WO2016147847A1 - Resin composition and optical lens - Google Patents

Abstract

The present invention relates to a resin composition obtained by adding a compound which has polar substituents, is represented by the following formula (2), and includes a 9,9-bisarylfluorene skeleton, to a cycloolefin-based resin having a functional group, the resin composition having a moderate Abbe number. [In the formula, ring Z represents an arene ring; R³ and R⁴ each represent a substituent; group X represents -[(OR⁵)_n1-Y¹] (wherein substituent Y¹ represents a hydroxyl, mercapto, glycidyloxy, or (meth)acryloyloxy group, R⁵ represents an alkylene group, and n1 is 0 or an integer of 1 or larger) or -[(CH₂)_n2-Y²] (wherein substituent Y² represents a carboxyl, alkoxycarbonyl, amino, or substituted amino group and n2 is 0 or an integer of 1 or larger); k is an integer of 0-4; m is 0 or an integer of 1 or larger; and p is an integer of 1 or larger.] This resin composition has an Abbe number in an intermediate range (Abbe number of about 28-55) and is useful as an optical lens, etc.

Description

Resin composition and optical lens

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

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

In recent years, with the thinning and multi-functionalization of such mobile phones and smartphone terminals, it is required to reduce the size of the imaging lens mounted on the imaging device in order to secure a space for mounting components and elements. ing. In addition, along with downsizing, as the number of pixels in image sensors such as sensors using charge-coupled devices (CCD sensors) and sensors using complementary metal oxide semiconductors (CMOS sensors) increases, the resolution of imaging lenses also increases. It is requested. Such an imaging lens is compact and has high imaging performance and correction of various aberrations under cost constraints, so that various designs can be made in selecting the lens configuration, shape, and material using the optical design. Has been made. The optical design of the imaging lens unit is performed by inputting the refractive index data at a plurality of wavelengths of the lens material into calculation software and repeating the adjustment while automatically calculating according to the algorithm. However, since the resin (or material) that can be used for the optical lens is limited, the degree of design freedom is limited, and there is a limit to highly effective or various designs. That is, the imaging lens unit is composed of a plurality of lenses having different Abbe numbers and refractive indexes. Therefore, in general, one or a plurality of lenses having a large Abbe number and a medium refractive index are used. (For example, 2 to 4 lenses formed of cyclic olefin resin having an Abbe number of 56 to 57 and a refractive index of 1.51 to 1.54) and a lens having a small Abbe number and a large refractive index A plurality of sheets (for example, one or two lenses made of a fluorene-based resin having an Abbe number of 22 to 27 and a refractive index of 1.61 to 1.64) are combined. If there is a material in the middle region (the Abbe number is about 28 to 55) between the high Abbe number and the low Abbe number, the degree of freedom in design is improved and optimization can be expected. For thermosetting resins and glass, although there are materials with an Abbe number in the middle region, glass is expensive, and thermosetting resins have low lens productivity, so they can be used in optical lenses such as mobile phones and smartphones. not being used.

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

In addition, JP-A-2014-205734 (Patent Document 3) adds 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. This document also exemplifies a cyclic olefin resin as a resin, and also describes that an optical lens, an optical film, and the like may be formed. In the examples, a specific fluorene compound (for example, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF), etc.) is added to polycarbonate resin or polyethylene naphthalate, and the Abbe number is calculated. It is getting bigger. However, the ratio that the Abbe number increases with respect to the addition amount of the fluorene compound is small, and the Abbe adjusting agent is not sufficiently adjusted. In Examples of Patent Documents 1 to 3, there is no specific description regarding the cyclic olefin resin.

Further, JP 2013-194186 A (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 a product. In this document, a polyester is formed from a fluorene compound containing an alicyclic diol component in order to increase the compatibility (miscibility) with polycycloolefin. However, this document does not describe the adjustment of the Abbe number.

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 Examples of this document, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene (BCF) is added to “Arton4531F” or “APEL5014DP” of a cyclic olefin copolymer to obtain a resin composition. ing. Although the latter resin composition describes that the Abbe number is reduced, the degree of reduction of the Abbe number is small with respect to the amount of BCF added. When the present inventors prepared these resin compositions, the latter resin composition has low miscibility (compatibility) between the resin and BCF, and at first glance it appears to have transparency. When processing such as hot pressing or molding was performed, it was found that the resin composition might become cloudy, and the Abbe number could not be measured. It has also been found that these resin compositions have insufficient heat resistance (glass transition temperature). For this reason, it has been found that it cannot be used for applications such as optical lenses.

JP 2005-162785 A (claims, [0015] [0059] [0079], Examples) Japanese Patent Laying-Open No. 2011-8017 (Claims, [0017] [0082], Examples) JP 2014-205734 A (claims, [0087] [0126], Examples) JP 2013-194186 A (claims, [0015] [0025], Examples) JP 2014-218660 A (Claims, [0028] [0029] [0034], Examples)

Therefore, the object of the present invention is to effectively reduce the Abbe number of the cyclic olefin resin even when the content of the fluorene compound is small, and adjust the Abbe number in the intermediate region (for example, Abbe number of about 28 to 55). It is possible to provide a resin composition 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 diligent studies to achieve the above-mentioned problems, the present inventors have determined that a compound having a predetermined 9,9-bisarylfluorene skeleton with respect to a cyclic olefin resin having a functional group (sometimes referred to as a fluorene compound). 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 resin can be effectively reduced to the intermediate region, and the Abbe number of the intermediate region can be adjusted. The present inventors have found that a resin composition having high heat resistance (glass transition temperature) can be obtained and completed the present invention.

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. 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, group R ¹ represents a hydrogen atom or an alkyl group, group R ² represents a hydrogen atom, an alkyl group or an aryl group, and 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, and q represents 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, cyano group, alkyl group, aryl group, carboxyl group or alkoxycarbonyl group, R ⁴ is a halogen atom, alkyl group, cycloalkyl 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 group, amino group or substituted amino group Or R ^{4 in the} two rings Z may be bonded to each other to form a direct bond or an alkylene group to form a hydrocarbon ring with adjacent carbon atoms, and the group X may be a group — [ (OR ⁵ ) _n1 -Y ¹ ] (wherein the substituent Y ¹ is a hydroxyl group, a mercap Group, glycidyloxy group or (meth) acryloyloxy group, R ⁵ is an alkylene group, n1 represents 0 or an integer of 1 or more) or a group-[(CH ₂ ) _n2 -Y ² ] (wherein substituted The group Y ² is a carboxyl group, an alkoxycarbonyl group, an amino group or a substituted amino group, n2 is 0 or an integer of 1 or more), k is an integer of 0 to 4, m is an integer of 0 or 1 or more, p Represents an integer of 1 or more. ]
In the 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 from 0 to 2, and p may be 1 or 2.

Specifically, the compound represented by the 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 alkoxyC _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 diglyceryl di sill oxy _{C 6-12} aryl), 9,9-bi _{(C 6-12} aryl - Gurijishiruokishi _{C 6-12} aryl) fluorene, 9,9-bis (mono- or _{di-C 1-4} alkyl - Gurijishiruokishi _{C 6-12} aryl) fluorene, 9,9-bis (mono- or Jiguriji Siloxy (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 It may contain at least one selected from -bis [mono or di C _1-4 alkyl-glycidyloxy (poly) C _2-4 alkoxy C _6-12 aryl] 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 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 C-line, D-line and F-line spectra is 28 to 55 and / or the refractive index at a wavelength of 589 nm is about 1.51 to 1.60. Also good.

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

In this specification, “(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 and easily adjust the Abbe number in the intermediate region because the cyclic olefin resin has a predetermined functional group. In addition, since the cyclic olefin-based resin has a polycyclic structure having the functional group, the heat resistance (glass transition temperature) is high, and the heat resistance can be maintained 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, since the compatibility of both is high, even if the ratio of a fluorene compound is large, it can mix uniformly, without becoming cloudy, has high transparency, and can also reduce the Abbe number greatly. Such a resin composition can expand the degree of freedom in designing a lens or the like, and is useful for applications such as an optical material (for example, an optical lens).

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]
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). It may be. In addition, the said functional group (A) may be contained in the cyclic olefin and / or the copolymerizable monomer, Preferably it may be contained in the cyclic olefin at least.

The cyclic olefin having the functional group (A) may be a monocyclic olefin, but is usually a polycyclic olefin (for example, a bicyclic to tetracyclic olefin) 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 (for example, cyclopentadiene, dicyclo) which may contain a substituent (C). It can be prepared using Diels-Alder reaction with pentadiene and the like.

Examples of the unsaturated compound include compounds having a carboxyl group {for example, unsaturated mono- or dicarboxylic acid [for example, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid, etc.]}, alkoxycarbonyl A compound having a group [for example, (meth) alkyl (meth) acrylate (for example, (meth) methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate) acrylic acid _{C 1-6} alkyl, preferably (meth) acrylic acid _{C 1-4} alkyl), unsaturated dicarboxylic acid alkyl ester (e.g., itaconic acid _{C 1-4} alkyl esters of itaconic acid methyl ester, dimethyl maleate Maleic acid di-C _1-4 alkyl ester, etc.)], cycloa A compound having an alkyloxycarbonyl group [for example, a cycloalkyl (meth) acrylate (for example, a C _5-8 cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate), etc.), an aryloxycarbonyl group Compound [for example, (meth) acrylic acid C _6-10 aryl such as phenyl (meth) acrylate], etc., compound having hydroxyl group [for example, hydroxyalkyl (meth) acrylate (for example, hydroxyethyl (meth) acrylate) (Meth) acrylic acid hydroxy C _2-4 alkyl etc.)], compounds having alkoxy groups [eg, (meth) acrylic acid C _2-4 alkoxy C _2-4 alkyl such as methoxyethyl (meth) acrylate, etc. Etc.], a compound having a mercapto group (for example, A compound corresponding to a compound having a hydroxyl group), a compound having a glycidyl group (for example, glycidyl (meth) acrylate), a compound having an amide group (for example, (meth) acrylamide), a compound having a cyano group ( For example, (meth) acrylonitrile etc. can be illustrated. These unsaturated compounds can be used alone or in combination of two or more. Of these unsaturated compounds, compounds having a carboxyl group, a C _1-2 alkoxy-carbonyl group, a cyano group or an amide group are preferred.

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

Among the cyclic olefins having the functional group (A), bicyclic olefins (bicycloalkenes) include, for example, cyclic olefins (2-norbornene, 2,5-norbornadiene, etc.) substituted with at least the functional group (A) ( For example, 5-C _1-4 alkyl-5 such as 5-carboxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-ethoxycarbonyl-2-norbornene, 5-methyl-5-carboxy-2-norbornene, etc. 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 - _{5-C 1-4} alkyl _{-5-C 5-10} cycloalkoxy such as norbornene - carbonyl-2-norbornene, 5-hydroxy-ethoxycarbonyl-2-norbornene such as 5-hydroxy straight-chain or branched _{C 2 5 such as -3} alkoxy-carbonyl-2-norbornene, 5-cyano-2-norbornene, 5-amido-2-norbornene, 5,6-dicarboxy-2-norbornene, 5,6-dimethoxycarbonyl-2-norbornene, etc. , 6-diC _1-2 alkoxy-carbonyl-2-norbornene, 6-phenyl-5-carboxy-2-norbornene, etc.).

Examples of the tricyclic olefins (tricycloalkenes) having a functional group (A) include, for example, tricyclo [5.2.1.0 ^2,6 ] decan-3-ene substituted with at least the functional group (A). Cyclic olefins such as 8-hydroxy-tricyclo [5.2.1.0 ^2,6 ] decan-3-ene, 9-hydroxy-tricyclo [5.2.1.0 ^2,6 ] decan-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 ] decan-3-ene 3-ene, 8-cyano - tricyclo [5.2.1.0 ^{, 6]} decane-3-ene, 9-cyano - tricyclo [5.2.1.0 ^{2, 6]} decane-3-ene), and others.

Examples of tetracyclic olefins (tetracycloalkenes) having a functional group (A) include tetracyclo [4.4.0.1 ^2,5 . 1, ¹⁰ ] -3-dodecene etc.) and at least a functional group (A) substituted cyclic olefin {eg, 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 . 1 ^{7, 10} ] dodec-3-ene and the like. 1 ^7,10 ] dodec-3-ene, 8-methyl-8-carboxy-tetracyclo [4.4.0.1 ^2,5 . ^1-7,10 ] 8-C _1-4 alkyl-8-carboxy-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 . 8-C _1-4 alkyl-8-C _1-2 alkoxy-carbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like. 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyclohexyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . ^1-7,10 ] 8-C _1-4 alkyl-8-C _5-8 cycloalkoxy-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 . 8,9-diC _1-2 alkoxy-carbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodec-3-ene and the like. 1 ^7,10 ] dodec-3-ene, 8-phenyl-9-carboxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene etc.}. These cyclic olefins can be used alone or in combination of two or more. Among these cyclic olefins, from the viewpoint of heat resistance, cyclic olefins containing a norbornene skeleton (in particular, bicyclic olefins, tetracyclic olefins, etc.) are preferable.

The cyclic olefin having the 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-dodecene and other bi- to tetracyclic olefins).

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 of the cyclic olefin having no A) is, for example, the former / the 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 to 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.

Specifically, examples of the cyclic olefin-based resin include a resin (homopolymer or copolymer) including at least a structural unit represented by the following formula (1).

(In the formula, group R ¹ represents a hydrogen atom or an alkyl group, group R ² represents a hydrogen atom, an alkyl group or an aryl group, and 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, and q represents 0 or 1)
Examples of the alkyl group for the substituents R ¹ and R ² include C _1-4 alkyl groups such as a methyl group and an ethyl group. Examples of the aryl group for the substituent R ² include a phenyl group. R ¹ is preferably a hydrogen atom or a methyl group, and R ² is preferably a hydrogen atom.

In the group W, examples of the alkoxycarbonyl group include linear or branched C _1-6 alkoxy-carbonyl groups such as a methoxycarbonyl group and an ethoxycarbonyl group, preferably a linear or branched chain And a C _1-4 alkoxy-carbonyl group. Since the alkoxycarbonyl group often has a higher glass transition temperature as the number of carbon atoms becomes shorter, a C _1-2 alkoxy-carbonyl group is particularly preferable.

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

Examples of the aryloxycarbonyl group include C _6-10 aryloxy-carbonyl groups 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.

Of 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). In many cases, q is 0 or 1, usually 0.

The cyclic olefin-based resin may be a homopolymer, but may usually 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, C _2-12 alkene such as 1-dodecene) and the like, preferably α-olefins (for example, ethylene, propylene, C _2-10 α-olefins such as 1-butene, 1-pentene and 1-hexene, preferably C _2-6 α-olefins, particularly ethylene) may be used. The copolymerizable monomer may have a functional group (A). For example, the same compound as the unsaturated compound exemplified above (for example, (meth) acrylic acid, methyl (meth) acrylate) ( _C1-2 alkyl (meth) acrylate such as ethyl (meth) acrylate).

Of 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-based resin (for example, the 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 ratio of the cyclic olefin is too small, the miscibility (or affinity) with the fluorene compound is lowered, and the Abbe number may not be effectively reduced, and the heat resistance (glass transition temperature) may be lowered. .

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

(R and s represent the number of repeating 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.

The cyclic olefin-based resin often has improved heat resistance (glass transition temperature) when the proportion of the cyclic olefin having the functional group (A) increases. 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, for example, 140 to 250 ° C., preferably 150 to 220 ° C., more preferably 160 It may be about -200 ° C (eg, 160-180 ° C). The glass transition temperature of the cyclic olefin resin may be, for example, about 120 to 180 ° C., preferably about 130 to 180 ° C., and more preferably about 140 to 170 ° C. If the ratio of the cyclic olefin having the functional group (A) is too small, the miscibility (or affinity) with the fluorene compound may be lowered, the heat resistance (glass transition temperature) may be lowered, and the Abbe number is effective. May not be able to be reduced. Depending on the type of resin, it may not be detected below the decomposition temperature. The glass transition temperature can be measured 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 (for example, 20,000 to 190,000), preferably 30,000 to 170,000 (for example, 40,000 to 40,000) as measured by gel permeation chromatography (GPC). It is about 150,000, more preferably about 40,000 to 130,000 (for example, 50,000 to 130,000) If the molecular weight is too large, the melt viscosity becomes high, and the productivity and workability of the optical material may be lowered, and if the molecular weight is too small. Mechanical strength decreases.

As the cyclic olefin-based resin, a commercially available product (for example, “ARTONF4520” 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. “APEL5014DP” manufactured by Mitsui Chemicals, Inc. is an addition polymer of bicyclic olefin (2-norbornene) having no functional group and ethylene.

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

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

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

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

[Wherein, ring Z is an arene ring, R ³ is a halogen atom, cyano group, alkyl group, aryl group, carboxyl group or alkoxycarbonyl group, R ⁴ is a halogen atom, alkyl group, cycloalkyl 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 group, amino group or substituted amino group Or R ^{4 in the} two rings Z may be bonded to each other to form a direct bond or an alkylene group to form a hydrocarbon ring with adjacent carbon atoms, and the group X may be a group — [ (OR ⁵ ) _n1 -Y ¹ ] (wherein the substituent Y ¹ is a hydroxyl group, a mercap Group, glycidyloxy group or (meth) acryloyloxy group, R ⁵ is an alkylene group, n1 represents 0 or an integer of 1 or more) or — [(CH ₂ ) _n2 —Y ² ] (wherein the substituent Y ² represents a carboxyl group, an alkoxycarbonyl group, an amino group or a substituted amino group, n2 represents 0 or an integer of 1 or more.), K is an integer of 0 to 4, m is an integer of 0 or 1 or more, p is An integer of 1 or more is shown. ]
In the formula (2), examples of the arene ring represented by the ring Z include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, and the like. The polycyclic arene ring includes a condensed polycyclic ring. An arene ring (condensed polycyclic hydrocarbon ring), a ring assembly arene ring (ring assembly aromatic hydrocarbon ring) and the like are included.

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

Examples of the ring-assembled arene ring include biarene rings such as bi-C _6-12 arene rings such as biphenyl ring, binaphthyl ring, and phenylnaphthalene ring (1-phenylnaphthalene ring, 2-phenylnaphthalene ring, etc.), Examples thereof include a tel C _6-12 arene ring such as a terphenylene ring. Preferred ring-assembled arene rings include bi-C _6-10 arene rings, particularly 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.), cyano group, alkyl group (for example, 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 (for example, 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 C _1-6 such as a carboxyl group, an alkoxycarbonyl group (for example, a methoxycarbonyl group). Alkoxy-carbonyl group, preferably C _1-4 alkoxy-carbonyl group 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 number of substitutions k may be the same or different from each other. When k is 2 or more, the types of the substituents R ³ may be the same or different from each other, and are substituted with two benzene rings of the fluorene ring. The type of the substituent R ³ may be the same or different. Further, the substitution position of the substituent R ³ is not particularly limited, and may be, for example, 2-position to 7-position (2-position, 3-position and / or 7-position, etc.) of the fluorene ring.

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

In the formula (2), the group R ⁴ includes a halogen atom (for example, 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 a -butyl group or a t-butyl group, preferably a linear or branched C _1-6 alkyl group), a cycloalkyl group (cyclopentyl group, cyclo C _5-10 cycloalkyl group such as hexyl group), aralkyl group (C _6-10 aryl-C _1-4 alkyl group such as benzyl group and phenethyl group), nitro group and the like. The group R ⁴ may be a polar substituent (B). Examples of such a polar substituent (B) include an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, C _1-10 alkoxy group such as isobutoxy group and t-butoxy group), cycloalkoxy group (eg C _5-10 cycloalkyloxy group such as cyclohexyloxy group), aryloxy group (eg phenoxy group etc.) C _6-10 aryloxy group, etc.), aralkyloxy groups (eg, C _6-10 aryl-C _1-4 alkyloxy groups such as benzyloxy group), alkylthio groups (eg, methylthio group, ethylthio group, etc.) C such as _1-10 alkylthio group), _{C 5-10} such cycloalkylthio group (e.g., cyclohexylthio group cyclohexylene Shi Roarukiruchio group etc.), an arylthio group (e.g., a _{C 6-10} arylthio group such as thiophenoxy group), aralkylthio group (e.g., _{C 6-10} aryl _{-C 1-4} alkylthio group such as benzylthio group), A carboxyl group, an alkoxycarbonyl group (for example, a C _1-6 alkoxy-carbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, preferably a C _1-4 alkoxy-carbonyl group), an alkylcarbonyl group (for example, an acetyl group, propionyl) _{C 1-4} alkyl, such groups - such as a carbonyl group), a cyano group, a substituted amino group (e.g., _{di-C 1-4} alkylamino group such as dimethylamino group, _{di-C 1-4} alkyl, such as di-acetylamino group - carbonyl An amino group etc.) can be illustrated.

Of these substituents R ⁴ , typically, polar substituents (B) such as alkoxy groups, carboxyl groups, alkoxycarbonyl groups, alkylcarbonyl groups, cyano groups, substituted amino groups, halogen atoms, alkyl groups, 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, and particularly a C _1-4 alkyl group such as a methyl group. The type of the substituent R ⁴ may be the same or different in the same or different ring Z.

In addition, R ⁴ of the two rings Z are bonded to each other to form a direct bond or an alkylene group (eg, a C _1-6 alkylene group such as a methylene group or an ethylene group, preferably a C _1-4 alkylene group). And a hydrocarbon ring may be formed together with adjacent carbon atoms. The hydrocarbon ring may be, for example, a 5- to 10-membered (for example, 5- to 8-membered) hydrocarbon ring. Further, when R ^{4 of} two rings Z and a carbon atom adjacent to each other form a hydrocarbon ring, the bonding position of R ⁴ is, for example, when the ring Z is a benzene ring, the 2-position of the phenyl group, 3 Often in the -position (especially the 2-position), when the ring Z is a naphthalene ring and 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, Often in the β-position (especially 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 optical isomer R-form or S-form. As a typical compound, the compound etc. which are represented by following formula (3) can be illustrated.

(Wherein X, R ³ , k, and p are the same as above)
The number of substitution m can be appropriately selected according to the type of ring Z, the number of m, and the like, and may be an integer of about 0 to 8, for example, an integer of 0 to 4, preferably 0 to 3 (for example, , 0 to 2), in particular 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, for example, a C _2-6 alkylene group such as an ethylene group, trimethylene group, 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, 1,2-butanediyl group, 1,3-butanediyl group, etc. Chain C _3-4 alkylene group, especially propylene group). In the case n1 is an integer of 2 or more types of alkylene groups R ⁵ may be the same or different. Further, the type of alkylene group R ⁵ may be the same or different in the same or different ring Z.

The number n1 of the oxyalkylene group (OR ⁵ ) can be selected from a range of about an integer of 0 to 15 (eg, an integer of 0 to 10), for example, an integer of 0 to 8 (eg, 1 to 8), preferably It may be an integer of 0 to 5 (eg 1 to 5), more preferably an integer of 0 to 4 (eg 1 to 4), especially an integer of about 0 to 3 (eg 1 to 3). , An integer from 0 to 2 (for example, 0 or 1) may be used.

N2 may be 0 or an integer of 1 or more (eg, 1 to 6, preferably 1 to 4, more preferably about 1 to 2). n2 may usually be 0 or an integer of 1 to 2.

The substituent Y ^1, part number polarity is a substituent (B), for example, a hydroxyl group, a mercapto group, glycidyloxy group, and the like (meth) acryloyloxy group, the substituent Y ^2, carboxyl Group, alkoxycarbonyl group (eg, C _1-6 alkoxy-carbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxy group carbonyl group, etc.), amino group, substituted amino group (eg, 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 kind of the ring Z, for example, an integer of 1 to 4, preferably an integer of 1 to 3, more preferably May be an integer from 1 to 2, in particular 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 of the ring Z. For example, when the ring Z is a benzene ring, the 2-, 3-, 4-position of the phenyl group (particularly the 3-position and / or 4-position) is often substituted, and when ring Z is a naphthalene ring, it is often the 5- to 8-position of the naphthyl group, for example, the naphthalene ring relative to the 9-position of fluorene In the 1-position or 2-position of (substitute in the relationship of 1-naphthyl or 2-naphthyl), and in relation to this substitution position, the 1,5-position, 2,6-position, etc. (especially p In the case where is 1, the group X is often substituted in the 2,6-position relationship). Moreover, when p is 2 or more, the substitution position is not particularly limited. In addition, in the ring assembly arene ring Z, the substitution position of the group X is not particularly limited, and for example, an arene ring bonded to the 9-position of fluorene and / or an arene ring adjacent to the arene ring may be substituted. 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′-, and 4′-positions, and is usually 2-, 3′-, 4′-position, preferably 2-, 4 It may be substituted at the '-position (particularly the 2-position).

In the group X {group-[(OR ⁵ ) _n1 -Y ¹ ]}, the substituent Y ¹ is preferably a hydroxy group or a glycidyloxy group.

In addition, the polar substituent (B) of the fluorene compound may be derived, for example, from any of the substituents Y ¹ and Y ² and the substituents R ³ and R ⁴ , and usually at least the substituents Y ¹ and 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, (Meth) acryloyloxy, carboxyl group, alkoxycarbonyl group, amino group, substituted amino group, alkylcarbonyl group, cyano group, substituted amino group and the like can be mentioned. The fluorene compound may contain a single or two or more polar substituents (B). Of these polar substituents (B), a hydroxyl group, a glycidyloxy group and the like are preferable.

Specifically, in the formula (2), as the compound in which the substituent Y ¹ is a hydroxy group or a glycidyloxy group in the group X, the substituent Y ¹ is a hydroxy group, n1 is 0, and p is 1. Certain compounds, such as 9,9-bis (hydroxyarene) fluorenes {eg, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-hydroxyphenyl) fluorene, 9,9-bis 9,9-bis (hydroxyC _6-12 aryl) fluorene, such as (6-hydroxy-2-naphthyl) fluorene, 9,9-bis (5-hydroxy-1-naphthyl) fluorene, 9,9-bis (3 9,9-bis (C _6- ) such as -phenyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-phenyl-3-hydroxyphenyl) fluorene 9,9 such as ₁₂ aryl-hydroxy C _6-12 aryl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-methyl-3-hydroxyphenyl) fluorene -Bis (mono- or di-C _1-4 alkyl-hydroxy C _6-12 aryl) fluorene}, 2,7-dihydroxy-9,9′-spirobifluorene and the like dihydroxy-9,9′-spirobifluorene It can be illustrated.

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, for example, 9,9-bis [(poly) hydroxyarene] fluorene {9,9-bis (3,4-dihydroxyphenyl) fluorene, 9,9-bis (dihydroxyC _6-12 aryl) fluorene such as 9,9-bis (2,4-dihydroxyphenyl) fluorene} Can be illustrated.

In the above formula (2), in the group X, the compound in which 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-naphthyl] 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 such as 9,9-bis (hydroxy _{C 2-4} alkoxy _{C 6-12} a Fluorene, 9,9-bis [4-phenyl-3- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4-phenyl-3- (2-hydroxypropoxy) phenyl] fluorene, etc. 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, 9,9-bis [mono- or di-C _1-4 alkyl-hydroxy C _2-4 alkoxy C _6-12 aryl] fluorene such as 9-bis [4-methyl-3- (2-hydroxypropoxy) phenyl] fluorene }, Di (hydroxy C _2-4 alkoxy) -9,9 such as 2,7-di (2-hydroxyethoxy) -9,9′-spirobifluorene Examples include '-spirobifluorene.

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

In the above formula (2), in the group X, the substituent Y ¹ is a hydroxyl group, n1 is 2 or more, and p is 1, corresponding to the compound in which n1 is 0 or 1, an oxyalkylene group (Especially an oxy C _2-4 alkylene group) in which the repeating unit n1 is 2 to 5, such as 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] phenyl} fluorene, 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] na Chill] fluorene such as 9,9-bis (mono- or dihydroxy poly _{C 2-4} alkoxy _{C 6-12} aryl) fluorene, 9,9-bis [4-phenyl-3- [2- (2-hydroxyethoxy) ethoxy ] 9,9-bis [C _6-12 aryl-hydroxy poly C _2-4 alkoxy C _6-12 aryl] fluorene, such as phenyl] fluorene, 9,9-bis [4-methyl-3- [2- (2 9,9-bis [mono or di C _1-4 alkyl-hydroxy poly C _2-4 alkoxy C _6-12 aryl] fluorene such as -hydroxyethoxy) ethoxy] phenyl] fluorene, 2,7-di [2- ( di, such as 2-hydroxyethoxy) ethoxy] -9,9'-spirobifluorene (polyhydroxy _{C 2-4} alkoxy) -9,9' Supirobifuru Such as Ren can be exemplified.

In the formula (2), as the compound in which the substituent Y ¹ is a glycidyloxy group in the group X, for example, a compound in which a glycidyloxy group is substituted in place of the exemplified hydroxyl group, 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, 9,9-bis (4-phenyl-3-glycidyloxyphenyl) fluorene _-12 aryl) fluorene, 9,9-bis (3-methyl-4-glycidyloxyphenyl) fluorene, etc. 9-bis (mono or di C _1-4 alkyl-glycidyloxy C _6-12 aryl) fluorene, 9,9-bis [4- (2-glycidyloxyethoxy) phenyl] fluorene, 9,9-bis [6- 9,9-bis (mono or diglycidyloxy ((2) glycidyloxyethoxy) -2-naphthyl] fluorene, 9,9-bis [3-methyl-4- (2-glycidyloxyethoxy) phenyl] fluorene, etc. 9,9-bis [C _6-12 aryl such as poly) C _2-4 alkoxy C _6-12 aryl) fluorene, 9,9-bis [4-phenyl-3- (2-glycidyloxyethoxy) phenyl] fluorene -Glycidyloxy (poly) C _2-4alkoxy C _6-12 aryl] fluorene, 9,9-bis [3-methyl-4- (2-glyci 9,9-bis [mono or di C _1-4 alkyl-glycidyloxy (poly) C _2-4 alkoxy C _6-12 aryl] fluorene, 2,7-diglycidyloxy-, such as (diyloxyethoxy) phenyl] fluorene Di (glycidyloxy) such as diglycidyloxy-9,9′-spirobifluorene such as 9,9′-spirobifluorene, 2,7-di (2-glycidyloxyethoxy) -9,9′-spirobifluorene Examples include (poly) C _2-4 alkoxy) -9,9′-spirobifluorene.

“(Poly) C _2-4 alkoxy” means a group in which the number of repeating C _2-4 alkoxy n1 or n2 is an integer of 1 or more.

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

In the formula (2), in the group X {group-[(CH ₂ ) _n2 -Y ² ]}, the compound in which the substituent Y ² is a carboxyl group is a compound in which n2 is 0 and p is 1 For example, 9,9-bis (carboxyaryl) fluorenes {eg, 9,9-bis (3-carboxyphenyl) fluorene, 9,9-bis (4-carboxyphenyl) fluorene, 9,9-bis (5 9,9-bis (carboxy C _6-12 aryl) fluorene such as -carboxy-1-naphthyl) fluorene, 9,9-bis (6-carboxy-2-naphthyl) fluorene; n2 is 1 and p is 1 Examples of the compound are 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 Examples include 9,9-bis (carboxy C _1-6 alkyl-C _6-12 aryl) fluorene such as -naphthyl) fluorene and 9,9-bis (6- (carboxymethyl) -2-naphthyl) fluorene.

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

Among these compounds, from the viewpoint of heat resistance, in the 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 A} compound that is a _-4 alkyl group, for example, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene (BCF); in 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; 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, p = For example, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene (BNEF), 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene , 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] fluorene; In the above formula (2), ring Z is a bi- or tel C _6-12 arene ring, Y ¹ is a hydroxyl group, n1 = 1 to 3, R ⁵ ═C _2-4 alkylene group, compound wherein 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 such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF), 9,9-bis [3- (2-hydroxyethoxy) phenyl] fluorene; 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, for example, BNEF, 9,9-bis [5- (2-hydroxy Ethoxy) -1-naphthyl] fluorene, 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] fluorene; in formula (2), ring Z is a benzene ring, Y ¹ is a glycidyl group, n1 = 0, p 1, compound, for example, 9,9-bis (4-glycidyloxyphenyl) fluorene (BPFG), 9,9-bis (3-glycidyloxy phenyl) fluorene is preferable.

In particular, in the above formula (2), a compound in which 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) 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, 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, It is preferable from the viewpoint that the Abbe number can be reduced while effectively maintaining the high heat resistance (glass transition temperature) of the cyclic olefin resin, and the fluidity (or moldability) can be greatly improved. In Ring Z is fused polycyclic _{C 10-14} arene ring, ^{Y 1} is a hydroxyl group, n1 = 1 ~ 2 (particularly 1), the compound is p = 1, for example, BNEF is, heat resistance, optical characteristics, moldability Is particularly preferable from the viewpoint that both can be achieved at a high level.

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, a compound in which the substituent Y ¹ is a hydroxyl group includes 9-fluorenones and a hydroxyl group-containing arene ring compound in which the group [HO— (R ⁵ O) _n1 —] is substituted on the ring Z (for example, A method of reacting phenoxyalkanols such as 2-phenoxyethanol) in the presence of an acid catalyst, a fluorene compound in which a hydroxyaryl group is substituted at the 9-position of fluorenes [for example, 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 a fluorene 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 the addition or mixing (or melt-kneading) of 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. Moreover, even if it is cyclic olefin resin (for example, polycyclic olefin resin), since it has a predetermined functional group, the compatibility with the fluorene compound which has a polar group is high, and the ratio of a fluorene compound Even if there is much, it can mix uniformly, without becoming cloudy, can greatly reduce the Abbe number, and is excellent in transparency. Such a cyclic olefin-based resin has a rigid cross-linked structure having the functional group (for example, a bicyclic structure having a norbornene skeleton, a tricyclic structure, etc.), and thus has a high glass transition temperature. Even if a fluorene compound is added, high heat resistance (glass transition temperature) can be maintained. Furthermore, since the refractive index can be effectively increased as the Abbe number is reduced, the refractive index is high even at the Abbe number in the intermediate region. Therefore, the freedom degree of optical design can be improved and it can utilize for optical material uses (for example, an optical lens, an optical sheet, an optical film, etc.).

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

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

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

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 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, about 30 to 56 nm, preferably 33 to 55 nm, and more preferably about 35 to 54 nm. In addition, birefringence can be measured by the method of an Example.

In addition, the said resin composition (or molded object) can make compatible the Abbe number and heat resistance (high glass transition temperature) of an intermediate | middle area | region. 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. May be about 140 to 170 ° C. (for example, 145 to 165 ° C.), for example, 135 to 250 ° C. (for example, 150 to 230 ° C.), preferably 160 It may be about -210 ° C, more preferably about 170-200 ° C. If the glass transition temperature is too low, the heat resistance and the like may be reduced, and if it is too high, the moldability may be reduced. The glass transition temperature can be measured by differential scanning calorimetry (measurement).

Further, the resin composition may contain various additives [for example, fillers or reinforcing agents, colorants (dyes, fluorescent brighteners, etc.), conductive agents, flame retardants, plasticizers, lubricants, stabilizers. (Antioxidants, UV absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress 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 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, tetrakis (Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, stearyl-β- (3,5-di-tert-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-methyl Phenyl) propionyloxy) ethyl], 2,4,8,10-tetraoxaspiro [5.5] undecane, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis ( 2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2-methylenebis (4,6- And 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 ratio of the additive depends on the type 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 to 100 parts by weight of the resin composition. It may be about 05 to 5 parts by weight.

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

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

Furthermore, the present invention 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.), a three-dimensional shape [uneven shape, aspherical surface] Shape (for example, elliptical shape), tubular shape, rod shape, tube shape, hollow shape, and the like].

The molded body can be manufactured 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, and the like.

Moreover, since the molded article or resin composition of the present invention is excellent in optical properties, it can be suitably used for optical materials (for example, optical lenses, optical sheets, optical films, etc.). In particular, since the resin composition of the present invention has a moderate Abbe number, it 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 with 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 a curved surface with high accuracy using a resin with low fluidity, and the resin temperature and mold temperature during molding are high. However, in many cases, the molding is performed with improved fluidity. However, when the resin temperature and the mold temperature are increased, problems such as decomposition of the resin, decomposition of additives, volatilization, sticking to the mold, and contamination 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 that is 10 to 30 ° C. lower than the glass transition temperature (Tg) of the resin (or cyclic olefin resin). It 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 an Example and a comparative example are as follows.

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

(Measurement of glass transition temperature (Tg))
It measured based on JISK7121 using the differential scanning calorimeter (Perkin Elmer Co., Ltd. product, DSC8500).

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

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

(Evaluation of birefringence)
Using a heat press machine (B-012C, manufactured by Imoto Seisakusho Co., Ltd.), a film having a thickness of 200 μm was formed to prepare a test piece having a length of 1 cm and a width of 6 cm. The specimen was stretched 3 times at a temperature [glass transition temperature (Tg) + 10 ° C.] using uniaxial stretching. The retardation of the sample after stretching was measured using a retardation film / optical material measuring apparatus (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 pellets of “ARTON” (manufactured by JSR Corporation, F4520, Tg = 164 ° C., Mw = 60000) and 9,9-bis (4- (2-hydroxy) as a fluorene compound are used. Ethoxy) phenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEF) and 15 parts by weight are kneaded using a twin screw extruder (manufactured by Technobel Co., Ltd., model number KZW15 / 45), the strand is extruded, and a cutter is used. The pellet was obtained by cutting. The appearance of the resin composition was a colorless and transparent pellet.

(Example 2)
A resin composition was obtained in the same manner as in Example 1 except that 90 parts by weight of the 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 the 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 the 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 the 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 (Osaka Gas Chemical Co., Ltd., hereinafter referred to as BOPPEF) was used as the fluorene compound. Except for this, a resin composition was obtained in the same manner as in Example 1.

(Example 8)
Instead of BPEF, 15 parts by weight of 9,9-bis (6-hydroxy-2-naphthyl) fluorene (synthesized according to Example 1 of JP-A-2007-099741; hereinafter referred to as BNF) was used as the fluorene compound. In the same manner as in Example 1, a resin composition was obtained.

Example 9
Resin 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 Chemical Co., Ltd., hereinafter referred to as BCF) was used as the fluorene compound. A composition was obtained.

(Example 10)
Resin composition in the same manner as in Example 1 except that 15 parts by weight of 9,9-bis (4-glycidyloxy) phenyl) fluorene (Osaka Gas Chemical Co., Ltd., hereinafter referred to as 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 JP 2011-68624 A, BNEF) was used as the fluorene compound. In the same manner as above, a resin composition was obtained.

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 device (FANUC ROBOSHOT 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. Produced. It was confirmed that the obtained lens molding was accurately molded. In addition, no stain was observed in any lens molded product. Also, there were no molding problems such as molding defects, spool runner breakage, 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, physical properties and optical properties of “ARTON” (F4520) were measured. 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” (brand name D5014DP, Tg135 ° C., manufactured by Mitsui Chemicals, Inc.) was used as the cyclic olefin-based resin. It was. The physical properties and optical properties of the resin composition were not measurable.

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

In particular, a composition containing BNEF units is excellent in the balance of various properties, has the highest heat resistance, and the highest fluidity, and is suitable for molding applications. Birefringence is also lower than the cyclic olefin resin (Comparative Example 1) that does not contain BNEF units.

In Comparative Example 2, the miscibility (compatibility) was low and clouded.

The resin composition and the molded body of the present invention have high heat resistance (glass transition temperature), a medium Abbe number and a high refractive index, so that the degree of freedom in optical design can be improved. Therefore, it can be used as an optical material (for example, optical sheet, optical film, 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, or a network camera incorporated in a portable communication device such as a mobile phone or a smartphone.

Claims (14)

1. 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.
2. The resin composition according to claim 1, wherein the cyclic olefin-based resin is a resin containing a norbornene skeleton.
3. The resin composition according to claim 1 or 2, wherein the cyclic olefin-based resin is a resin containing at least a structural unit represented by the following formula (1).
   

   

   (In the formula, group R ¹ represents a hydrogen atom or an alkyl group, group R ² represents a hydrogen atom, an alkyl group or an aryl group, and 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, and q represents 0 or 1)
4. 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.
5. 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.
6. 6. The resin composition according to claim 1, wherein the compound having a 9,9-bisarylfluorene skeleton is a compound represented by the following formula (2).
   

   

   [Wherein, ring Z is an arene ring, R ³ is a halogen atom, cyano group, alkyl group, aryl group, carboxyl group or alkoxycarbonyl group, R ⁴ is a halogen atom, alkyl group, cycloalkyl 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 group, amino group or substituted amino group Or R ^{4 in the} two rings Z may be bonded to each other to form a direct bond or an alkylene group to form a hydrocarbon ring with adjacent carbon atoms, and the group X may be a group — [ (OR ⁵ ) _n1 -Y ¹ ] (wherein the substituent Y ¹ is a hydroxyl group, a mercap Group, glycidyloxy group or (meth) acryloyloxy group, R ⁵ is an alkylene group, n1 represents 0 or an integer of 1 or more) or a group-[(CH ₂ ) _n2 -Y ² ] (wherein substituted The group Y ² is a carboxyl group, an alkoxycarbonyl group, an amino group or a substituted amino group, n2 is 0 or an integer of 1 or more), k is an integer of 0 to 4, m is an integer of 0 or 1 or more, p Represents an integer of 1 or more. ]
7. In the 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, and R ³ is C _1-4 alkyl group, k is 0 or 1, R ⁴ is C _1-4 alkyl group or C _1-4 alkoxy group, m is an integer of 0 or 1, R ⁵ is C _2-4 alkylene group, and n1 is 0 The resin composition according to claim 6, wherein an integer of ˜2 and p is 1 or 2.
8. The resin composition according to claim 6 or 7, wherein in formula (2), ring Z is a naphthalene ring.
9. The compound represented by the formula (2) is 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 diC _1-4 alkyl- _{hydroxyC 6-12} aryl) fluorene, 9,9-bis (mono or dihydroxy (poly) C _2-4alkoxy C _6-12 aryl) fluorene, 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 diglyceryl di sill oxy _{C 6-12} aryl) fluorene, 9,9-bis _{(C 6-12} A Lumpur - Gurijishiruokishi _{C 6-12} aryl) fluorene, 9,9-bis (mono- or _{di-C 1-4} alkyl - Gurijishiruokishi _{C 6-12} aryl) fluorene, 9,9-bis (mono- or diglyceryl di sill oxy (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 a resin composition according to any one of claims 6 to 8, comprising at least one selected from diC _1-4 alkyl-glycidyloxy (poly) C _2-4 alkoxy C _6-12 aryl] fluorene.
10. 10. The resin composition according to claim 1, wherein the compound represented by the formula (2) is 9,9-bis (mono or dihydroxy (poly) C _2-4 alkoxynaphthyl) fluorene.
11. 11. The resin according to claim 1, wherein the ratio of the cyclic olefin resin and the compound having a 9,9-bisarylfluorene skeleton is the former / the latter (weight ratio) = 99/1 to 30/70. Composition.
12. The Abbe number calculated from the refractive index for the spectrum of C-line, D-line and F-line is 28 to 55 and / or the refractive index at a wavelength of 589 nm is 1.51 to 1.60. Resin composition.
13. A molded body formed of the resin composition according to any one of claims 1 to 12.
14. An optical lens formed of the resin composition according to any one of claims 1 to 12.