopentyl group, cyclo) Examples thereof include a C _5-10 cycloalkyl group such as a hexyl group), an aralkyl group (a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group and a phenethyl group), and a nitro group. The group R ⁴ may be a polar substituent (B), and examples of such a polar substituent (B) include an alkoxy group (eg, a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, Isobutoxy group, C _1-10 alkoxy group such as t-butoxy group), cycloalkoxy group (for example, C _5-10 cycloalkyloxy group such as cyclohexyloxy group), aryloxy group (for example, phenoxy group etc.) C _6-10 aryloxy group etc.), an aralkyloxy group (eg C _6-10 aryl-C _1-4 alkyloxy group etc. such as benzyloxy group), an alkylthio group (eg methylthio group, ethylthio group etc. C _1-10 alkylthio group, etc.), cycloalkylthio group (for example, C _5-10 cycloalkylthio group such as cyclohexylthio group), arylthio group (for example, C _6-10 arylthio group such as thiophenoxy group), Aralkylthio groups (eg, C _6-10 aryl-C _1-4 alkylthio groups such as benzylthio group), carboxyl groups, alkoxycarbonyl groups (eg, C _1-6 alkoxy-carbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group). Group, preferably C _1-4 alkoxy-carbonyl group etc.), alkylcarbonyl group (eg C _1-4 alkyl-carbonyl group such as acetyl group, propionyl group etc.), cyano group, substituted amino group (eg dimethylamino) Groups such as diC _1-4 alkylamino groups, diacetylamino groups such as diC _1-4 alkyl-carbonylamino groups, etc.) and the like.

Of these substituents R ⁴ , typically, a polar substituent (B) such as an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group, a cyano group, and a substituted amino group, a halogen atom, an alkyl group, a cyclo Examples thereof include an alkyl group, an aralkyl group and a nitro group. Preferable substituent R ⁴ includes an alkoxy group, an alkyl group and the like, particularly a C _1-4 alkyl group such as a methyl group. The types of the substituents R ⁴ may be the same or different in the same or different ring Z.

Further, R ^{4 s} of the two rings Z are bonded to each other to form a direct bond or an alkylene group (for example, a C _1-6 alkylene group such as a methylene group or an ethylene group, preferably a C _1-4 alkylene group). However, it may form a hydrocarbon ring with the adjacent carbon atom. The hydrocarbon ring may be, for example, a 5- to 10-membered (for example, 5 to 8-membered) hydrocarbon ring. When R ^{4 of} two rings Z and a carbon atom adjacent thereto form a hydrocarbon ring, the bonding position of R ⁴ is, for example, 2-position of the phenyl group, 3 when the ring Z is a benzene ring. Often in the -position (particularly 2-position), the ring Z is a naphthalene ring, and when the 9-position of fluorene is bonded to the 1-position or 2-position of the naphthalene ring, the α-position of the naphthalene ring, It is often the β-position (particularly the α-position). The ring formed by the hydrocarbon ring and the two rings Z may be, for example, a fluorene ring. The 9-position spiro carbon atom of fluorene may be an asymmetric carbon atom and may form an R isomer or an S isomer of optical isomers. Examples of typical compounds include compounds represented by the following formula (3).

(In the formula, X, R ³ , k and p are the same as above)
The number of substitutions m can be appropriately selected according to the type of ring Z, the number of m, and the like, and may be, for example, an integer of 0 to 8, an integer of 0 to 4, preferably 0 to 3 (for example, , 0-2), especially 0 or 1. In particular, when m is 1 or 2, the ring Z may be a benzene ring, a naphthalene ring or a biphenyl ring, and the substituent R ⁴ may be a methyl group.

In the group X of the formula (2), the alkylene group R ⁵ includes a linear or branched alkylene group, and includes, for example, a C _2-6 alkylene group (such as an ethylene group, a trimethylene group, a tetramethylene group ( Preferably a linear C _2-4 alkylene group, particularly an ethylene group), for example, a branched C _3-6 alkylene group (preferably branched) such as a propylene group, a 1,2-butanediyl group, a 1,3-butanediyl group. A chain C _3-4 alkylene group, especially a propylene group) and the like can be mentioned. When n1 is an integer of 2 or more, the alkylene groups R ⁵ may be the same or different. Further, the types of the alkylene group R ⁵ may be the same or different in the same or different ring Z.

The number n1 of oxyalkylene groups (OR ⁵ ) can be selected from the range of about an integer of 0 to 15 (for example, an integer of 0 to 10), for example, an integer of 0 to 8 (for example, 1 to 8), preferably It may be an integer of 0 to 5 (for example, 1 to 5), more preferably an integer of 0 to 4 (for example, 1 to 4), particularly an integer of about 0 to 3 (for example, 1 to 3), and usually , 0 to 2 (for example, 0 or 1).

Further, n2 may be 0 or an integer of 1 or more (for example, 1 to 6, preferably 1 to 4, more preferably about 1 to 2). n2 may be 0 or an integer of 1-2.

The substituent Y ¹ has many parts which are polar substituents (B), and examples thereof include a hydroxyl group, a mercapto group, a glycidyloxy group, and a (meth)acryloyloxy group. The substituent Y ² is a carboxyl group. Group, alkoxycarbonyl group (for example, C _1-6 alkoxy-carbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxy group carbonyl group), amino group, substituted amino group (for example, di C _1-4 alkylamino group such as dimethylamino group, di-C _1-4 alkyl, such as di-acetylamino group - carbonyl amino group) and the like.

In the formula (2), the substitution number p of the group X may be an integer of 1 or more, depending on the type of the ring Z, for example, an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably May be an integer from 1 to 2, especially 1. The number of substitutions n1 or n2 may be the same or different in each ring Z.

The group X can be substituted at an appropriate position on the ring Z, and, for example, when the ring Z is a benzene ring, the 2-,3-,4-position of the phenyl group (particularly 3-position and/or 4-position) is often substituted, and when ring Z is a naphthalene ring, it is often 5-8-position of the naphthyl group, for example, a naphthalene ring with respect to 9-position of fluorene. At the 1-position or 2-position (substituting in the relationship of 1-naphthyl or 2-naphthyl), and the relationship of 1,5-position, 2,6-position and the like (particularly p- When X is 1, the group X is often substituted in the 2,6-position). Further, when p is 2 or more, the substitution position is not particularly limited. Further, in the ring-assembled arene ring Z, the substitution position of the group X is not particularly limited, and, for example, even if it is substituted with an arene ring bonded to the 9-position of fluorene and/or an arene ring adjacent to this arene ring. Good. For example, the 3-position or 4-position of the biphenyl ring Z may be bonded to the 9-position of fluorene, and when the 4-position of the biphenyl ring Z is bonded to the 9-position of fluorene, The substitution position may be any of 2-, 3-, 2'-, 3'-, 4'-positions, usually 2-, 3'-, 4'-positions, preferably 2-, 4-positions. It may be substituted at the'-position (particularly at the 2-position).

Incidentally, group X {group _{^{- [(OR 5) n1 -Y}} 1]} In the substituent ^{Y 1} is hydroxy group is preferably a glycidyl group.

The polar substituent (B) of the fluorene compound may be derived from any of the substituents Y ¹ , Y ² and the substituents R ³ , R ⁴ , and is usually at least the substituents Y ¹ , Y ^2. Often derived from. Examples of the polar substituent (B) include a hydroxyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, a mercapto group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, a glycidyloxy group, Examples thereof include (meth)acryloyloxy, a carboxyl group, an alkoxycarbonyl group, an amino group, a substituted amino group, an alkylcarbonyl group, a cyano group, and a substituted amino group. The fluorene compound may contain a single or two or more polar substituents (B). Among these polar substituents (B), a hydroxyl group and a glycidyloxy group are preferred.

Specifically, in the formula (2), in the group X, the substituent Y ¹ is a hydroxy group or a glycidyloxy group, and the substituent Y ¹ is a hydroxy group, n1 is 0, and p is 1 Certain compounds, for example, 9,9-bis(hydroxyarene)fluorenes {for example, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(3-hydroxyphenyl)fluorene, 9,9-bis 9,6-Bis(hydroxy C _6-12 aryl)fluorene such as (6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene, 9,9-bis(3 -Phenyl-4-hydroxyphenyl)fluorene, 9,9-bis(4-phenyl-3-hydroxyphenyl)fluorene and other 9,9-bis( _C6-12aryl - _{hydroxyC6-12aryl} )fluorene, 9 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene, 9,9-bis(4-methyl-3-hydroxyphenyl)fluorene and other 9,9-bis(mono or diC _1-4 alkyl-hydroxy) C _6-12 aryl) fluorene}, etc. dihydroxy-9,9'-spirobifluorene, such as 2,7-dihydroxy-9,9'-spirobifluorene can be exemplified.

In the above formula (2), in the group X, the substituent Y ¹ is a hydroxy group, n1 is 0, and p is 2 or more, and examples thereof include 9,9-bis[(poly)hydroxyarene]fluorene. Class {9,9-bis(3,4-dihydroxyphenyl)fluorene, 9,9-bis(2,4-dihydroxyphenyl)fluorene and other 9,9-bis(dihydroxyC _6-12 aryl)fluorene, etc.} Can be illustrated.

In the formula (2), in the group X, the substituent Y ¹ is a hydroxy group, n1 is 1, and p is 1, for example, 9,9-bis(hydroxyalkoxyarene)fluorenes {for example, , 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[6-(2-hydroxyethoxy) )-2-Naphtyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene, 9,9-Bis[5-(2-hydroxypropoxy)-1-naphthyl]fluorene and other 9,9-bis(hydroxy C _2-4 alkoxy C _6-12 aryl)fluorenes, 9,9-bis[4- Phenyl-3-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-phenyl-3-(2-hydroxypropoxy)phenyl]fluorene, and other 9,9-bis[C _6-12 aryl-hydroxy. C _2-4 alkoxy C _6-12 aryl]fluorene, 9,9-bis[3-methyl-4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-methyl-3-(2- 9,9-bis[mono- or di-C _1-4 alkyl-hydroxy C _2-4 alkoxy C _6-12 aryl]fluorene etc. such as hydroxypropoxy)phenyl]fluorene},2,7-di(2-hydroxyethoxy) Examples include di(hydroxy C _2-4 alkoxy)-9,9′-spirobifluorene such as −9,9′-spirobifluorene.

In the formula (2), in the group X, the substituent Y ¹ is a hydroxy group, n1 is 1, and p is 2 or more, for example, 9,9-bis[(poly)hydroxyalkoxyarene] Fluorenes 9,9-bis[3,4-di(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[5,6-di(2-hydroxyethoxy)naphthyl]fluorene, etc. Bis(dihydroxy C _2-4 alkoxy C _6-12 aryl)fluorene and the like} and the like.

In the formula (2), in the group X, the compound in which the substituent Y ¹ is a hydroxyl group, n1 is 2 or more, and p is 1 corresponds to the compound in which n1 is 0 or 1, and is an oxyalkylene group. A compound in which the repeating unit n1 of (in particular, an oxy C _2-4 alkylene group) is 2 to 5, for example, 9,9-bis{4-[2-(2-hydroxyethoxy)ethoxy]phenyl}fluorene, 9, 9-bis{6-[2-(2-hydroxyethoxy)ethoxy]-2-naphthyl}fluorene, 9,9-bis{5-[2-(2-hydroxyethoxy)ethoxy]-1-naphthyl}fluorene, 9,9-bis[3,4-di[2-(2-hydroxyethoxy)ethoxy]phenyl]fluorene, 9,9-bis[5,6-di[2-(2-hydroxyethoxy)ethoxy]naphthyl] 9,9-bis(mono- or dihydroxypoly C _2-4 alkoxy C _6-12 aryl)fluorene such as fluorene, 9,9-bis[4-phenyl-3-[2-(2-hydroxyethoxy)ethoxy]phenyl ] 9,9-Bis[C _6-12 aryl-hydroxy poly C _2-4 alkoxy C _6-12 aryl]fluorene, such as fluorene, 9,9-bis[4-methyl-3-[2-(2-hydroxy 9,9-Bis[mono or di C _1-4 alkyl-hydroxypoly C _2-4 alkoxy C _6-12 aryl]fluorene such as ethoxy)ethoxy]phenyl]fluorene, 2,7-di[2-(2- Examples include di(hydroxypoly C _2-4 alkoxy)-9,9′-spirobifluorene such as hydroxyethoxy)ethoxy]-9,9′-spirobifluorene.

Further, in the formula (2), in the group X, the compound in which the substituent Y ¹ is a glycidyloxy group is, for example, a compound in which a glycidyloxy group is substituted in place of the hydroxyl group exemplified above, for example, 9,9. 9,9- such as -bis(4-glycidyloxyphenyl)fluorene, 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene, 9,9-bis(3,4-diglycidyloxyphenyl)fluorene 9,9-bis(C _6-12 aryl-glycidyloxy C ₆ such as bis(mono or diglycidyloxy C _6-12 aryl)fluorene and 9,9-bis(4-phenyl-3-glycidyloxyphenyl)fluorene _-12 aryl)fluorene, 9,9-bis(mono- or di-C _1-4 alkyl-glycidyloxy C _6-12 aryl)fluorene such as 9,9-bis(3-methyl-4-glycidyloxyphenyl)fluorene, 9,9-bis[4-(2-glycidyloxyethoxy)phenyl]fluorene, 9,9-bis[6-(2-glycidyloxyethoxy)-2-naphthyl]fluorene, 9,9-bis[3-methyl 4,5-(2-glycidyloxyethoxy)phenyl]fluorene and other 9,9-bis(mono- or diglycidyloxy(poly)C _2-4 alkoxy C _6-12 aryl)fluorene, 9,9-bis[4- 9,9-Bis[C _6-12 aryl-glycidyloxy(poly)C _2-4 alkoxy C _6-12 aryl]fluorene, such as phenyl-3-(2-glycidyloxyethoxy)phenyl]fluorene, 9,9- 9,9-Bis[mono or diC _1-4 alkyl-glycidyloxy(poly)C _2-4 alkoxy C _6-12 aryl such as bis[3-methyl-4-(2-glycidyloxyethoxy)phenyl]fluorene ] Fluorene, diglycidyloxy-9,9'-spirobifluorene such as 2,7-diglycidyloxy-9,9'-spirobifluorene, 2,7-di(2-glycidyloxyethoxy)-9,9 '- di (glycidyloxy _{(poly) C 2-4} alkoxy) such as spirobifluorene-9,9'-like spirobifluorene can be exemplified.

In addition, "(poly) _C2-4 alkoxy" means the group whose repeating number n1 or n2 of _C2-4 alkoxy is an integer greater than or equal to 1.

Further, the compound represented by the formula (2) also includes a compound in which a mercapto group or a (meth)acryloyloxy group is substituted in place of the hydroxyl group or the glycidyloxy group shown in the specific examples.

In the formula (2), group X {group ^{_{- [(CH 2) n2 -Y}} 2]} , examples of the compound substituent ^{Y 2} is a carboxyl group, n2 is 0, compound p is 1 , For example, 9,9-bis(carboxyaryl)fluorenes {for example, 9,9-bis(3-carboxyphenyl)fluorene, 9,9-bis(4-carboxyphenyl)fluorene, 9,9-bis(5 -Carboxy-1-naphthyl)fluorene, 9,9-bis( _carboxyC6-12 aryl)fluorene such as 9,9-bis(6-carboxy-2-naphthyl)fluorene; n2 is 1 and p is 1 Examples of the compound represented by the formula: 9,9-bis(carboxyalkyl-aryl)fluorenes {for example, 9,9-bis(4-(carboxymethyl)phenyl)fluorene, 9,9-bis(4-(2 -Carboxyethyl)phenyl)fluorene, 9,9-bis(3-(carboxymethyl)phenyl)fluorene, 9,9-bis(5-(carboxymethyl)-1-naphthyl)fluorene, 9,9-bis(6 Examples include 9,9-bis(carboxy C _1-6 alkyl-C _6-12 aryl)fluorene such as -(carboxymethyl)-2-naphthyl)fluorene.

The compound represented by the formula (2) also includes a compound in which an alkylcarbonyl group, an amino group or a substituted amino group is substituted in place of the carboxyl group shown in the specific examples.

From the viewpoint of heat resistance, among these compounds, in the above formula (2), ring Z is a benzene ring, Y ¹ is a hydroxyl group, n1=0, p=1, m=1 or 2, R ⁴ =C _{1 -4} alkyl group compound, for example, 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene (BCF); in the above formula (2), ring Z is a condensed polycyclic C _10-14 arene ring. , Y ¹ is a hydroxyl group, n1=0, p=1, for example, 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF), 9,9-bis(5-hydroxy-1) - naphthyl) fluorene, 9,9-bis (4-methyl-3-hydroxyphenyl) fluorene; the formula (2), the ring Z fused polycyclic _{C 10-14} arene ring, ^{Y 1} is a hydroxyl group, n1 =1 to 3 and p=1, for example, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF), 9,9-bis[5-(2-hydroxy) Ethoxy)-1-naphthyl]fluorene, 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene; in the above formula (2), ring Z is a bi or ter C _6-12 arene ring, Compounds in which Y ¹ is a hydroxyl group, n1=1 to 3, R ⁵ =C _2-4 alkylene group, p=1, for example, 9,9-bis[3-phenyl-4-(2-hydroxyethoxy)phenyl ] Fluorene (BOPPEF), 9,9-bis[4-phenyl-3-(2-hydroxyethoxy)phenyl]fluorene and the like are preferable.

From the viewpoint of fluidity (or moldability), in the formula (2), ring Z is a benzene ring, Y ¹ is a hydroxyl group, n1=1 to 3, R ⁵ is a C _2-4 alkylene group, and p=1. Certain compounds, for example, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 9,9-bis[3-(2-hydroxyethoxy)phenyl]fluorene; in formula (2) above. , A compound in which ring Z is a fused polycyclic C _10-14 arene ring, Y ¹ is a hydroxyl group, n1=1 to 3 and p=1, for example, BNEF, 9,9-bis[5-(2-hydroxy Ethoxy)-1-naphthyl]fluorene, 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene; in the formula (2), ring Z is a benzene ring, Y ¹ is a glycidyl group, and n1. =0, p=1, for example, 9,9-bis(4-glycidyloxyphenyl)fluorene (BPFG) and 9,9-bis(3-glycidyloxyphenyl)fluorene are preferable.

In particular, in the above formula (2), a compound in which the ring Z is a condensed polycyclic C _10-14 arene ring, Y ¹ is a hydroxyl group, n1=0 and p=1 [for example, 9,9-bis(6- Hydroxy-2-naphthyl)fluorene (BNF) and the like]; in the above formula (2), ring Z is a condensed polycyclic C _10-14 arene ring, Y ¹ is a hydroxyl group, n1=1 to 3 and p=1. Certain compounds such as BNEF, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene are It is preferable because the Abbe number can be reduced while the high heat resistance (glass transition temperature) of the cyclic olefin-based resin is effectively maintained, and the fluidity (or moldability) can be greatly improved. In the formula, ring Z is a condensed polycyclic C _10-14 arene ring, Y ¹ is a hydroxyl group, n1=1 to 2 (particularly 1), and p=1, for example, BNEF has heat resistance, optical properties, It is particularly preferable from the viewpoint that moldability is highly compatible.

The compound represented by the formula (2) may be a commercially available product or may be produced by a conventional method. For example, in the group X, the compound in which the substituent Y ¹ is a hydroxyl group is a 9-fluorenone compound and a hydroxyl group-containing arene ring compound in which the group [HO—(R ⁵ O) _n1 −] is substituted in the ring Z (for example, And a phenoxyalkanol such as 2-phenoxyethanol) in the presence of an acid catalyst, a fluorene compound having a hydroxyaryl group substituted at the 9-position of fluorene [eg, 9,9-bis(4-hydroxyphenyl) ) Fluorene and the like] and at least one selected from alkylene oxide, alkylene carbonate and haloalkanol corresponding to the group OR ⁵ may be synthesized. In addition, for example, a compound in which the substituent Y ¹ of the group X is represented by a glycidyloxy group can be prepared by reacting fluorenes in which the group [HO-(R ⁵ O) _n1- ] is substituted on the ring Z with epichlorohydrin. ..

[Resin composition]
The resin composition of the present invention contains the cyclic olefin-based resin having a functional group (A) and the fluorene compound having a polar substituent (B), and is added or mixed (or melt-kneaded) with the fluorene compound. Even if the ratio is small, the Abbe number of the cyclic olefin resin can be effectively reduced, and a resin composition having an Abbe number in the intermediate region can be obtained. Further, even if it is a cyclic olefin-based resin (for example, a polycyclic olefin-based resin), it has high compatibility with a fluorene compound having a polar group, probably because it has a predetermined functional group, and the proportion of the fluorene compound is high. Even if the amount is large, it can be mixed uniformly without clouding, the Abbe number can be greatly reduced, and the transparency is excellent. Further, since such a cyclic olefin resin has a rigid crosslinked structure having the functional group (for example, a bicyclic structure or a tricyclic structure having a norbornene skeleton), it has a high glass transition temperature. Even if a fluorene compound is added, high heat resistance (glass transition temperature) can be maintained. Further, since the Abbe number can be reduced and the refractive index can be effectively increased, the refractive index is high even at the Abbe number in the intermediate region. Therefore, the degree of freedom in optical design can be improved, and it can be used for optical material applications (for example, optical lenses, optical sheets, optical films, etc.).

The ratio of the cyclic olefin-based resin and the fluorene compound can be selected from the range of the former/latter (weight ratio)=99/1 to 40/60 (97/3 to 40/60), for example, 95/5. To 45/55 (for example, 93/7 to 45/55), preferably 90/10 to 50/50 (for example, 87/13 to 60/40), and more preferably 85/15 to 70/30. May be. If the proportion of the cyclic olefin resin is too small, the heat resistance may be insufficient, and if it is too large, the Abbe number may not be effectively reduced, and the moldability (or fluidity) may be deteriorated. is there.

The Abbe number may be, for example, about 28 to 55, preferably 30 to 53 (eg, 32 to 51), and more preferably 35 to 50 (eg, 40 to 50). The Abbe number can be calculated from the refractive index for the spectra of C line (656 nm), D line (589 nm) and F line (456 nm).

The refractive index of the resin composition (or molded product) at a wavelength of 589 nm is, for example, 1.51 to 1.60, preferably 1.52 to 1.58, more preferably 1.53 to 1.57. May be

Further, the fluorene compound has a conformation (cardo structure) in which a fluorene ring and two aryl rings (such as a benzene ring) are orthogonal to each other, and exhibits optical isotropy. Therefore, the addition of the fluorene compound can further reduce the birefringence of the cycloolefin resin having an alicyclic structure and having a relatively low birefringence. Therefore, the resin composition has a relatively low birefringence. That is, the birefringence of the resin composition may be, for example, 30 to 56 nm, preferably 33 to 55 nm, more preferably 35 to 54 nm. The birefringence can be measured by the method of the example.

The resin composition (or molded product) can achieve both the Abbe number in the intermediate region and the heat resistance (high glass transition temperature). That is, the glass transition temperature (Tg) of the resin composition depends on the type of functional group (or type of resin), but is, for example, 100 to 200° C. (for example, 120 to 190° C.), preferably 130 to 180. C (for example, 135 to 180° C.), more preferably 140 to 170° C. (for example, 145 to 165° C.), for example, 135 to 250° C. (for example, 150 to 230° C.), preferably 160. ˜210° C., more preferably 170 to 200° C. If the glass transition temperature is too low, heat resistance may decrease, and if it is too high, moldability may decrease. The glass transition temperature can be measured by differential scanning calorimetry (measurement).

In addition, the resin composition may include various additives [eg, a filler or a reinforcing agent, a colorant (a dye, an optical brightener, etc.), a conductive agent, a flame retardant, a plasticizer, a lubricant, a stabilizer, if necessary. (Antioxidants, UV absorbers, heat stabilizers, etc.), release agents, antistatic agents, dispersants, flow control agents, leveling agents, defoamers, surface modifiers, stress reducing agents, carbon materials, etc. ] May be included. These additives may be used alone or in combination of two or more. An antioxidant may be used from the viewpoint of heat resistance stability, and an ultraviolet absorber may be used from the viewpoint of weather resistance stability.

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane and tetrakis. (Methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate)methane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-Trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, stearyl-β-(3,5-di-t-butyl-4- Hydroxyphenyl)propionate, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-diethylphenylmethane, 3,9-bis[1,1-dimethyl-2-(β-( 3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl], 2,4,8,10-tetraoxaspiro[5.5]undecane, tris(2,4-di-t-butyl) Phenyl)phosphite, cyclic neopentanetetraylbis(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetraylbis(2,6-di-t-butyl-4-methylphenyl) Examples thereof include phosphite and 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenyl). Ethyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-t-pentylphenol, 2-(benzotriazol-2-yl)-4,6-di-t-butylphenol, 2 , 2'-methylenebis{4-(1,1,3,3-tetramethylbutyl)-6-[(2H-benzotriazol-2-yl)phenol]} and the like.

The proportion of the additive depends on the kind of the additive, but is, for example, 0.001 to 10 parts by weight, preferably 0.01 to 7 parts by weight, and more preferably 0, relative to 100 parts by weight of the resin composition. It may be about 0.05 to 5 parts by weight.

Further, the resin composition can be obtained by mixing the cyclic olefin resin, the fluorene compound, and [if necessary, other components (for example, the additive)]. The mixing method is not particularly limited, and for example, it may be mixed by melt-kneading, or may be mixed by dissolving the respective components in a solvent.

The resin composition can significantly improve fluidity and moldability while maintaining high heat resistance. The melt flow rate (MFR) of the resin composition depends on the type of the resin, but is, for example, 5 to 50 g/10 minutes, preferably 7 by a method (temperature 280° C., load 2.16 kgf) according to JIS K7210. It may be about 47 g/10 minutes, more preferably about 10 to 45 g/10 minutes.

Furthermore, the present invention also includes a molded body formed of such a resin composition. The shape of such a molded body is not particularly limited and can be appropriately selected according to the application. For example, a two-dimensional shape (planar shape, film shape, sheet shape, etc.), three-dimensional shape [uneven shape, aspherical shape Shape (for example, elliptical shape), tubular shape, rod shape, tube shape, hollow shape, etc.] and the like.

The molded body can be manufactured by using, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a casting molding method or the like.

Moreover, since the molded product or resin composition of the present invention has excellent optical properties, it can be suitably used for applications of optical materials (for example, optical lenses, optical sheets, optical films, etc.). In particular, the resin composition of the present invention has a medium Abbe number, and thus is useful for forming optical lenses and the like.

For example, an optical lens is usually manufactured by an injection molding method from the viewpoint of productivity. In the injection molding method, an optical lens having a small optical distortion can be obtained by appropriately adjusting molding conditions such as resin temperature, mold temperature and pressure. In addition, since it is necessary to precisely control the shape of the lens surface in an optical lens, it is difficult to transfer the curved surface with high accuracy using a resin with low fluidity, and the resin temperature and mold temperature during molding are high. In many cases, however, the fluidity is improved for molding. However, if the resin temperature and the mold temperature are increased, problems such as decomposition of the resin, decomposition of additives and the like, volatilization, sticking to the mold, and dirt may occur. Since the resin composition of the present invention can improve the fluidity of the resin while maintaining the heat resistance (high glass transition temperature) of the resin, these problems can be prevented. The resin temperature may be, for example, about 200 to 350° C., and the mold temperature is, for example, a temperature 10 to 30° C. lower than the glass transition temperature (Tg) of the resin (or the cyclic olefin resin). May be

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, each measuring method and evaluation method in Examples and Comparative Examples are as follows.

(Measurement of molecular weight (Mw))
The sample was dissolved in tetrahydrofuran (THF), and the weight average molecular weight (Mw) in terms of polystyrene was measured using gel permeation chromatography (HLC-8120GPC, manufactured by Tosoh Corporation).

(Measurement of glass transition temperature (Tg))
It was measured according to JIS K 7121 using a differential scanning calorimeter (DSC 8500 manufactured by Perkin Elmer Co., Ltd.).

(Measurement of melt flow rate)
The melt flow rate (MFR) was measured in accordance with JIS K7210 under the conditions of a temperature of 280° C. and a load of 2.16 kg in Examples 1 to 10 and Comparative Example 2, and a temperature of 280° C. and a load of 16 kg in Comparative Example 1.

(Measurement of refractive index and Abbe number)
The refractive index and the Abbe's number were measured using a Calnew precision refractometer [KPR2000 manufactured by Shimadzu Device Co., Ltd.] at a measurement temperature of 20° C. and a refractive index nD with respect to a D line (wavelength 589 nm). The Abbe number (vD) was calculated using the formula vD=(nD-1)/(nF-nC). nF represents the refractive index with respect to the F line (wavelength 486 nm), and nC represents the refractive index with respect to the C line (wavelength 656 nm).

(Evaluation of birefringence)
Using a heat press machine (B-012C manufactured by Imoto Machinery Co., Ltd.), a film having a thickness of 200 μm was molded to prepare a test piece having a length of 1 cm and a width of 6 cm. The test piece was stretched 3 times using uniaxial stretching at a temperature [glass transition temperature (Tg)+10° C.]. The retardation of the stretched sample was measured using a retardation film/optical material measuring device (RETS100 manufactured by Otsuka Electronics Co., Ltd.). The measured value was a value converted to a thickness of 50 μm.

(Measurement of physical properties of resin composition)
The glass transition temperature (Tg), melt flow rate (MFR), refractive index, Abbe number and birefringence of the obtained resin composition were measured. The measurement results are shown in Table 1.

(Example 1)
As a cyclic olefin resin, 85 parts by weight of "ARTON" (JSR Corporation product, F4520, Tg = 164°C, Mw = 60,000) pellets, and as a fluorene compound, 9,9-bis(4-(2-hydroxy) 15 parts by weight of (ethoxy)phenyl)fluorene (manufactured by Osaka Gas Chemicals Co., Ltd., hereinafter BPEF) is kneaded using a twin-screw extruder (manufactured by Technobel Co., Ltd., model number KZW15/45), and a strand is extruded with a cutter. It was cut to obtain pellets. The appearance of the resin composition was colorless and transparent pellets.

(Example 2)
A resin composition was obtained in the same manner as in Example 1 except that 90 parts by weight of cyclic olefin resin and 10 parts by weight of BPEF were used.

(Example 3)
A resin composition was obtained in the same manner as in Example 1 except that 95 parts by weight of the cyclic olefin resin and 5 parts by weight of BPEF were used.

(Example 4)
A resin composition was obtained in the same manner as in Example 1 except that 80 parts by weight of cyclic olefin resin and 20 parts by weight of BPEF were used.

(Example 5)
A resin composition was obtained in the same manner as in Example 1 except that 70 parts by weight of cyclic olefin resin and 30 parts by weight of BPEF were used.

(Example 6)
A resin composition was obtained in the same manner as in Example 1 except that 50 parts by weight of cyclic olefin resin and 50 parts by weight of BPEF were used.

(Example 7)
Instead of BPEF, 15 parts by weight of 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (manufactured by Osaka Gas Chemicals Co., Ltd., hereinafter, BOPPEF) was used as a fluorene compound. A resin composition was obtained in the same manner as in Example 1 except for the above.

(Example 8)
Instead of BPEF, 15 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (synthesized according to Example 1 of JP2007-099741, hereinafter, BNF) was used as the fluorene compound. A resin composition was obtained in the same manner as in Example 1.

(Example 9)
Resin was prepared in the same manner as in Example 1 except that 15 parts by weight of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (manufactured by Osaka Gas Chemicals Co., Ltd., hereinafter, BCF) was used as the fluorene compound. A composition was obtained.

(Example 10)
A resin composition was prepared in the same manner as in Example 1 except that 15 parts by weight of 9,9-bis(4-glycidyloxy)phenyl)fluorene (manufactured by Osaka Gas Chemicals Co., Ltd., hereinafter, BPFG) was used as the fluorene compound. Got

(Example 11)
Example 1 except that 20 parts by weight of 9,9-bis(6-hydroxyethoxy-2-naphthyl)fluorene (synthesized according to Example 1 of JP2011-68624A, hereinafter, BNEF) was used as the fluorene compound. A resin composition was obtained in the same manner as.

(Example 12)
A resin composition was obtained in the same manner as in Example 1 except that 15 parts by weight of 9,9-bis(6-hydroxyethoxy-2-naphthyl)fluorene was used as the fluorene compound.

(Example 13)
A resin composition was obtained in the same manner as in Example 1 except that 10 parts by weight of 9,9-bis(6-hydroxyethoxy-2-naphthyl)fluorene was used as the fluorene compound.

(Example 14)
(Lens molding, evaluation)
Using an aspherical mold, an injection molding machine (FANUC ROBOSHOTS S-2000i50B, manufactured by FANUC CORPORATION) was used to mold 10,000 shots continuously at a resin temperature of 300°C and a mold temperature of 120°C. It was made. It was confirmed that the obtained lens molded product could be molded accurately. No stain was observed on any of the lens molded products. Also, there were no molding problems such as defective molding, broken spool runners, and gas generation.

The physical properties [glass transition temperature (Tg), melt flow rate (MFR)] and optical properties [refractive index, Abbe number, birefringence] of the resin compositions obtained in Examples 1 to 13 were measured. The measurement results are shown in Table 1.

(Comparative Example 1)
As a cyclic olefin resin, "ARTON" (F4520) was measured for its physical properties and optical properties. The measurement results are shown in Table 1.

(Comparative example 2)
A resin composition was prepared in the same manner as in Example 1 except that “APEL” (manufactured by Mitsui Chemicals, Inc., brand D5014DP, Tg135° C.) was used as the cyclic olefin resin, but a cloudy pellet was obtained. Was given. The physical properties and optical characteristics of the resin composition could not be measured.

As is clear from Table 1, in Examples 1 to 6, as the addition amount of the fluorene compound increased, the Abbe number decreased and the refractive index improved, as compared with Comparative Example 1. Further, also in Examples 7 to 13 using the fluorene compound having a structure different from that of BPEF, the Abbe number similarly decreased and the refractive index improved. The resin compositions obtained in Examples 1 to 13 have an Abbe number and a high refractive index in the intermediate region and a relatively high glass transition temperature. Further, in Examples 1 to 13, the birefringence was also reduced as compared with Comparative Example 1. Furthermore, in Examples 1 to 13, although the load was smaller than in Comparative Example 1, the MFR value was larger and the fluidity was significantly improved as compared with Comparative Example 1. In particular, among BPEF, BOPPEF, BNF, BCF, BPFG, and BNEF, a composition containing a BNEF or BNF (particularly BNEF) unit has excellent heat resistance. Moreover, the composition containing the BOPPEF unit has high heat resistance and the degree of reduction of Abbe number is also high. Further, the composition containing BPFG units has high fluidity and low birefringence.

In particular, the composition containing the BNEF unit has an excellent balance of various properties, the highest heat resistance, and the highest fluidity, and is suitable for molding applications. The birefringence is also lower than that of the cyclic olefin resin containing no BNEF unit (Comparative Example 1).

In Comparative Example 2, the miscibility (compatibility) was low and it became cloudy.

Since the resin composition and the molded product of the present invention have high heat resistance (glass transition temperature), have a medium Abbe number and a high refractive index, the degree of freedom in optical design can be improved. Therefore, it can be used as an optical material (for example, an optical sheet, an optical film, an optical lens, etc.). In particular, it is useful as an optical lens of a small camera such as a camera, a digital camera, a surveillance camera, an in-vehicle camera, and a network camera built in a portable communication device such as a mobile phone or a smartphone.

Claims (11)

A resin composition comprising a cyclic olefin resin having a functional group and a compound having a 9,9-bisarylfluorene skeleton having a polar substituent,
A resin composition in which the compound having the 9,9-bisarylfluorene skeleton is a compound represented by the following formula (2).

[In the formula, Ring Z is a condensed polycyclic C _10-14 arene ring, R ³ is a halogen atom, a cyano group, an alkyl group, an aryl group, a carboxyl group or an alkoxycarbonyl group, and R ⁴ is a halogen atom, an alkyl group, a cyclo group. Alkyl group, aralkyl group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, alkylcarbonyl group, nitro group, cyano R ⁴ of a group, an amino group or a substituted amino group, or R 2 of two rings Z may be bonded to each other to form a direct bond or an alkylene group to form a hydrocarbon ring with an adjacent carbon atom. the group X is a group ^{_{- [(OR 5) n1 -Y}} 1] (. wherein the substituents ^{Y 1} is hydroxyl group, ^{R 5} is an alkylene group, n1 is indicating an integer of 1 to 8), k is An integer of 0 to 4, m is an integer of 0 or 1 or more, and p is an integer of 1 or more. ] The resin composition according to claim 1, wherein the cyclic olefin resin is a resin containing a norbornene skeleton. The resin composition according to claim 1 or 2, wherein the cyclic olefin resin is a resin containing at least a structural unit represented by the following formula (1).

(In the formula, the group R ¹ represents a hydrogen atom or an alkyl group, the group R ² represents a hydrogen atom, an alkyl group or an aryl group, and the group W represents a carboxyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, hydroxyalkyl group, glycidyloxy group, a cyano group or an amide group, q is indicates 0 or 1, when q is 0, there is a hydrogen atom instead of the group W.) In the formula (1), the group R ¹ is a hydrogen atom or a methyl group, the group R ² is a hydrogen atom, the group W is a carboxyl group, a C _1-2 alkoxy-carbonyl group, a cyano group or an amide group, and q is 0. Item 4. The resin composition according to Item 3. The resin composition according to any one of claims 1 to 4, wherein the cyclic olefin resin has a glass transition temperature of 140 to 250°C. In formula (2), ring Z is a naphthalene ring, R ³ is a C _1-4 alkyl group, k is 0 or 1, R ⁴ is a C _1-4 alkyl group or a C _1-4 alkoxy group, and m is 0 or 1. Of the above, R ⁵ is a C _2-4 alkylene group, n 1 is an integer of 1 to 2, and p is 1 or 2. 6. The resin composition according to claim 1. The resin composition according to any one of claims 1 to 6, wherein the compound represented by the formula (2) is 9,9-bis(hydroxy C _2-4 alkoxynaphthyl)fluorene. The resin according to any one of claims 1 to 7, wherein the ratio of the cyclic olefin resin and the compound having a 9,9-bisarylfluorene skeleton is former/latter (weight ratio) = 99/1 to 30/70. Composition. The Abbe number calculated from the refractive index with respect to the spectrum of C-line, D-line, and F-line is 28-55, and/or the refractive index in wavelength 589nm is 1.51-1.60. Resin composition. A molded body formed of the resin composition according to claim 1. An optical lens formed of the resin composition according to claim 1.