CN107429033B - Resin composition and optical lens - Google Patents

Abstract

A resin composition having an intermediate Abbe number is obtained by adding a compound having a 9, 9-bisarylfluorene skeleton represented by the following formula (2) and having a polar substituent to a cycloolefin resin having a functional group. [ wherein the ring Z represents an aromatic hydrocarbon ring, R³And R⁴Represents a substituent, and the group X represents a group- [ (OR)⁵)_n1‑Y¹](in the formula, substituent Y¹Represents a hydroxyl group, a mercapto group, a glycidoxy group or a (meth) acryloyloxy group, R⁵Represents an alkylene group, n1 represents an integer of 0 or 1 or more), or a group- [ (CH)₂)_n2‑Y²](in the formula, substituent Y²Represents a carboxyl group, an alkoxycarbonyl group, an amino group or a substituted amino group, n2 represents an integer of 0 or 1 or more), k represents an integer of 0 to 4, m represents an integer of 0 or 1 or more, and p represents an integer of 1 or more]. The resin composition has an Abbe number in the middle region (Abbe number of about 28 to 55) and is useful as an optical lens or the like.

Description

Resin composition and optical lens

Technical Field

The present invention relates to a resin composition which comprises a cycloolefin resin and a compound having a 9, 9-bisarylfluorene skeleton (hereinafter, may be referred to as a fluorene compound) and is useful as an optical lens.

Background

Cycloolefin resins have excellent properties such as high transparency, high heat resistance, and low birefringence, and are therefore used in optical materials, for example, photographic lenses (or optical lenses) included in portable communication devices such as mobile phones and smartphones.

In recent years, with the reduction in thickness and the increase in functionality of such mobile phones and smartphone terminals, there has been a demand for a smaller imaging lens to be mounted in an imaging device in order to secure a space for mounting components and elements. In addition, along with miniaturization, the resolution of the photographing lens is required to be improved as the pixelation of the photographing element such as a sensor using a charge coupled device (CCD sensor) or a sensor using a complementary metal oxide semiconductor (CMOS sensor) is increased. In order to cope with the small size and high imaging performance and the correction of various aberrations for such a taking lens, various efforts have been made to select a lens configuration, a shape and a material by applying an optical design under the limitation of cost. The optical design of the photographing lens unit is performed by inputting refractive index data of a lens material at a plurality of wavelengths in calculation software, automatically calculating according to an algorithm, and repeatedly adjusting. However, since the resin (or material) that can be used for the optical lens is limited, the degree of freedom of design is limited, and there is a limit to efficient and versatile design. That is, since the taking lens unit includes a plurality of lenses having different abbe numbers and refractive indices, it is generally configured by combining 1 or more lenses having a large abbe number and a medium refractive index (for example, 2 to 4 lenses made of a cycloolefin-based resin having an abbe number of 56 to 57 and a refractive index of 1.51 to 1.54) and a plurality of lenses having a small abbe number and a large refractive index (for example, 1 to 2 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). 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), it is expected that the degree of freedom of design is improved and optimization is possible. Although there are materials having an abbe number in the intermediate region in thermosetting resins, glasses, and the like, the cost of glass is high and the productivity of lenses made of thermosetting resins is low, and thus they are not used for optical lenses of mobile phones, smart phones, and the like.

On the other hand, a resin composition obtained by adding a compound having a fluorene skeleton or a resin containing a fluorene component to a thermoplastic resin is disclosed. For example, jp 2005-162785 a (patent document 1) or jp 2011-8017 a (patent document 2) describe that a compound having a 9, 9-bisarylfluorene skeleton is added to a resin (particularly, a resin containing an aromatic ring) to increase the refractive index of the resin or reduce birefringence. In these documents, an olefin-based resin or a cycloolefin-based resin is also exemplified as a resin, and it is described that the resin can be used for applications such as an optical lens.

Further, jp 2014-205734 a (patent document 3) describes that the abbe number of a resin can be increased by adding a compound having a 9, 9-bisarylfluorene skeleton to a resin having a small abbe number (particularly, a resin containing an aromatic ring). In this document, a cyclic olefin resin is also exemplified as the resin, and it is described that an optical lens, an optical film, and the like can be formed. In the examples, a predetermined fluorene compound (e.g., 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (BPEF) or the like) is added to a polycarbonate resin or polyethylene naphthalate to increase the abbe number. However, the ratio of the increase in abbe number with respect to the amount of the fluorene compound added is extremely small, and the adjustment is insufficient as an abbe adjusting agent. In the examples of patent documents 1 to 3, no specific description is given of the cycloolefin-based resin.

Further, japanese patent laid-open publication No. 2013-194186 (patent document 4) describes forming a retardation film from a resin composition comprising: an alicyclic polyester containing a 9, 9-bisarylfluorene compound in a diol component, and a polycycloolefin (cycloolefin-based resin). In this document, in order to improve compatibility (miscibility) with a polycycloolefin, a polyester is formed from a fluorene compound containing an alicyclic diol component. However, this document does not describe the adjustment of abbe number.

Further, Japanese patent application laid-open No. 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 (e.g., tensile strength) of the cyclic olefin copolymer can be improved, and that the abbe number is reduced. In examples of this document, 9-bis (3-methyl-4-hydroxyphenyl) fluorene (BCF) is added to a cyclic olefin copolymer "Arton 4531F" or "APEL 5014 DP" to obtain a resin composition. In the latter resin composition, although the abbe number is described to be reduced, the degree of the abbe number reduction is small relative to the amount of BCF added. The present inventors have found that when these resin compositions are prepared, the mixing property (compatibility) of the resin with BCF is low in the latter resin composition, and the resin composition seems to have transparency, but when the resin composition is subjected to a treatment such as hot pressing or molding, the resin composition may be clouded and the abbe number may not be measured. Further, it was found that these resin compositions were insufficient in heat resistance (glass transition temperature). Therefore, they have not been found to be useful for applications such as optical lenses.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2005-162785 (claims, [0015] [0059] [0079], examples)

Patent document 2: japanese patent laid-open publication No. 2011-8017 (claims, [0017] [0082], examples)

Patent document 3: japanese patent laid-open No. 2014-205734 (claims, [0087] [0126], examples)

Patent document 4: japanese patent laid-open publication No. 2013-194186 (claims, [0015] [0025], examples)

Patent document 5: japanese patent laid-open No. 2014-218660 (claims, [0028] [0029] [0034], examples).

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to provide a resin composition which can effectively reduce the abbe number of a cycloolefin resin and can adjust the abbe number to an intermediate region (for example, abbe number of about 28 to 55) even when the content of a fluorene compound is small, and which 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.

Means for solving the problems

As a result of intensive studies to achieve the above object, the present inventors have found that, when a compound having a predetermined 9, 9-bisarylfluorene skeleton (also referred to as a fluorene compound) is added or mixed to a functional group-containing cycloolefin resin in the form of a monomer, the abbe number of the cycloolefin resin can be effectively reduced to an intermediate region even when the content of the fluorene compound is small, and a resin composition having high heat resistance (glass transition temperature) can be obtained even when the abbe number of the cycloolefin resin is adjusted to the intermediate region, thereby completing the present invention.

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

[ chemical formula 1]

(in the formula, the group R¹Represents a hydrogen atom or an alkyl group, a group R²Represents a hydrogen atom, an alkyl group orAryl, the radical W represents a carboxyl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, hydroxyalkylcarbonyl, glycidoxycarbonyl, cyano or amido group, q represents 0 or 1).

In the formula (1), the formula may be: radical R¹Is a hydrogen atom or a methyl group, the radical R²Is a hydrogen atom, the radical W is a carboxyl radical, C_1-2Alkoxy-carbonyl, cyano or amido group, q is 0. The cycloolefin resin may have a glass transition temperature of about 140 to 250 ℃.

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

[ chemical formula 2]

[ wherein the ring Z represents an aromatic hydrocarbon ring, R³Represents a halogen atom, a cyano group, an alkyl group, an aryl group, a carboxyl group or an alkoxycarbonyl group, R⁴R represents a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkoxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group, a nitro group, a cyano group, an amino group or a substituted amino group, or 2 rings Z⁴Optionally bonded to each other to form a direct bond OR an alkylene group to form a hydrocarbon ring together with the adjacent carbon atom, the group X representing a group- [ (OR)⁵)_n1-Y¹](in the formula, substituent Y¹Represents a hydroxyl group, a mercapto group, a glycidoxy group or a (meth) acryloyloxy group, R⁵Represents an alkylene group, n1 represents an integer of 0 or 1 or more), or a group- [ (CH)₂)_n2-Y²](in the formula, substituent Y²Represents a carboxyl group, an alkoxycarbonyl group, an amino group or a substituted amino group, n2 represents an integer of 0 or 1 or more), k represents an integer of 0 to 4, m represents an integer of 0 or 1 or more, and p represents an integer of 1 or more]。

In the formula (2), the group X is [ (OR)⁵)_n1-Y¹]When, can be: substituent Y¹Is a hydroxyl group or a glycidoxy group,ring Z is benzene ring, naphthalene ring or biphenyl ring (especially naphthalene ring), R³Is C_1-4Alkyl, k is 0 or 1, R⁴Is C_1-4Alkyl radical, C_1-4Alkoxy, m is 0 or 1, R⁵Is C_2-4An alkylene group, n1 is an integer of 0 to 2, and p is 1 or 2.

Specifically, the compound represented by the formula (2) may contain a compound selected from 9, 9-bis (mono-or dihydroxy-C)_6-12Aryl) fluorenes, 9-bis (C)_6-12Aryl-hydroxy C_6-12Aryl) fluorenes, 9-bis (mono-or di-C)_1-4Alkyl-hydroxy C_6-12Aryl) fluorenes, 9-bis (mono-or dihydroxy (poly) C_2-4Alkoxy radical C_6-12Aryl) fluorenes, 9-bis (C)_6-12Aryl-hydroxy (poly) C_2-4Alkoxy radical C_6-12Aryl) fluorenes, 9-bis [ mono-or di-C_1-4Alkyl-hydroxy (poly) C_2-4Alkoxy radical C_6-12Aryl radicals]Fluorene, 9-bis (mono-or di-glycidoxy C)_6-12Aryl) fluorenes, 9-bis (C)_6-12Aryl-glycidoxy C_6-12Aryl) fluorenes, 9-bis (mono-or di-C)_1-4Alkyl-glycidoxy C_6-12Aryl) fluorene, 9-bis (mono-or di-glycidoxy (poly) C_2-4Alkoxy radical C_6-12Aryl) fluorenes, 9-bis (C)_6-12Aryl-hydroxy (poly) C_2-4Alkoxy radical C_6-12Aryl) fluorenes, 9-bis [ mono-or di-C_1-4Alkyl-glycidoxy (poly) C_2-4Alkoxy radical C_6-12Aryl radicals]At least 1 of the fluorenes. In particular, the compound represented by the aforementioned formula (2) may be 9, 9-bis (mono-or dihydroxy (poly) C_2-4Alkoxynaphthyl) fluorene.

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

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

In the present specification, "(meth) acryloyloxy" means acryloyloxy and methacryloyloxy.

ADVANTAGEOUS EFFECTS OF INVENTION

In the resin composition of the present invention, since the cycloolefin resin has a predetermined functional group, the abbe number of the cycloolefin resin can be effectively reduced, and the abbe number in the intermediate region can be easily adjusted. Further, since the cycloolefin resin has a polycyclic structure having the functional group, heat resistance (glass transition temperature) is high, and heat resistance can be maintained even when a fluorene compound is added. Therefore, the abbe number and the heat resistance (high glass transition temperature) in the intermediate region can be both satisfied. Further, since both have high compatibility, even if the ratio of the fluorene compound is large, the fluorene compound can be uniformly mixed without causing white turbidity, and the fluorene compound has high transparency and can greatly reduce the abbe number. Such a resin composition can broaden the degree of freedom in designing lenses and the like, and is useful for applications such as optical materials (for example, optical lenses).

Detailed Description

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 (also referred to as a fluorene compound).

[ cycloolefin resin ]

The cycloolefin-based resin has a functional group (A). The cycloolefin resin may be a resin containing, as a polymerization component, at least a cycloolefin having an olefinic double bond in the ring (for example, a homopolymer of the cycloolefin, or a copolymer of the cycloolefin and a copolymerizable monomer). The functional group (a) may be contained in the cyclic olefin and/or the copolymerizable monomer, and is preferably contained in at least 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 two-to four-ring olefin). The polycyclic olefin can be produced by means of a Diels-Alder reaction of an unsaturated compound having a functional group (A) and a carbon-carbon unsaturated double bond with a cyclic diene or triene (e.g., cyclopentadiene, dicyclopentadiene, etc.) optionally containing a substituent (C).

Examples of the unsaturated compound include a compound having a carboxyl group { for example, an unsaturated mono-or dicarboxylic acid [ for example, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid, and the like ]]And the like [ for example, a (meth) acrylic acid C such as an alkyl (meth) acrylate (e.g., methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, etc. ]_1-6Alkyl esters, preferably C (meth) acrylic acid_1-4Alkyl esters, etc.), unsaturated dicarboxylic acid alkyl esters (e.g., itaconic acid C such as methyl itaconate, etc.)_1-4Maleic acid di-C such as alkyl ester and dimethyl maleate_1-4Alkyl esters, etc.) and the like]And a compound having a cycloalkoxycarbonyl group [ e.g., cycloalkyl (meth) acrylate (e.g., C (meth) acrylic acid such as cyclohexyl (meth) acrylate)_5-8Cycloalkyl esters, etc.) and the like]And a compound having an aryloxycarbonyl group [ e.g., (meth) acrylic acid C such as phenyl (meth) acrylate_6-10Aryl esters and the like]And a compound having a hydroxyl group [ e.g., hydroxyalkyl (meth) acrylate (e.g., hydroxy C (meth) acrylate such as hydroxyethyl (meth) acrylate)_2-4Alkyl esters, etc.) and the like]And a compound having an alkoxy group [ e.g., (meth) acrylic acid C such as methoxyethyl (meth) acrylate_2-4Alkoxy radical C_2-4Alkyl esters and the like]A compound having a mercapto group (e.g., a compound corresponding to the above-mentioned compound having a hydroxyl group), a compound having a glycidyl group (e.g., glycidyl (meth) acrylate), a compound having an amide group (e.g., (meth) acrylamide), a compound having a cyano group (e.g., (meth) acrylonitrile), and the like. These unsaturated compounds may be used alone or in combination of two or more. Among these unsaturated compounds, those having a carboxyl group or C are preferable_1-2Alkoxy-carbonyl, cyano or amido compounds.

Examples of the substituent (C) of the cyclic olefin include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (e.g., C such as a methyl group and an ethyl group), and the like_1-6Alkyl, preferably C_1-4Alkyl, etc.), cycloalkyl (e.g. C such as cyclohexyl, etc.)_5-10Cycloalkyl), aryl (e.g. phenyl, etc. C_6-10Aryl), aralkyl (Benzyl, phenethyl, etc. C_6-10aryl-C_1-4Alkyl, etc.), and the like. The cyclic olefin may contain a single substituent (C) or two or more substituents.

Examples of the bicyclic olefins (bicycloalkenes) having functional group (A) include cyclic olefins having functional group (A) at least substituted with 2-norbornene, 2, 5-norbornadiene and the like (for example, 5-C olefins such as 5-carboxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-ethoxycarbonyl-2-norbornene, 5-methyl-5-carboxy-2-norbornene and the like_1-4Alkyl-5-carboxy-2-norbornene; 5-C such as 5-methyl-5-methoxycarbonyl-2-norbornene, 5-methyl-5-ethoxycarbonyl-2-norbornene_1-4alkyl-5-C_1-2Alkoxy-carbonyl-2-norbornene; 5-C such as 5-methyl-5-cyclohexyloxycarbonyl-2-norbornene_1-4alkyl-5-C_5-10Cycloalkoxy-carbonyl-2-norbornene; 5-hydroxy straight or branched C such as 5-hydroxyethoxycarbonyl-2-norbornene_2-3Alkoxy-carbonyl-2-norbornene; 5-cyano-2-norbornene; 5-amido-2-norbornene; 5, 6-dicarboxy-2-norbornene; 5, 6-Di C such as 5, 6-Dimethoxycarbonyl-2-norbornene_1-2Alkoxy-carbonyl-2-norbornene; 6-phenyl-5-carboxy-2-norbornene, etc.).

Examples of the tricycloalkenes (tricycloalkenes) having functional group (A) include tricyclo [5.2.1.0 ]^2,6]Cyclic olefins having at least the functional group (A) substituted on dec-3-ene (e.g. 8-hydroxy-tricyclo [ 5.2.1.0)^2,6]Dec-3-ene, 9-hydroxy-tricyclo [5.2.1.0^2,6]Dec-3-ene, 8-methoxy-tricyclo [5.2.1.0^2,6]8-C such as dec-3-ene_1-4Alkoxy-tricyclo [5.2.1.0^2,6]Dec-3-ene, 9-methoxy-tricyclo [5.2.1.0^2,6]9-C such as dec-3-ene_1-4Alkoxy-tricyclo [5.2.1.0^2,6]Dec-3-ene, 8-cyano-tricyclo [5.2.1.0^2,6]Dec-3-ene, 9-cyano-tricyclo [5.2.1.0^2,6]Dec-3-ene), and the like.

Examples of tetracyclic olefins (tetracyclic olefins) having functional group (A) include tetracyclic [4.4.0.1 ] and tetracyclic olefins^2,5.1^7,10]-3-dodecene, etc.) up toCyclic olefins less substituted with functional group (A) [ e.g. 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 [4.4.0.1^2,5.1^7,10]8-C such as dodec-3-ene_1-2Alkoxycarbonyl-tetracyclic [4.4.0.1^2,5.1^7,10]Dodec-3-ene; 8-methyl-8-carboxy-tetracyclo [4.4.0.1^2,5.1^7,10]8-C such as dodec-3-ene_1-4Alkyl-8-carboxy-tetracyclic [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]8-C such as dodec-3-ene_1-4alkyl-8-C_1-2Alkoxy-carbonyl-tetracyclic [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]8-C such as dodec-3-ene_1-4alkyl-8-C_5-8Cycloalkoxy-carbonyl-tetracyclic [4.4.0.1^2,5.1^7,10]Dodec-3-ene; 8-Hydroxyethoxycarbonyl-tetracyclic [4.4.0.1 ]^2,5.1^7,10]8-hydroxy straight or branched C such as dodec-3-ene_2-3Alkoxycarbonyl-tetracyclic [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]8, 9-Di C such as dodec-3-ene_1-2Alkoxy-carbonyl-tetracyclic [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]Dodec-3-ene, etc. These cyclic olefins may be used alone or in combination of two or more. Among these cyclic olefins, cyclic olefins having a norbornene skeleton (particularly, bicyclic olefins, tetracyclic olefins, and the like) are preferable from the viewpoint of heat resistance.

The cyclic olefin having the functional group (A) may be reacted with 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]Di-to tetracyclic olefins such as-3-dodecene, etc.).

In the 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)), the ratio of the cyclic olefin having a functional group (a) to the cyclic olefin having no functional group (a) may be, for example, about the 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), and particularly 90/10 to 100/0 (for example, 95/5 to 100/0). If the proportion of the cyclic olefin having the functional group (A) is too small, there is a fear that the Abbe number cannot be effectively reduced.

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

[ chemical formula 3]

(in the formula, the group R¹Represents a hydrogen atom or an alkyl group, a group R²Represents a hydrogen atom, an alkyl group or an aryl group, the group W represents a carboxyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyalkylcarbonyl group, a glycidoxycarbonyl group, a cyano group or an amido group, and q represents 0 or 1).

As substituents R¹And R²Examples of the alkyl group of (3) include C such as methyl and ethyl_1-4Alkyl groups, and the like. As substituents R²Examples of the aryl group in (2) include phenyl and the like. R¹Preferably a hydrogen atom, a methyl group, R²Preferably a hydrogen atom.

In the group W, the alkoxycarbonyl group includes, for example, a linear or branched C group such as methoxycarbonyl and ethoxycarbonyl_1-6Alkoxy-carbonyl group, etc., preferably straight-chainOr branched C_1-4Alkoxy-carbonyl, and the like. It is particularly preferable that C is the lower the number of carbon atoms of the alkoxycarbonyl group, the higher the glass transition temperature is in many cases_1-2Alkoxy-carbonyl.

Examples of the cycloalkoxycarbonyl group include C such as cyclohexyloxy-carbonyl_5-8Cycloalkoxy-carbonyl, and the like.

Examples of the aryloxycarbonyl group include, for example, a phenoxycarbonyl group and the like_6-10Aryloxy-carbonyl, and the like.

Examples of the hydroxyalkylcarbonyl group include a hydroxyl group such as a 2-hydroxyethylcarbonyl group or a 2-hydroxypropylcarbonyl group, and a linear or branched C_2-4Alkyl-carbonyl, and the like.

Among the groups W, preferred are a carboxyl group and C from the viewpoint of heat resistance (glass transition temperature)_1-2Alkoxycarbonyl, cyano, amido, and the like. In addition, q is 0 or 1, and usually at most 0.

The cycloolefin resin may be a homopolymer, or may be a copolymer with a copolymerizable monomer.

Examples of the copolymerizable monomer include linear olefins [ olefins (e.g., C.Cc.olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 2-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-hexene, 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, and 1-dodecene ]_2-12Olefins) and the like]And the like, preferably alpha-olefins (e.g., C such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and the like)_2-10Alpha-olefins, preferably C_2-6Alpha-olefins, in particular ethylene). The copolymerizable monomer may have the functional group (A), and may be, for example, the same compounds as the unsaturated compounds exemplified above (e.g., (meth) acrylic acid C such as (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, etc.)_1-2Alkyl esters, etc.).

Among these copolymerizable monomers, C is preferred_2-6Alpha-olefins, (meth) acrylic acid C_1-2Alkyl esters, and the like.

In the cycloolefin resin (for example, a copolymer of the above-mentioned copolymerizable monomer and a cycloolefin), the proportion of the cycloolefin may be, for example, about 20 to 99 mol% (for example, about 25 to 90 mol%), preferably about 30 to 95 mol% (for example, about 35 to 90 mol%), more preferably about 40 to 90 mol% (for example, about 50 to 80 mol%), and may be, for example, about 30 to 70 mol%, preferably about 40 to 60 mol% (for example, about 45 to 55 mol%). If the proportion of the cyclic olefin is too small, there is a concern that the miscibility (or affinity) with the fluorene compound is reduced, the abbe number cannot be effectively reduced, and the heat resistance (glass transition temperature) is also reduced.

The copolymer may have a structural unit represented by the formula (1) and a chain alkylene group (e.g., with C such as ethylene, propylene, butene, etc.)_2-6Olefin corresponds to) units. For example, the copolymer may have a structural unit represented by the following formula (1 a).

[ chemical formula 4]

(r and s represent the number of repetition of each structural unit and represent an integer of 1 or more; the ratio of r to s is r/s =90/10 to 10/90 (molar ratio); W, R¹、R²And 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 the above-mentioned cycloolefin-based resin, if the proportion of the cycloolefin having the functional group (a) is increased, the heat resistance (glass transition temperature) is often improved. The glass transition temperature of the cycloolefin resin may be selected from the range of about 120 to 250 ℃ as measured according to JIS K7121, and is, for example, about 140 to 250 ℃, preferably about 150 to 220 ℃, and more preferably about 160 to 200 ℃ (for example, about 160 to 180 ℃). The glass transition temperature of the cycloolefin resin may be, for example, 120 to 180 ℃, preferably 130 to 180 ℃, and more preferably 140 to 170 ℃. If the proportion of the cyclic olefin having the functional group (a) is too small, there is a concern that the miscibility (or affinity) with the fluorene compound is lowered, the heat resistance (glass transition temperature) is lowered, and the abbe number cannot be effectively reduced. Depending on the type of resin, detection may not be possible at a temperature equal to or lower than the decomposition temperature. Further, the glass transition temperature can be measured using a differential scanning calorimeter or the like.

The weight average molecular weight (in terms of polystyrene) of the cycloolefin resin is, for example, 10000 to 200000 (for example, 20000 to 190000), preferably 30000 to 170000 (for example, 40000 to 150000), and more preferably 40000 to 130000 (for example, 50000 to 130000) as measured by Gel Permeation Chromatography (GPC). If the molecular weight is too large, there is a concern that the melt viscosity becomes high, the productivity and processability of the optical material are lowered, and if the molecular weight is too small, the mechanical strength is lowered.

As the cycloolefin resin, a commercially available product (for example, "ARTONF 4520" manufactured by JSR corporation) can be used. Incidentally, "ARTONF 4520" is directed to a tetracyclic olefin having an alkoxycarbonyl group such as a carboxyl group, a methoxycarbonyl group or an ethoxycarbonyl group as the functional group (A) (tetracyclic [4.4.0.1 ] or the like^2,5.1^7,10]-3-dodecene) by hydrogenation. "APEL 5014 DP" manufactured by Mitsui chemical corporation is an addition polymer of a bicyclic olefin (2-norbornene) having no functional group and ethylene.

The method for producing the cycloolefin resin may be a conventional method [ for example, a method such as addition polymerization or ring-opening polymerization (ring-opening metathesis polymerization), or a method in which hydrogenation is carried out using a hydrogenation catalyst (for example, a palladium catalyst, an alumina-supported palladium catalyst, a ruthenium catalyst, or the like) after the ring-opening polymerization (ring-opening metathesis polymerization or the like) ].

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

[ fluorene compound ]

The fluorene compound has a 9, 9-bisarylfluorene skeleton and a polar substituent (B). By combining the polar substituent (B) with the functional group (a), it is estimated that the compatibility (or mixability) of the fluorene compound with the cycloolefin-based resin is improved, and the abbe number can be effectively reduced.

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

[ chemical formula 5]

[ wherein the ring Z represents an aromatic hydrocarbon ring, R³Represents a halogen atom, a cyano group, an alkyl group, an aryl group, a carboxyl group or an alkoxycarbonyl group, R⁴R represents a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkoxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group, a nitro group, a cyano group, an amino group or a substituted amino group, or 2 rings Z⁴Optionally bonded to each other to form a direct bond OR an alkylene group to form a hydrocarbon ring together with the adjacent carbon atom, the group X representing a group- [ (OR)⁵)_n1-Y¹](in the formula, substituent Y¹Represents a hydroxyl group, a mercapto group, a glycidoxy group or a (meth) acryloyloxy group, R⁵Represents an alkylene group, n1 represents an integer of 0 or 1 or more), or- [ (CH)₂)_n2-Y²](in the formula, substituent Y²Represents a carboxyl group, an alkoxycarbonyl group, an amino group or a substituted amino group, n2 represents an integer of 0 or 1 or more), k represents an integer of 0 to 4, m represents an integer of 0 or 1 or more, and p represents an integer of 1 or more]。

In the formula (2), examples of the aromatic hydrocarbon ring represented by the ring Z include monocyclic aromatic hydrocarbon rings such as benzene rings, polycyclic aromatic hydrocarbon rings, and the like, and polycyclic aromatic hydrocarbon rings include condensed polycyclic aromatic hydrocarbon rings (condensed polycyclic hydrocarbon rings), polycyclic aromatic hydrocarbon rings (polycyclic aromatic hydrocarbon rings), and the like.

Examples of the fused polycyclic aromatic hydrocarbon ring include a fused bisCyclic aromatic hydrocarbons (e.g. fused bicyclic C such as naphthalene)_10-16Aromatic hydrocarbon) rings, fused tricyclic aromatic hydrocarbon (e.g., anthracene, phenanthrene, etc.) rings, etc., fused two-to tetracyclic aromatic hydrocarbon rings, etc. Preferred fused polycyclic aromatic hydrocarbon rings include fused C rings such as naphthalene ring and anthracene ring_10-14Polycyclic aromatic hydrocarbon rings and the like, and particularly preferred is a naphthalene ring.

Examples of the polycyclic aromatic hydrocarbon ring include biaryl rings, for example, biphenyl ring, binaphthyl ring, phenylnaphthalene ring (e.g., 1-phenylnaphthalene ring, 2-phenylnaphthalene ring), etc., and bi-C_6-12An aromatic hydrocarbon ring; terphenyl rings, e.g. terphenyl rings, etc. triple C_6-12Aromatic hydrocarbon rings, and the like. As a preferable polycyclic aromatic hydrocarbon ring, there may be mentioned BiC_6-10Aromatic hydrocarbon rings, particularly biphenyl rings, and the like. It should be noted that the 2 rings Z may be the same or different rings.

In the above formula (2), as the group R³Examples thereof include a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom), a cyano group, and an alkyl group (e.g., a C group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group)_1-6Alkyl, aryl (phenyl, etc. C)_6-10Aryl, etc.), carboxyl group, alkoxycarbonyl group (e.g., C such as methoxycarbonyl, ethoxycarbonyl, etc.)_1-6Alkoxy-carbonyl, preferably C_1-4Alkoxy-carbonyl, etc.) and the like. Radical R³The polar substituent (B) may be the above-mentioned one, and examples of the polar substituent (B) include a carboxyl group, an alkoxycarbonyl group (e.g., C such as methoxycarbonyl group)_1-6Alkoxy-carbonyl, preferably C_1-4Alkoxy-carbonyl, etc.) and the like. In particular, the radical R³The substituent (B) may be a polar substituent such as a carboxyl group, or an alkyl group. The number of substitution k is an integer of 0 to 4 (e.g., 0 to 3), preferably an integer of 0 to 2 (e.g., 0 or 1). The substituent R may be the same or different in the number of substitution k, or 2 or more in k³May be the same as or different from each other, a substituent R substituted on 2 benzene rings of the fluorene ring³May be the same or different. In addition, the substituents R³The substitution position(s) of (a) is not particularly limited, and may be, for example, 2-to 7-positions (2-position, 3-position and/or 7-position, etc.) of the fluorene ring.

Among these rings Z, polycyclic aromatic hydrocarbon rings are preferable, and naphthalene rings are particularly preferable, from the viewpoint of an excellent balance between heat resistance and optical characteristics.

In the above formula (2), as the group R⁴Examples thereof include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, etc.) and a linear or branched C_1-10The alkyl group is preferably a linear or branched C_1-6Alkyl, etc.), cycloalkyl (C such as cyclopentyl, cyclohexyl, etc.)_5-10Cycloalkyl group, etc.), aralkyl group (C such as benzyl, phenethyl, etc.)_6-10aryl-C_1-4Alkyl, etc.), nitro, etc. Radical R⁴Examples of such a polar substituent (B) include an alkoxy group (e.g., C such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and tert-butoxy)_1-10Alkoxy, etc.), cycloalkoxy (e.g. C such as cyclohexyloxy, etc.)_5-10Cycloalkoxy group and the like), aryloxy group (e.g., C such as phenoxy group and the like)_6-10Aryloxy group and the like), aralkyloxy group (e.g., C such as benzyloxy_6-10aryl-C_1-4Alkoxy, etc.), alkylthio (e.g. methylthio, ethylthio, etc. C_1-10Alkylthio, etc.), cycloalkylthio (e.g. C such as cyclohexylthio, etc.)_5-10Cycloalkylthio and the like), arylthio (e.g. C such as thiophenoxy and the like)_6-10Arylthio, etc.), aralkylthio (e.g., C such as benzylthio, etc.)_6-10aryl-C_1-4Alkylthio group, etc.), carboxyl group, alkoxycarbonyl group (e.g., C such as methoxycarbonyl, ethoxycarbonyl, etc.)_1-6Alkoxy-carbonyl, preferably C_1-4Alkoxy-carbonyl group and the like), alkylcarbonyl group (e.g., C such as acetyl, propionyl and the like)_1-4Alkyl-carbonyl group, etc.), cyano group, substituted amino group (e.g., di-C such as dimethylamino group, etc.)_1-4di-C such as alkylamino, diethylamino, etc_1-4Alkyl-carbonylamino, etc.), etc.

These substituents R⁴Among them, there are representatively exemplified polar substituent (B) such as alkoxy group, carboxyl group, alkoxycarbonyl group, alkylcarbonyl group, cyano group, substituted amino group and the like, halogen atom, alkyl group, cycloalkyl group, aralkyl group, nitro group and the like. As preferred substituents R⁴Examples thereof include alkoxy and alkyl groups, etcOther being C such as methyl_1-4An alkyl group. Substituent R⁴May be the same or different in the same or different rings Z.

Furthermore, R of 2 rings Z⁴Optionally bonded to each other to form a direct bond or alkylene (e.g. methylene, ethylene, etc. C)_1-6Alkylene, preferably C_1-4Alkylene, etc.) to form a hydrocarbon ring together 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. Furthermore, R of 2 rings Z⁴When forming a hydrocarbon ring with an adjacent carbon atom, R⁴When the ring Z is a benzene ring, for example, the bonding position(s) of (1) or (2) is (are) the alpha-position or (especially) the beta-position of the naphthalene ring, and when the ring Z is a naphthalene ring and the 1-position or 2-position of the naphthalene ring is bonded to the 9-position of fluorene, the bonding position(s) of (2) is (are) the alpha-position or (especially) the beta-position of the naphthalene ring. The ring formed by the hydrocarbon ring and 2 rings Z may be, for example, a fluorene ring. The spiro carbon atom at the 9-position of fluorene may be an asymmetric carbon atom, and may form an optical isomer R or S. As a representative compound, a compound represented by the following formula (3) and the like can be given.

[ chemical formula 6]

(in the formula, X, R³K, p are the same as described above).

The number of the substitution numbers m is appropriately selected depending on the kind of the ring Z, the number of m, and the like, and may be, for example, an integer of about 0 to 8, an integer of 0 to 4, preferably an integer of 0 to 3 (e.g., 0 to 2), and particularly 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 R⁴May be a methyl group.

In the group X of the formula (2), alkylene R⁵Including linear or branched alkylene groups, and examples thereof include C such as ethylene, trimethylene and tetramethylene_2-6Alkylene (preferably straight chain C)_2-4Alkylene, particularly ethylene), for example, propylene, 1, 2-butylene, 1, 3-butylene, and the like_3-6Alkylene (preferably branched C)_3-4Alkylene radicals, in particularIs propylene) and the like. When n1 is an integer of 2 or more, the alkylene group R⁵May be the same or different. Furthermore, alkylene radicals R⁵May be the same or different in the same or different rings Z.

Oxyalkylene Radical (OR)⁵) The number n1 of (a) may be selected from the range of about 0 to 15 integers (e.g., about 0 to 10 integers), for example, about 0 to 8 integers (e.g., about 1 to 8), preferably about 0 to 5 integers (e.g., about 1 to 5), more preferably about 0 to 4 integers (e.g., about 1 to 4), particularly about 0 to 3 integers (e.g., about 1 to 3), and usually about 0 to 2 integers (e.g., about 0 or 1).

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

As substituents Y¹The polar substituent (B) is a majority, and examples thereof include a hydroxyl group, a mercapto group, a glycidoxy group, a (meth) acryloyloxy group and the like, and the substituent Y is a substituent²Examples thereof include a carboxyl group, an alkoxycarbonyl group (e.g., a C group such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, a tert-butoxycarbonyl group and the like)_1-6Alkoxy-carbonyl group, etc.), amino group, substituted amino group (e.g., di-C such as dimethylamino group, etc.)_1-4di-C such as alkylamino, diethylamino, etc_1-4Alkyl-carbonylamino, etc.), etc.

In the formula (2), the number of substitution p of the group X varies depending on the kind of the ring Z, and may be an integer of 1 or more, for example, an integer of 1 to 4, preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and particularly 1. Note that the number of substitutions n1 or n2 may be the same or different in each ring Z.

The group X may be substituted at an appropriate position on the ring Z, and when the ring Z is a benzene ring, it is often substituted at the 2-, 3-, or 4-position (particularly, the 3-and/or 4-position) of the phenyl group; when the ring Z is a naphthalene ring, it is often substituted at the 5-to 8-position of the naphthalene group, for example, the 1-position or 2-position of the naphthalene ring is substituted for the 9-position of fluorene (in the relationship of 1-naphthyl or 2-naphthyl), and the group X is often substituted in the relationship of the 1, 5-position, 2, 6-position, etc. (particularly in the relationship of the 2, 6-position when p is 1) with respect to the substituted position. When p is 2 or more, the substitution position is not particularly limited. In addition, in the polycyclic aromatic hydrocarbon ring Z, the substitution position of the group X is not particularly limited, and may be substituted on, for example, an aromatic hydrocarbon ring bonded to the 9-position of fluorene and/or an aromatic hydrocarbon ring adjacent to the aromatic hydrocarbon ring. For example, the 3-position or the 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 of the group X may be any of the 2-, 3-, 2' -, 3' -, 4' -, and 2-, 4' -, preferably 2-, 4' -, and particularly 2-position.

Here, the group X { the group- [ (OR) }⁵)_n1-Y¹]In the formula (III) }, the substituent Y¹Preferably hydroxyl group or glycidoxy group.

The polar substituent (B) of the fluorene compound may be derived from, for example, the substituent Y¹、Y²A substituent R³、R⁴Most of any of them are usually derived from at least the substituent Y¹、Y². 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 glycidoxy group, a (meth) acryloyloxy group, 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), hydroxyl group, glycidoxy group, and the like are preferable.

Specifically, in the formula (2), the substituent Y is a substituent X¹Compounds which are hydroxy or glycidoxy, may be illustrated by the substituent Y¹A compound having a hydroxyl group, n1 is 0, and p is 1, for example, 9-bis (hydroxyaromatic) fluorenes { e.g., 9-bis (4-hydroxyphenyl) fluorene, 9-bis (3-hydroxyphenyl) fluorene, 9-bis (6-hydroxy-2-naphthyl) fluorene, 9-bis (5-hydroxy-1-naphthyl) fluorene, and the like, 9-bis (hydroxy-C)_6-12Aryl) fluorene; 9, 9-bis (C) such as 9, 9-bis (3-phenyl-4-hydroxyphenyl) fluorene and 9, 9-bis (4-phenyl-3-hydroxyphenyl) fluorene_6-12Aryl-hydroxy C_6-12Aryl) fluorene; 9, 9-bis (mono-or di-C) fluorene such as 9, 9-bis (3-methyl-4-hydroxyphenyl) fluorene and 9, 9-bis (4-methyl-3-hydroxyphenyl) fluorene_1-4Alkyl-hydroxy C_6-12Aryl) fluorene }, dihydroxy-9, 9 '-spirobifluorene such as 2, 7-dihydroxy-9, 9' -spirobifluorene, and the like.

In the formula (2), as the substituent Y in the group X¹Examples of the compound include a compound having a hydroxyl group, n1 of 0 and p of 2 or more, such as 9, 9-bis [ (poly) hydroxyaromatic hydrocarbon]9, 9-bis (dihydroxy C) fluorene such as {9, 9-bis (3, 4-dihydroxyphenyl) fluorene and 9, 9-bis (2, 4-dihydroxyphenyl) fluorene_6-12Aryl) fluorene, etc.

In the formula (2), as the substituent Y in the group X¹Examples of the compound having a hydroxyl group, n1 of 1 and p of 1 include 9, 9-bis (hydroxyalkoxyarenes) fluorenes { e.g., 9-bis [4- (2-hydroxyethoxy) phenyl]Fluorene, 9-bis [4- (2-hydroxypropoxy) phenyl]Fluorene, 9-bis [6- (2-hydroxyethoxy) -2-naphthyl]Fluorene, 9-bis [5- (2-hydroxyethoxy) -1-naphthyl]Fluorene, 9-bis [6- (2-hydroxypropoxy) -2-naphthyl]Fluorene, 9-bis [5- (2-hydroxypropoxy) -1-naphthyl]9, 9-bis (hydroxy C) s such as fluorene_2-4Alkoxy radical C_6-12Aryl) fluorene; 9, 9-bis [ 4-phenyl-3- (2-hydroxyethoxy) phenyl]Fluorene, 9-bis [ 4-phenyl-3- (2-hydroxypropoxy) phenyl]9, 9-bis [ C ] fluorene and the like_6-12Aryl-hydroxy C_2-4Alkoxy radical C_6-12Aryl radicals]Fluorene, 9-bis [ 3-methyl-4- (2-hydroxyethoxy) phenyl]Fluorene, 9-bis [ 4-methyl-3- (2-hydroxypropoxy) phenyl]9, 9-bis [ mono-or di-C ] fluorene and the like_1-4Alkyl-hydroxy C_2-4Alkoxy radical C_6-12Aryl radicals]Fluorene, etc., and bis (hydroxy-C) such as 2, 7-bis (2-hydroxyethoxy) -9,9' -spirobifluorene_2-4Alkoxy) -9,9' -spirobifluorene, and the like.

In the formula (2), as the substituent Y in the group X¹Examples of the compound having a hydroxyl group, n1 of 1 and p of 2 or more include 9, 9-bis [ (poly) hydroxyalkoxyarenes]Fluorene {9, 9-bis [3, 4-bis (2-hydroxyethoxy) phenyl]Fluorene, 9-bis [5, 6-bis (2-hydroxyethoxy) naphthyl]9, 9-bis (dihydroxy C) s such as fluorene_2-4Alkoxy radical C_6-12Aryl) fluorene, etc.

In the formula (2), as the substituent Y in the group X¹A compound having a hydroxyl group, n1 of 2 or more and p of 1, corresponding to the compound wherein n1 is 0 or 1, and an oxyalkylene group (particularly, oxy C)_2-4Alkylene radical) The repeating unit n1 in (A) 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-bis {5- [2- (2-hydroxyethoxy) ethoxy]-1-naphthyl } fluorene, 9-bis [3, 4-bis [2- (2-hydroxyethoxy) ethoxy]Phenyl radical]Fluorene, 9-bis [5, 6-bis [2- (2-hydroxyethoxy) ethoxy]Naphthyl radical]9, 9-bis (mono-or dihydroxypoly-C) s such as fluorene_2-4Alkoxy radical C_6-12Aryl) fluorene; 9, 9-bis [ 4-phenyl-3- [2- (2-hydroxyethoxy) ethoxy]Phenyl radical]9, 9-bis [ C ] fluorene and the like_6-12Aryl-hydroxy poly C_2-4Alkoxy radical C_6-12Aryl radicals]Fluorene; 9, 9-bis [ 4-methyl-3- [2- (2-hydroxyethoxy) ethoxy]Phenyl radical]9, 9-bis [ mono-or di-C ] fluorene and the like_1-4Alkyl-hydroxy poly C_2-4Alkoxy radical C_6-12Aryl radicals]Fluorene; 2, 7-bis [2- (2-hydroxyethoxy) ethoxy]Bis (hydroxypolyC) s such as-9, 9' -spirobifluorene_2-4Alkoxy) -9,9' -spirobifluorene, and the like.

In the formula (2), the substituent Y in the group X is¹Examples of the glycidoxy group-containing compound include compounds having a glycidoxy group substituted for the above-mentioned hydroxyl group, for example, 9-bis (4-glycidoxyphenyl) fluorene, 9-bis (6-glycidoxy-2-naphthyl) fluorene, 9-bis (3, 4-diepoxoxyphenyl) fluorene and the like, 9-bis (mono-or diepoxypropoxy C_6-12Aryl) fluorene; 9, 9-bis (C) such as 9, 9-bis (4-phenyl-3-glycidoxyphenyl) fluorene_6-12Aryl-glycidoxy C_6-12Aryl) fluorene; 9, 9-bis (mono-or di-C) such as 9, 9-bis (3-methyl-4-glycidoxyphenyl) fluorene_1-4Alkyl-glycidoxy C_6-12Aryl) fluorene; 9, 9-bis [4- (2-glycidoxyethoxy) phenyl]Fluorene, 9-bis [6- (2-glycidoxyethoxy) -2-naphthyl]Fluorene, 9-bis [ 3-methyl-4- (2-glycidoxyethoxy) phenyl]9, 9-bis (mono-or di-glycidoxy (poly) C such as fluorene_2-4Alkoxy radical C_6-12Aryl) fluorene; 9, 9-bis [ 4-phenyl-3- (2-glycidoxyethoxy) phenyl]9, 9-bis [ C ] fluorene and the like_6-12Aryl-glycidoxy (poly) C_2-4Alkoxy radical C_6-12Aryl radicals]Fluorene; 9, 9-bis [ 3-methyl-4- (2-glycidoxyethoxy) phenyl]9, 9-bis [ mono-or di-C ] fluorene and the like_1-4Alkyl-glycidoxyRadical (poly) C_2-4Alkoxy radical C_6-12Aryl radicals]Fluorene; diepoxy group-9, 9 '-spirobifluorene such as 2, 7-diepoxy group-9, 9' -spirobifluorene; bis (glycidoxy (poly) C such as 2, 7-bis (2-glycidoxyethoxy) -9,9' -spirobifluorene_2-4Alkoxy) -9,9' -spirobifluorene, and the like.

In addition, "(poly) C_2-4Alkoxy "denotes C_2-4The number n1 or n2 of repeating units of the alkoxy group is an integer of 1 or more.

The compound represented by the formula (2) also includes compounds in which a mercapto group or a (meth) acryloyloxy group is substituted instead of a hydroxyl group or a glycidoxy group shown in specific examples.

In the above formula (2), as the group X { the group- [ (CH)₂)_n2-Y²]In the substituent Y²Examples of the compound having a carboxyl group include compounds wherein n2 is 0 and p is 1, such as 9, 9-bis (carboxyaryl) fluorenes { e.g., 9-bis (3-carboxyphenyl) fluorene, 9-bis (4-carboxyphenyl) fluorene, 9-bis (5-carboxy-1-naphthyl) fluorene, 9-bis (6-carboxy-2-naphthyl) fluorene and the like 9, 9-bis (carboxy C)_6-12Aryl) fluorene; examples of the compound in which n2 is 1 and p is 1 include 9, 9-bis (carboxyalkyl-aryl) fluorenes { e.g., 9-bis (4- (carboxymethyl) phenyl) fluorene, 9-bis (4- (2-carboxyethyl) phenyl) fluorene, 9-bis (3- (carboxymethyl) phenyl) fluorene, 9-bis (5- (carboxymethyl) -1-naphthyl) fluorene, 9-bis (6- (carboxymethyl) -2-naphthyl) fluorene and the like, 9-bis (carboxyC) fluorene_1-6alkyl-C_6-12Aryl) fluorene, and the like.

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

Among these compounds, from the viewpoint of heat resistance, preferred are: the ring Z in the formula (2) is benzene ring and Y¹Is hydroxy, n1=0, p =1, m =1 or 2, R⁴=C_1-4Compounds of alkyl groups, such as 9, 9-bis (3-methyl-4-hydroxyphenyl) fluorene (BCF); in the above formula (2), the ring Z is a condensed polycyclic ring C_10-14Aromatic hydrocarbon ring, Y¹Is hydroxy, n1=0, p =1, such as 9, 9-bis (6-hydroxy-2-naphthyl) fluorene (BNF), 9-bis (b5-hydroxy-1-naphthyl) fluorene, 9-bis (4-methyl-3-hydroxyphenyl) fluorene; in the above formula (2), the ring Z is a condensed polycyclic ring C_10-14Aromatic hydrocarbon ring, Y¹A compound which is hydroxy, n1= 1-3, p =1, such as 9, 9-bis [6- (2-hydroxyethoxy) -2-naphthyl]Fluorene (BNEF), 9-bis [5- (2-hydroxyethoxy) -1-naphthyl]Fluorene, 9-bis [6- (2-hydroxypropoxy) -2-naphthyl]Fluorene; in the above formula (2), the ring Z is a union or triplet C_6-12Aromatic hydrocarbon ring, Y¹Is hydroxyl, n1=1~3, R⁵=C_2-4Alkylene, p =1 compounds, e.g. 9, 9-bis [ 3-phenyl-4- (2-hydroxyethoxy) phenyl]Fluorene (BOPPEF), 9-bis [ 4-phenyl-3- (2-hydroxyethoxy) phenyl]Fluorene, and the like.

From the viewpoint of fluidity (or moldability), it is preferably: the ring Z in the formula (2) is benzene ring and Y¹Is hydroxyl, n1=1~3, R⁵Is C_2-4Alkylene, p =1 compounds, e.g. 9, 9-bis [4- (2-hydroxyethoxy) phenyl]Fluorene (BPEF), 9-bis [3- (2-hydroxyethoxy) phenyl]Fluorene; in the above formula (2), the ring Z is a condensed polycyclic ring C_10-14Aromatic hydrocarbon ring, Y¹A compound of hydroxy, n1= 1-3, p =1, such as BNEF, 9-bis [5- (2-hydroxyethoxy) -1-naphthyl]Fluorene, 9-bis [6- (2-hydroxypropoxy) -2-naphthyl]Fluorene; the ring Z in the formula (2) is benzene ring and Y¹Glycidyl, n1=0, p =1, such as 9, 9-bis (4-glycidoxyphenyl) fluorene (BPFG), 9-bis (3-glycidoxyphenyl) fluorene, and the like.

In particular, from the viewpoint of being able to reduce the abbe number while effectively maintaining high heat resistance (glass transition temperature) of the cycloolefin-based resin and also being able to greatly improve flowability (or moldability), it is preferable that: in the above formula (2), the ring Z is a condensed polycyclic ring C_10-14Aromatic hydrocarbon ring, Y¹A compound of hydroxyl group, n1=0, p =1 [ e.g. 9, 9-bis (6-hydroxy-2-naphthyl) fluorene (BNF) and the like](ii) a In the above formula (2), the ring Z is a condensed polycyclic ring C_10-14Aromatic hydrocarbon ring, Y¹A compound of hydroxy, n1= 1-3, p =1, such as BNEF, 9-bis [5- (2-hydroxyethoxy) -1-naphthyl]Fluorene, 9-bis [6- (2-hydroxypropoxy) -2-naphthyl]The fluorene is particularly preferable from the viewpoint of being able to highly satisfy heat resistance, optical characteristics, and moldabilityIn the formula (2), the middle ring Z is a condensed polycyclic ring C_10-14Aromatic hydrocarbon ring, Y¹The compound is a hydroxyl group, n1= 1-2 (particularly 1), and p =1, such as BNEF.

The compound represented by the formula (2) may be a commercially available compound or may be produced by a conventional method. For example the substituent Y in the group X¹The compound which is a hydroxyl group can be prepared by reacting 9-fluorenones with a group [ HO- (R) substituted on the ring Z in the presence of an acid catalyst⁵O)_n1-]A method of reacting a hydroxy-aromatic hydrocarbon ring-containing compound (for example, phenoxyalkanols such as 2-phenoxyethanol); a fluorene compound [ e.g. 9, 9-bis (4-hydroxyphenyl) fluorene, etc. ] having hydroxyaryl substituted at the 9-position of the fluorene]And is selected from radicals corresponding to OR⁵At least 1 of alkylene oxide, alkylene carbonate and halogenated alkanol. Furthermore, substituents Y, such as the radicals X¹The compounds shown for glycidoxy may be prepared by substitution of the ring Z with the group [ HO- (R)⁵O)_n1-]By reaction of the fluorene with epichlorohydrin.

[ resin composition ]

The resin composition of the present invention comprises the cycloolefin resin having the functional group (a) and the fluorene compound having the polar substituent (B), and even when the amount of the fluorene compound added or mixed (or melt-kneaded) is small, the abbe number of the cycloolefin resin can be effectively reduced, and a resin composition having an intermediate abbe number can be obtained. Further, even a cycloolefin resin (for example, a polycyclic olefin resin) has a predetermined functional group, and therefore has high compatibility with a fluorene compound having a polar group, and even if the proportion of the fluorene compound is large, cloudiness does not occur, and the fluorene compound can be uniformly mixed, so that the abbe number can be greatly reduced, and the resin has excellent transparency. In addition, since such a cycloolefin resin has a rigid bridged structure having the functional group (for example, a bicyclic structure, a tricyclic structure, or the like having a norbornene skeleton), the glass transition temperature is high, and 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 in the intermediate region. Therefore, the degree of freedom in optical design can be increased, and the optical material can be used for optical material applications (for example, optical lenses, optical sheets, optical films, and the like).

The ratio of the cycloolefin resin to the fluorene compound is selected from the range of, for example, about the former/latter (weight ratio) =99/1 to 40/60(97/3 to 40/60), and is, for example, about 95/5 to 45/55 (e.g., 93/7 to 45/55), preferably about 90/10 to 50/50 (e.g., 87/13 to 60/40), and more preferably about 85/15 to 70/30. If the proportion of the cycloolefin resin is too small, there is a fear that the heat resistance is insufficient, whereas if it is too large, there is a fear that the abbe number cannot be effectively reduced and the moldability (or flowability) is reduced.

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

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

Further, the aforementioned fluorene compound has a steric configuration (Cardo structure) in which a fluorene ring and two aryl rings (benzene rings, etc.) are perpendicular to each other, and shows optical isotropy. Therefore, the addition of the fluorene compound can further reduce the birefringence of the alicyclic cycloolefin resin having a low birefringence. Therefore, the aforementioned resin composition has low birefringence. That is, the birefringence of the resin composition may be, for example, about 30 to 56nm, preferably about 33 to 55nm, and more preferably about 35 to 54 nm. The birefringence can be measured by the method of examples.

The resin composition (or molded article) can satisfy both the abbe number of the intermediate region and the heat resistance (high glass transition temperature). That is, the glass transition temperature (Tg) of the resin composition may be, for example, about 100 to 200 ℃ (e.g., 120 to 190 ℃), preferably about 130 to 180 ℃ (e.g., 135 to 180 ℃), more preferably about 140 to 170 ℃ (e.g., about 145 to 165 ℃), or, for example, about 135 to 250 ℃ (e.g., 150 to 230 ℃), preferably about 160 to 210 ℃, more preferably about 170 to 200 ℃ depending on the kind of the functional group (or the kind of the resin). If the glass transition temperature is too low, there is a concern that heat resistance and the like may be reduced, and if it is too high, there is a concern that moldability may be reduced. The glass transition temperature can be measured by differential scanning calorimetry (measurement).

The resin composition may contain various additives [ for example, a filler or a reinforcing agent, a colorant (a dye, a fluorescent whitening agent, or the like), a conductive agent, a flame retardant, a plasticizer, a lubricant, a stabilizer (an antioxidant, an ultraviolet absorber, a heat stabilizer, or the like), a mold release agent, an antistatic agent, a dispersant, a flow control agent, a leveling agent, an antifoaming agent, a surface modifier, a stress reducing agent, a carbon material, or the like ] as required. These additives may be used alone or in combination of two or more. From the viewpoint of heat resistance stability, and from the viewpoint of antioxidant and weather resistance stability, an ultraviolet absorber or the like can be used.

Examples of the antioxidant include 2, 6-di-t-butyl-4-methylphenol, 2 '-dioxy-3, 3' -di-t-butyl-5, 5 '-dimethyldiphenylmethane, tetrakis (methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionato) methane, 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' -dioxy-3, 3 '-di-t-butyl-5, 5' -diethylphenylmethane, 3, 9-bis [1, 1-dimethyl-2- (. beta. - (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl ], 2,4,8, 10-tetraoxaspiro [5.5] undecane, tris (2, 4-di-t-butylphenyl) phosphite, pentaerythritol bis (2, 6-di-t-butyl-4-methylphenyl) phosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, and the like.

Examples of the ultraviolet absorber include 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4, 6-di-tert-amylphenol, 2- (benzotriazol-2-yl) -4, 6-di-tert-butylphenol, and 2,2' -methylenebis {4- (1,1,3, 3-tetramethylbutyl) -6- [ (2H-benzotriazol-2-yl) phenol }.

The proportion of the additive varies depending on the kind of the additive, and may be, for example, about 0.001 to 10 parts by weight, preferably about 0.01 to 7 parts by weight, and more preferably about 0.05 to 5 parts by weight, based on 100 parts by weight of the resin composition.

The resin composition can be obtained by mixing the cycloolefin resin with the fluorene compound [ and other components (for example, the additives) as needed ]. The mixing method is not particularly limited, and for example, the components may be mixed by melt kneading or may be mixed by dissolving the components in a solvent.

The resin composition can remarkably improve fluidity and moldability while maintaining high heat resistance. The Melt Flow Rate (MFR) of the resin composition varies depending on the type of the resin, and may be, for example, about 5 to 50g/10 min, preferably about 7 to 47g/10 min, and more preferably about 10 to 45g/10 min by a method (temperature 280 ℃ C., load 2.16kgf) in accordance with JIS K7210.

Further, the present invention also includes a molded article formed from such a resin composition. The shape of such a molded article is not particularly limited, and may be appropriately selected depending on the application, and examples thereof include a two-dimensional shape (a planar shape, a film shape, a sheet shape, and the like), and a three-dimensional shape [ a concave-convex shape, an aspherical shape (an elliptical shape, for example), a tubular shape, a rod shape, a cylindrical shape, a hollow shape, and the like ].

The molded article can be produced by, for example, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, press molding, casting molding, or the like.

The molded article or the resin composition of the present invention is excellent in optical characteristics, and therefore can be suitably used for applications of optical materials (for example, optical lenses, optical sheets, optical films, and the like). In particular, the resin composition of the present invention has an intermediate abbe number and is therefore useful for forming optical lenses and the like.

For example, from the viewpoint of productivity, an optical lens is generally manufactured by injection molding. 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. Further, in an optical lens, since it is necessary to precisely control the shape of the lens surface, in the case of a resin having low flowability, it is difficult to perform curved surface transfer with high accuracy, and molding is often performed by increasing the flowability by increasing the resin temperature, the mold temperature, and the like at the time of molding. However, if the resin temperature, the mold temperature, or the like is increased, there may be problems such as decomposition of the resin, decomposition and volatilization of additives, sticking to the mold, and fouling. 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, and thus can prevent these problems. The resin temperature may be, for example, about 200 to 350 ℃, and the mold temperature may be, for example, 10 to 30 ℃ lower than the glass transition temperature (Tg) of the resin (or cycloolefin resin).

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The measurement methods and evaluation methods in examples and comparative examples are as follows.

(measurement of molecular weight (Mw))

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

(measurement of glass transition temperature (Tg))

Measured according to JIS K7121 using differential scanning calorimetry (manufactured by パーキンエルマー, DSC 8500).

(measurement of melt flow Rate)

Melt Flow Rate (MFR) was measured in accordance with JIS K7210, examples 1 to 10 and comparative example 2 at a temperature of 280 ℃ under a load of 2.16kg, and in comparative example 1 at a temperature of 280 ℃ under a load of 16 kg.

(measurement of refractive index and Abbe number)

The refractive index and Abbe number were measured at a measurement temperature of 20 ℃ for the refractive index nD of D line (wavelength 589nm) using a KALNEW precision refractometer (manufactured by Shimadzu デバイス, Ltd., KPR 2000). The abbe number (vD) is calculated by using the equation of vD = (nD-1)/(nF-nC). nF denotes the refractive index for the F-line (wavelength 486nm), and nC denotes the refractive index for the C-line (wavelength 656 nm).

(evaluation of birefringence)

A film having a thickness of 200 μm was formed by using a hot press (B-012C manufactured by Kogyo Co., Ltd.) to prepare a test piece having a length of 1 cm. times.6 cm. The test piece was stretched 3 times at a temperature of [ glass transition temperature (Tg) +10 ℃ C ] by uniaxial stretching. The retardation of the sample after stretching was measured using a retardation film seed optical material measuring apparatus (red jar electronic corporation, RETS 100). The measured value was expressed as a value converted into 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)

The resin composition was kneaded with 85 parts by weight of pellets of "ARTON" (manufactured by JSR corporation, F4520, Tg =164 ℃, Mw =60000) as a cyclic olefin resin and 15 parts by weight of 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (manufactured by osaka ガスケミカル, hereinafter referred to as BPEF) as a fluorene compound using a twin-screw extruder (manufactured by (corporation) テクノベル, model number KZW15/45), and the kneaded product was extruded into a strand and cut with a cutter to obtain pellets. The appearance of the resin composition was colorless transparent pellets.

(example 2)

A resin composition was obtained in the same manner as in example 1, except that 90 parts by weight of the cycloolefin-based 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 a cycloolefin-based 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 a cycloolefin-based 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 a cycloolefin-based 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 a cycloolefin-based resin and 50 parts by weight of BPEF were used.

(example 7)

A resin composition was obtained in the same manner as in example 1 except that 15 parts by weight of 9, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene (manufactured by osaka ガスケミカル (ltd., hereinafter referred to as BOPPEF) was used as the fluorene compound instead of BPEF.

(example 8)

A resin composition was obtained in the same manner as in example 1 except that 15 parts by weight of 9, 9-bis (6-hydroxy-2-naphthyl) fluorene (synthesized in example 1 of jp 2007-a 099741, hereinafter referred to as BNF) was used as the fluorene compound instead of BPEF.

(example 9)

A resin composition was obtained in the same manner as in example 1, except that 15 parts by weight of 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter referred to as BCF, manufactured by osaka ガスケミカル, inc.) was used as the fluorene compound.

(example 10)

A resin composition was obtained in the same manner as in example 1 except for using 15 parts by weight of 9, 9-bis (4-glycidoxy) phenyl) fluorene (manufactured by osaka ガスケミカル (ltd., hereinafter referred to as BPFG) as the fluorene compound.

(example 11)

A resin composition was obtained in the same manner as in example 1 except that 20 parts by weight of 9, 9-bis (6-hydroxyethoxy-2-naphthyl) fluorene (synthesized in accordance with example 1 of Japanese patent application laid-open No. 2011-one 68624, hereinafter referred to as BNEF) was used as the fluorene compound.

(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 and evaluation)

A lens was produced by injection molding using an aspherical mold in an injection molding apparatus (FANUC ROBOSHOT S-2000i50B, manufactured by ファナック K.) in which the injection molding was performed 1 ten thousand times continuously at a resin temperature of 300 ℃ and a mold temperature of 120 ℃. It was confirmed that the obtained lens molded article could be molded with good precision. In addition, no smudging was observed for all lens moldings. In addition, molding failures such as molding failure, breakage of the sprue runner, and generation of gas are also eliminated.

The resin compositions obtained in examples 1 to 13 were measured for physical properties [ glass transition temperature (Tg), Melt Flow Rate (MFR) ], and optical properties [ refractive index, Abbe number, and birefringence ]. The measurement results are shown in table 1.

Comparative example 1

The physical properties and optical properties of "ARTON" (F4520) as a cycloolefin resin 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" (product name D5014DP, Tg135 ℃ C., manufactured by Mitsui chemical Co., Ltd.) was used as the cycloolefin-based resin, and cloudy pellets were obtained. The physical properties and optical properties of the resin composition could not be measured.

[ Table 1]

。

As is clear from table 1, in examples 1 to 6, the larger the amount of the fluorene compound added, the smaller the abbe number and the higher the refractive index as compared with comparative example 1. In examples 7 to 13 using a fluorene compound having a structure different from that of BPEF, the abbe number was also reduced and the refractive index was also improved. The resin compositions obtained in examples 1 to 13 had high refractive indices and abbe numbers in the middle region, and had high glass transition temperatures. Further, in examples 1 to 13, birefringence was also reduced as compared with comparative example 1. Further, in examples 1 to 13, although the load was smaller than that in comparative example 1, the MFR value was larger than that in comparative example 1, and the flowability was greatly improved. In particular, among BPEF, BOPPEF, BNF, BCF, BPFG, and BNEF, a composition containing BNEF or BNF (particularly BNEF) units is excellent in heat resistance. Further, the composition containing a BOPPEF unit has high heat resistance and a high degree of abbe number reduction. Further, the composition comprising BPFG units has high flowability and low birefringence.

In particular, a composition containing BNEF units is excellent in balance of properties, has the highest heat resistance and the highest fluidity, and is suitable for molding applications. The birefringence was also lower than that of the cycloolefin-based resin containing no BNEF unit (comparative example 1).

In comparative example 2, the miscibility (compatibility) was low, and white turbidity occurred.

Industrial applicability

The resin composition and the molded article of the present invention have high heat resistance (glass transition temperature), and have a medium abbe number and a high refractive index, and therefore can improve the degree of freedom in optical design. Therefore, the resin composition can be used for optical materials (for example, optical sheets, optical films, optical lenses, etc.). In particular, the present invention is useful as an optical lens for a small camera such as a camera built in a mobile communication device such as a mobile phone or a smartphone, a digital camera, a monitoring camera, an in-vehicle camera, or a network camera.

Claims (13)

1. A resin composition comprising: a cycloolefin resin having a functional group and a compound having a 9, 9-bisarylfluorene skeleton having a polar substituent,

the compound having a 9, 9-bisarylfluorene skeleton is a compound represented by the following formula (2),

wherein ring Z represents a condensed polycyclic ring C_10-14Aromatic hydrocarbon ring, R³Represents a halogen atom, a cyano group, an alkyl group, an aryl group, a carboxyl group or an alkoxycarbonyl group, R⁴R represents a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkoxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group, a nitro group, a cyano group, an amino group or a substituted amino group, or 2 rings Z⁴Optionally bonded to each other to form a direct bond or an alkylene group to form a hydrocarbon ring together with the adjacent carbon atom,

the radical X represents a radical- [ (OR)⁵)_n1-Y¹]

In the formula, the substituent Y¹Represents a hydroxyl group, a mercapto group, a glycidoxy group or a (meth) acryloyloxy group, R⁵Represents an alkylene group, and n1 represents 0 or an integer of 1 or more; or

Group- [ (CH)₂)_n2-Y²]

In the formula, the substituent Y²Represents a carboxyl group, an alkoxycarbonyl group, an amino group or a substituted amino group, n2 represents an integer of 0 or 1 or more, k represents an integer of 0 to 4, m represents an integer of 0 or 1 or more, and p represents an integer of 1 or more.

2. The resin composition according to claim 1, wherein the cyclic olefin resin is a resin containing a norbornene skeleton.

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

in the formula, the group R¹Represents a hydrogen atom or an alkyl group, a group R²Represents a hydrogen atom, an alkyl group or an aryl group, the group W represents a carboxyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyalkylcarbonyl group, a glycidoxycarbonyl group, a cyano group or an amido group, and q represents 0 or 1.

4. The resin composition according to claim 3, wherein in formula (1), the group R¹Is a hydrogen atom or a methyl group, the radical R²Is a hydrogen atom, the radical W is a carboxyl radical, C_1-2Alkoxy-carbonyl, cyano or amido group, q is 0.

5. The resin composition according to claim 1 or 2, wherein the cycloolefin resin has a glass transition temperature of 140 to 250 ℃.

6. The resin composition according to claim 1 OR 2, wherein in formula (2), the group X is [ (OR)⁵)_n1-Y¹]When, substituent Y¹Is hydroxy, ring Z is naphthalene ring, R³Is C_1-4Alkyl, k is 0 or 1, R⁴Is C_1-4Alkyl or C_1-4Alkoxy, m is an integer of 0 or 1, R⁵Is C_2-4An alkylene group, n1 is an integer of 0 to 2, p is 1 or 2, or,

substituent Y¹Is glycidoxy, ring Z is naphthalene ring, R³Is C_1-4Alkyl, k is 0 or 1, R⁴Is C_1-4Alkyl or C_1-4Alkoxy, m is an integer of 0 or 1, R⁵Is C_2-4An alkylene group, n1 is an integer of 0 to 2, and p is 1 or 2.

7. The resin composition according to claim 1 or 2, wherein, in formula (2), ring Z is a naphthalene ring.

8. The resin composition according to claim 1 or 2, wherein the compound represented by formula (2) comprises a compound selected from the group consisting of 9, 9-bis (mono-or dihydroxynaphthyl) fluorene, 9-bis (mono-or dihydroxy (poly) C_2-4Alkoxynaphthyl) fluorene.

9. The resin composition according to claim 1 or 2, wherein the compound represented by formula (2) is 9, 9-bis (mono-or dihydroxy (poly) C_2-4Alkoxynaphthyl) fluorene.

10. The resin composition according to claim 1 or 2, wherein the ratio of the cycloolefin resin to the compound having a 9, 9-bisarylfluorene skeleton is 99/1 to 30/70 in terms of the weight ratio of the cycloolefin resin to the compound having a 9, 9-bisarylfluorene skeleton.

11. The resin composition according to claim 1 or 2, wherein an Abbe number calculated from refractive indices of spectra of C line, D line and F line is 28 to 55, and/or a refractive index at a wavelength of 589nm is 1.51 to 1.60, C line is 656nm, D line is 589nm, and F line is 456 nm.

12. A molded article comprising the resin composition according to any one of claims 1 to 11.

13. An optical lens formed from the resin composition according to any one of claims 1 to 12.