JP6235959B2 - Cyclic olefin resin composition - Google Patents

Description

  The present invention relates to a resin composition containing a cyclic olefin resin (particularly a cyclic olefin copolymer) and a molded product thereof.

  Compounds having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) are known to have excellent functions such as a high refractive index and high heat resistance. As a method for allowing the resin to exhibit such an excellent function of the fluorene skeleton and molding it, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene In general, a method in which (BCF), bisphenoxyethanol fluorene (BPEF), or the like is used as a constituent component of a resin and a fluorene skeleton is introduced into a part of the skeleton structure of the resin.

  For example, JP-A-2002-284864 (Patent Document 1) discloses a molding material composed of a polyester-based resin having a 9,9-bisphenylfluorene skeleton. JP 2002-284834 A (Patent Document 2) discloses a polyurethane resin having a 9,9-bisphenylfluorene skeleton and crosslinked with a crosslinking agent. In these documents, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (bisphenoxyethanol) are used as part of the diol component constituting the resin. Fluorene skeleton is introduced into the resin.

  However, in such a method, since the resin skeleton is replaced with a fluorene skeleton, a complicated polymerization reaction is required, and the method cannot be applied to a wide range of resins.

  On the other hand, attempts have been made to add a fluorene compound directly to a resin without polymerizing it.

  For example, Japanese Unexamined Patent Application Publication No. 2005-162785 (Patent Document 3) discloses a resin composition composed of a compound having a 9,9-bisphenylfluorene skeleton and a thermoplastic resin. This document describes that a compound having a 9,9-bisphenylfluorene skeleton can be added to a thermoplastic resin to impart a high refractive index to the thermoplastic resin. In the example, a transparent resin film is prepared by mixing 30 to 40 parts by weight of a specific compound (bisphenol fluorenediglycidyl ether, bisphenoxyethanol fluorene or bisphenoxyethanol fluoredenyl acrylate) with 100 parts by weight of polycarbonate resin. And that the refractive index has increased.

  Japanese Patent Laid-Open No. 2011-21083 (Patent Document 4) discloses that a phenol compound functions as a nucleating agent (β crystal nucleating agent) for forming a β crystal structure in a crystalline resin such as polylactic acid. Have been described. In the examples of this document, 1 to 5% by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is added to the α-crystal (melting point: 168 ° C.) poly-L lactic acid and melted. Kneaded to obtain poly L-lactic acid in which β crystals (melting point: 163 ° C.) were formed, and Tg was changed from 56.5 ° C. to 60.9-62.1 ° C. as the crystal structure was changed. It is described that changed.

  Furthermore, JP 2011-8017 A (Patent Document 5) discloses an optical resin composition composed of a transparent resin and a fluorene compound having a 9,9-bisarylfluorene skeleton. And in this document, it is described that the birefringence can be lowered without impairing the mechanical properties and heat resistance of the transparent resin. In a specific example, the fluorene-containing polyester resin and the polycarbonate resin 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis (4-glycidyloxyphenyl) fluorene, or 9,9-bis (4-hydroxy-3-methylphenyl) fluorene It is described that a stretched film was prepared from a resin composition containing and the birefringence was lowered. In this document, a cyclic olefin-based resin is described as an example of a transparent resin, but a polycarbonate-based resin or the like is preferable, and details thereof are not described at all. Not.

JP 2002-284864 A (Claims, Examples) JP 2002-284834 A (Claims, Examples) JP-A-2005-162785 (Claims, Examples) Examples) JP 2011-21083 A (Claims, Examples) JP 2011-8017 A (Claims, paragraph [0017], Examples)

  The objective of this invention is providing the novel resin composition containing a cyclic olefin resin, and the molded object formed with this resin composition.

  Another object of the present invention is to provide a cyclic olefin resin composition having improved mechanical properties and a molded body formed from this resin composition.

  Still another object of the present invention is to provide a cyclic olefin resin composition having a reduced Abbe number and a molded body formed from this resin composition.

  Cyclic olefin resin is a material excellent in solvent resistance and the like, but further improvement in characteristics is desired in such cyclic olefin resin. However, the cyclic olefin resin generally has a poor affinity for additives, and the current situation is that modification of the cyclic olefin resin is not easy.

  Under such circumstances, the present inventors have intensively studied to solve the above problems, and as a result, the compound having a 9,9-bisarylfluorene skeleton is a cyclic olefin resin (particularly a cyclic olefin copolymer). It can be added or mixed with high affinity (or compatibility), and the resulting resin composition surprisingly has various properties of the cyclic olefin resin, such as mechanical strength [for example, tensile strength, bending strength and storage elasticity. Not only the modulus E ′ (for example, at least one selected from storage elastic modulus E ′ at room temperature or room temperature (about 15-30 ° C.)), but also optical properties (for example, transparency, low birefringence, low Abbe number) Etc.) and the like were formed, and the present invention was completed.

  That is, the compound having the 9,9-bisarylfluorene skeleton is an agent for improving the mechanical properties (an agent for improving mechanical strength such as tensile strength, bending strength, storage elastic modulus E ′), or an agent for improving optical properties. It functions as a birefringence reducing agent, Abbe number adjusting agent (or Abbe number reducing agent, etc.).

  The resin composition of the present invention contains a cyclic olefin resin [particularly a cyclic olefin copolymer (for example, a cyclic olefin copolymer having a polar group)] and a compound having a 9,9-bisarylfluorene skeleton. The compound having a 9,9-bisarylfluorene skeleton may be, for example, a compound represented by the following formula (1).

[Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is a group — [(OR ³ ) nY] (wherein Y is a hydroxyl group, a mercapto group, glycidyl An oxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is an integer of 0 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is 1 or more. Indicates an integer. ]

  In particular, the compound having a 9,9-bisarylfluorene skeleton may be a compound represented by the following formula (1A).

(In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1).)
In the above formula (1) or (1A), the ring Z may be a benzene ring or a naphthalene ring, R ¹ may be an alkyl group, k may be 0 to 1, and R ² May be an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group, m may be 0 to 2, R ³ may be a C _2-4 alkylene group, and n is 0-2 may be sufficient and p may be 1-3.

  The compounds having a 9,9-bisarylfluorene skeleton typically include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl- Hydroxyphenyl) fluorene, 9,9-bis (di or trihydroxyphenyl) fluorene, 9,9-bis (hydroxynaphthyl) fluorene, 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-) It may be at least one selected from hydroxyalkoxyphenyl) fluorene, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene, and 9,9-bis (hydroxyalkoxynaphthyl) fluorene.

  In the resin composition of the present invention, the ratio of the compound having a 9,9-bisarylfluorene skeleton may be, for example, 0.5 to 50 parts by weight with respect to 100 parts by weight of the cyclic olefin resin.

  Moreover, the molded object formed with the said resin composition is also contained in this invention. Such a molded body is excellent in mechanical properties and optical properties, and has high transparency, high refractive index, low birefringence, and a low Abbe number. Therefore, the molded article of the present invention may be an optical molded article (such as an optical film or a lens). Further, the molded body of the present invention may be a film (film-shaped molded body), and such a molded body may be a stretched film.

  In the present specification, “9,9-bis (hydroxyaryl) fluorenes” and “9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes” mean “9,9-bis (hydroxyaryl)”. As long as it has “) fluorene skeleton” or “9,9-bis (hydroxy (poly) alkoxyaryl) fluorene skeleton”, it includes compounds having substituents on aryl groups and fluorene skeletons (specifically, positions 2 to 7 of fluorene) Use for meaning. Furthermore, in this specification, “9,9-bis (hydroxy (poly) alkoxyaryl) fluorene” means 9,9-bis (hydroxyalkoxyaryl) fluorene and 9,9-bis (hydroxypolyalkoxyaryl) fluorene. Used to mean including

  The resin composition of the present invention is a novel resin composition containing a cyclic olefin resin. Such a resin composition has excellent characteristics derived from a cyclic olefin resin, and is improved or improved in various characteristics (for example, improved mechanical characteristics, improved refractive index, reduced birefringence, and Abbe number). And is very useful.

[Resin composition]
The resin composition of the present invention contains a cyclic olefin resin and a compound having a fluorene skeleton (9,9-bisarylfluorene skeleton) (hereinafter sometimes referred to as a fluorene compound).

(Cyclic olefin resin)
Cyclic olefin resin is resin which uses cyclic olefin as a polymerization component at least. The cyclic olefin may be a monocyclic olefin or a polycyclic olefin. The cyclic olefin may be substituted with, for example, a hydrocarbon group [for example, an alkyl group (for example, a C _1-10 alkyl group such as a methyl group, preferably a C _1-5 alkyl group), a cycloalkyl group (for example, cyclohexyl). A C _5-10 cycloalkyl group such as a group), an aryl group (eg, a C _6-10 aryl group such as a phenyl group), an alkenyl group (eg, a C _2-10 alkenyl group such as a propenyl group), a cycloalkenyl group (For example, C _5-10 cycloalkenyl group such as cyclopentenyl group and cyclohexenyl group), alkylidene group (for example, C _2-10 alkylidene group such as ethylidene group, preferably C _2-5 alkylidene group, etc.) , polar group [e.g., alkoxy groups (e.g., _{C 1-10} alkoxy group such as methoxy group, preferred Ku is C _1-6 alkoxy group), an acyl group (e.g., a C _2-5 alkanoyl group such as acetyl group), an acyloxy group [e.g., an alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group C _1-10 alkoxy-carbonyl group), cycloalkoxycarbonyl group (for example, C _5-10 cycloalkyl-carbonyl group such as cyclohexyloxycarbonyl group, etc.), hydroxyl group, carboxyl group, amino group, substituted amino group , A halogen atom, a haloalkyl group, a nitro group, a cyano group, an oxo group (═O), a heterocyclic group (such as a nitrogen atom-containing heterocyclic group such as a pyridyl group). The cyclic olefin may have a substituent alone or in combination of two or more.

Specific cyclic olefins include monocyclic olefins [eg, cycloalkenes (eg, cycloC _3-10 alkenes such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, etc.), cycloalkadienes (eg, cyclopentadiene, etc. A cyclo C _3-10 alkadiene, etc.]], bicyclic olefins {eg norbornenes [eg norbornene (eg 2-norbornene), alkyl norbornene (eg 5-methyl-2-norbornene, 5, 5 or 5,6-dimethyl-2-norbornene, 5-ethylidene-2-norbornene), aryl norbornene (for example, 5-phenyl-2-norbornene), norbornene having a polar group (for example, 5-cyano-2-norbornene, etc.) Cyanonorbornene Acyloxynorbornene such as 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5,6-dimethoxycarbonyl-2-norbornene, 5-methyl-5-cyclohexyloxycarbonyl-2-norbornene (Alkoxycarbonyl norbornene, cycloalkoxycarbonyl norbornene, etc.); haloalkylnorbornene such as 5,6-di (trifluoromethyl) -2-norbornene; oxonorbornene such as 7-oxo-2-norbornene), etc.], norbornadienes [eg, , Norbornadiene (for example, 2,5-norbornadiene), alkylnorbornadiene (for example, 5-methyl-2,5-norbornadiene, 5,6-dimethyl-2,5-norbornadiene, etc.) Arylnorbornadiene (such as 5-phenyl-2,5-norbornadiene), norbornadiene having a polar group (for example, cyanonorbornadiene such as 5-cyano-2,5-norbornadiene; 5-methoxycarbonyl-2,5-norbornadiene, etc. Acyloxynorbornadiene (such as alkoxycarbonylnorbornadiene); haloalkylnorbornadiene such as 5,6-di (trifluoromethyl) -2,5-norbornadiene; oxonorbornadiene such as 7-oxo-2-norbornadiene)], tricyclic olefin { For example, tricycloalkenes [eg, C _6-25 tricycloalkenes such as dihydrodicyclopentadienes (such as dihydrodicyclopentadiene)], tricycloalkadienes [eg, Dicyclopentadiene (dicyclopentadiene, methyldicyclopentadiene, etc.), tricyclo [4.4.0.1 ^2,5 ] undeca-3,7-diene, tricyclo [4.4.0.1 ^2,5 ] C _6-25 tricycloalkadiene, such as undeca-3,8-diene, etc.]}, polycyclic olefins having four or more rings {eg, tetracyclic olefins [eg, tetracycloalkenes (eg, tetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-dimethyltetracyclo [4.4.0.1 ^2,5 . _C7-30 tetracycloalkene such as 1 ^{7, 10} ] -3-dodecene)], pentacyclic olefin [eg C _10-35 pentacycloalkadiene such as pentacycloalkadiene (eg tricyclopentadiene) ), etc.], six cyclic olefins [e.g., hexa cycloalkenes (e.g., hexacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- heptadecene _C such as _12-40 Hexacycloalkene) and the like} and the like.

  The cyclic olefin resin may be a cyclic olefin homopolymer or a copolymer (for example, a copolymer of a monocyclic olefin and a polycyclic olefin, a copolymer of a plurality of polycyclic olefins, etc.), or cyclic. A copolymer of an olefin and a copolymerizable monomer may be used.

Examples of the copolymerizable monomer include a chain olefin [alkene (for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 2-methyl-1-pentene). 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1 -Hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, _C2-20 alkene such as 1-eicocene), alkadienes (for example, , 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-nonconjugated _{C 5-20} a such octadiene Cadien etc.), polymerizable nitrile compounds (eg (meth) acrylonitrile etc.), (meth) acrylic monomers (eg (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate) Esters, (meth) acrylic acid and the like), unsaturated dicarboxylic acids or derivatives thereof (maleic anhydride and the like), and the like. The copolymerizable monomers may be used alone or in combination of two or more.

  In the copolymer of cyclic olefin and copolymerizable monomer, the ratio of cyclic olefin is, for example, 10 mol% or more (for example, 20 mol) with respect to the total amount of cyclic olefin and copolymerizable monomer. % Or more), preferably 30 mol% or more, more preferably 40 mol% or more.

Preferred cyclic olefin resins, cyclic olefin copolymer [e.g., cyclic olefins (e.g., including at least cyclic olefin norbornenes) and a copolymerizable monomer (e.g., linear olefins (e.g., such as ethylene C _{2- A} copolymer with a copolymerizable monomer containing at least ₆ alkene)).

In particular, among cyclic olefin copolymers, a cyclic olefin copolymer having a polar group, for example, a cyclic olefin having a polar group {for example, norbornene having a polar group [for example, acyloxynorbornene (for example, 5-methoxycarbonyl-2 An alkoxycarbonyl group such as norbornene and 5-methyl-5-methoxycarbonyl-2-norbornene (for example, norbornene substituted with a C _1-10 alkoxycarbonyl group, preferably a C _1-4 alkoxycarbonyl group), etc.] } And a copolymer of a cyclic olefin and a copolymerizable monomer [for example, a copolymerizable monomer including at least a chain olefin (for example, a C _2-6 alkene such as ethylene)] is preferable. .

  In the cyclic olefin copolymer having a polar group, the ratio of the cyclic olefin having a polar group to the whole cyclic olefin is, for example, 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more. May be.

  Cyclic olefin resins may be used alone or in combination of two or more.

  The molecular weight of the cyclic olefin resin can be selected according to the type of the resin. For example, the number average molecular weight can be selected from a range of 2000 or more (for example, 3000 or more), 5000 or more (for example, 8000 to 1000000), preferably May be 10,000 or more (for example, 12,000 to 800,000), more preferably 15,000 or more (for example, 20,000 to 500,000). The molecular weight can be measured using a conventional method such as gel permeation chromatography (GPC), and may be evaluated as a molecular weight in terms of polystyrene.

(Fluorene compound)
The fluorene compound only needs to have a 9,9-bisarylfluorene skeleton, and has no reactive group [for example, 9,9-bisarylfluorene (for example, 9,9-bisphenylfluorene). A compound in which p is 0 in formula (1) described later] may be used, but usually has a reactive group.

  Examples of the reactive group include a hydroxyl group, mercapto group, carboxyl group, amino group, (meth) acryloyloxy group, epoxy group (for example, glycidyloxy group) and the like. The fluorene compound may have these reactive groups singly or in combination of two or more.

  The reactive group may be directly bonded to 9,9-bisarylfluorene, or may be bonded via an appropriate linking group (for example, a (poly) oxyalkylene group).

  Specific examples of the fluorene compound include a compound represented by the following formula (1).

[Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is a group — [(OR ³ ) nY] (wherein Y is a hydroxyl group, a mercapto group, glycidyl An oxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is an integer of 0 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is 1 or more. Indicates an integer. ]

In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon (for example, indene, naphthalene, etc. C _8-20 condensed bicyclic hydrocarbons, preferably C _10-16 condensed bicyclic hydrocarbons), condensed tricyclic hydrocarbons (eg, anthracene, phenanthrene, etc.), etc. ], A ring assembly hydrocarbon ring (bi or tel C _6-10 arene ring such as biphenyl ring, terphenyl ring, binaphthyl ring). The two rings Z may be the same or different rings, and may usually be the same ring. Preferred rings Z include a benzene ring, a naphthalene ring, and a biphenyl ring, and may be a benzene ring.

In the formula (1), examples of the group R ¹ include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [eg, an alkyl group, an aryl group (C ₆ such as a phenyl group). _-10 aryl group) and the like] and acyl groups (for example, alkylcarbonyl groups such as methylcarbonyl, ethylcarbonyl, pentylcarbonyl, etc.) and the like, and in particular, alkyl groups are often used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, such as _{C 1-12} alkyl group _{(e.g., C 1-8} alkyl groups, especially methyl groups, such as t- butyl group _{C 1- 4} alkyl group) and the like. In addition, when k is plural (2 to 4), the types of the plural groups R ¹ may be the same or different from each other. The types of the groups R ¹ substituted on different benzene rings may be the same or different from each other. Further, the bonding position (substitution position) of the group R ¹ is not particularly limited, and examples thereof include the 2nd, 7th, 2nd and 7th positions of the fluorene ring. The preferred substitution number k is 0 to 1, in particular 0. The two substitution numbers k may be the same or different.

The substituent R ² substituted on the ring Z is usually a non-reactive substituent, for example, an alkyl group (eg, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, C _1-8 alkyl group etc.), cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group), aryl group (eg, phenyl group, tolyl group, xylyl group, naphthyl group etc.) _6-10 an aryl group), a hydrocarbon group such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group); an alkoxy group (methoxy group, _{C 1} such as ethoxy groups _-8 an alkoxy group), such as C _5-10 cycloalkyl group such as a cycloalkoxy group (hexyloxy group cyclohexylene), an aryloxy group (Fe _{C 6-10} aryloxy groups such as alkoxy groups), the radical -OR [expression such aralkyloxy groups _{(C 6-10} aryl _{-C 1-4} alkyl group such as a benzyl group), R is a hydrocarbon radical (Such as the hydrocarbon groups exemplified above). A group such as an alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group) —SR (wherein R is as defined above); an acyl group (such as a C _1-6 acyl group such as an acetyl group); Alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group; substituted amino group (for example, dimethyl) And a dialkylamino group such as an amino group).

Preferred group R ² includes a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _6-10 Aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group and the like), alkoxy group (C _1-4 alkoxy group and the like) and the like. Further preferred groups R ² include an alkyl group [C _1-4 alkyl group (particularly methyl group) and the like], an aryl group [eg C _6-10 aryl group (particularly phenyl group) and the like] and the like. Incidentally, when the group R ² is an aryl group, a group R ^2, together with the ring Z, it may form the ring assembly hydrocarbon ring.

In the same ring Z, when m is plural (two or more), the types of the groups R ² may be the same or different from each other. In the two rings Z, the types of the groups R ² may be the same or different from each other. The number of substitutions m can be selected according to the type of ring Z, and may be, for example, 0 to 8, preferably 0 to 4 (for example, 0 to 3), and more preferably 0 to 2. In different rings Z, the number of substitutions m may be the same or different from each other, and may usually be the same.

In the group X of the formula (1), examples of the alkylene group represented by the group R ³ include C _2-6 alkylene such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group. Group, preferably a _C2-4 alkylene group, more preferably a _C2-3 alkylene group. When n is 2 or more, the type of alkylene group may be composed of different alkylene groups, and may be generally composed of the same alkylene group. In the two aromatic hydrocarbon rings Z, the type of the group R ³ may be the same or different.

The number (additional number of moles) n of the oxyalkylene groups (OR ³⁾ may be any of 0 or more (e.g., 0-20), for example, 0 to 15 (e.g., 1-12), preferably 0-10 ( For example, 1 to 6), more preferably 0 to 4 (for example, 1 to 4), particularly 0 to 2 (for example, 0 to 1) may be used. Further, depending on the type of resin, there may be a case where a remarkable improvement effect is obtained when n is 0 or when n is 1 or more. Therefore, either a compound in which n is 0 or a compound in which n is 1 or more may be selected depending on the type of resin. The number of substitutions n may be the same or different for different rings Z.

Preferred X is a group-[(OR ³ ) nY], and particularly Y is preferably a hydroxyl group. In addition, in Formula (1), the compound whose Y is a hydroxyl group is represented by following formula (1A).

(In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1).)
The substitution number p of the group X may be 1 or more (for example, 1 to 6), and may be, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1. In addition, the substitution number p may be the same or different in each ring Z, and is usually the same in many cases.

  In the formula (1) [or (1A)], the substitution position of the group X is not particularly limited as long as it is substituted at an appropriate substitution position of the ring Z. For example, when the ring Z is a benzene ring, the group X may be substituted at the 2- to 6-position of the phenyl group, and preferably at the 4-position. In addition, when the ring Z is a condensed polycyclic hydrocarbon ring, the group X is a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of fluorene in the condensed polycyclic hydrocarbon ring (for example, naphthalene In many cases, the ring is substituted at least on the 5-position, 6-position, etc.

Specific fluorene compounds (or the compounds represented by the formula (1) or (1A)) include 9,9-bis (hydroxyaryl) fluorenes [or 9,9-bis (hydroxyaryl) fluorene skeletons. Compounds having, for example, 9,9-bis (hydroxyphenyl) fluorenes, 9,9-bis (hydroxynaphthyl) fluorenes], 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes [or 9,9 -Compounds having a bis (hydroxy (poly) alkoxyaryl) fluorene skeleton, such as 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes] X is a group in the formula (1), such as ^{- [(OR 3) n-} OH] , compound; this In al compounds, hydroxyl group, mercapto group, and the like glycidyloxy group or a (meth) acrylate compound substituted acryloyloxy group.

The 9,9-bis (hydroxyphenyl) fluorenes include, for example, 9,9-bis (hydroxyphenyl) fluorene [for example, 9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (alkyl -Hydroxyphenyl) fluorene [e.g., 9,9-bis such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene (Mono- or di-C _1-4 alkyl-hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, etc. , 9-bis (mono- or _{di-C 6-10} aryl - hydroxyphenyl) fluorene], 9,9-bis ( Rehydroxyphenyl) fluorene [for example, 9,9-bis (di- or trihydroxyphenyl) such as 9,9-bis (3,4-dihydroxyphenyl) fluorene, 9,9-bis (2,4-dihydroxyphenyl) fluorene ) Fluorene].

  In addition, as 9,9-bis (hydroxynaphthyl) fluorenes, compounds corresponding to the 9,9-bis (hydroxyphenyl) fluorenes in which a phenyl group is substituted with a naphthyl group, for example, 9,9-bis ( Hydroxynaphthyl) fluorene [eg, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9-bis (5-hydroxy-1-naphthyl) fluorene] and the like.

9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes include, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) phenyl] 9,9-bis (hydroxyC _2-4 alkoxyphenyl) fluorene} such as fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene}, 9,9-bis (alkyl-hydroxyalkoxyphenyl) Fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 9, Such as 9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene 9,9-bis (mono or di C _1-4 alkyl-hydroxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- 9,9-bis (mono or di C _6-10 ) such as (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-phenylphenyl] fluorene 9,9-bis (hydroxyalkoxyphenyl) fluorenes such as aryl- _{hydroxyC 2-4} alkoxyphenyl) fluorene} (a compound in which n is 1 in the formula (1)); 9,9-bis (hydroxydi) Alkoxyphenyl) fluorene {eg, 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] phenyl Eniru} 9,9-bis (hydroxy polyalkoxy phenyl) fluorene such as 9,9-bis fluorene _{(hydroxy-di-C 2-4} alkoxyphenyl) fluorene} (In Formula (1), with n is 2 or more A certain compound) and the like.

Further, as 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes, compounds corresponding to the 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, wherein a phenyl group is substituted with a naphthyl group, For example, 9,9-bis (hydroxyalkoxynaphthyl) fluorene {eg, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2-hydroxypropoxy) ), and the like-2-naphthyl] fluorene such as 9,9-bis (hydroxy _{C 2-4} alkoxy naphthyl) fluorene} etc. 9,9-bis (hydroxyalkoxy naphthyl) fluorenes.

Among these fluorene compounds, in particular, 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene [for example, 9,9-bis (mono or diC _1-4 alkyl- Hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [e.g., 9,9-bis (mono or di _C6-10 aryl-hydroxyphenyl) fluorene], 9,9-bis (di or A compound in which n is 0 in the formula (1A) such as trihydroxyphenyl) fluorene and 9,9-bis (hydroxynaphthyl) fluorene; 9,9-bis (hydroxyalkoxyphenyl) fluorene {for example, 9,9-bis (hydroxy _{C 2-4} alkoxyphenyl) fluorene}, 9,9-bis (alkyl - hydroxy alkoxyphenyl) fluorene {e.g., 9,9-bis (mono- or _{di-C 1-4} alkyl - hydroxy _{C 2-4} alkoxyphenyl) fluorene}, 9,9-bis (aryl - hydroxyalkoxy phenyl) fluorene {e.g. 9,9-bis (mono or di C _6-10 aryl-hydroxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (hydroxyalkoxynaphthyl) fluorene {eg, 9,9-bis (hydroxy C _{2 In the} formula (1A) such as -4alkoxynaphthyl) fluorene}, a compound in which n is 1 or more (for example, 1 to 4, preferably 1 to 2, more preferably 1) is preferable.

  The fluorene compound not only improves the mechanical properties (tensile strength, bending strength, storage elastic modulus E ′) of the cyclic olefin resin, but also improves the optical properties. For example, the fluorene compound reduces the birefringence of the cyclic olefin resin and the Abbe number. Therefore, the fluorene compound can also be referred to as a mechanical property improver or an optical property improver (for example, a birefringence reducing agent, Abbe number adjusting agent (or Abbe number reducing agent)).

  Fluorene compounds may be used alone or in combination of two or more. The fluorene compound may be a commercially available product or may be synthesized by a conventional method.

  The ratio of the fluorene compound can be selected, for example, from a range of about 0.01 parts by weight or more, for example, about 0.1 parts by weight or more (eg, 0.2 to 200 parts by weight) with respect to 100 parts by weight of the cyclic olefin resin. 0.3 to 100 parts by weight, preferably 0.5 to 80 parts by weight, more preferably about 1 to 50 parts by weight, and usually 0.5 to 50 parts by weight (for example, 0.5 to 40 parts by weight). Parts by weight, preferably 0.7 to 30 parts by weight, and more preferably 1 to 20 parts by weight.

  In the present invention, since various properties can be improved or improved efficiently even in a small amount, for example, the proportion of the fluorene compound is 20 parts by weight or less (for example, 0.1 to 18 parts by weight) with respect to 100 parts by weight of the cyclic olefin resin. , Preferably 15 parts by weight or less (for example, 0.2 to 12 parts by weight), more preferably 10 parts by weight or less (for example, 0.3 to 7 parts by weight), particularly 5 parts by weight or less (for example, 0.5 to 5 parts by weight).

  In addition, the fluorene compound is excellent in affinity for the cyclic olefin resin, and can often maintain or improve the resin characteristics at a high level even when added in a relatively large proportion. Therefore, the proportion of the fluorene compound is 20 parts by weight or more (for example, 20 to 100 parts by weight), preferably 25 parts by weight or more (for example, 25 to 80 parts by weight), more preferably 100 parts by weight of the cyclic olefin resin. May be 30 parts by weight or more (for example, 30 to 70 parts by weight).

  The resin composition may contain other resins (resins that are not cyclic olefin resins) as long as the effects of the present invention are not impaired. Examples of such other resins include chain olefin resins [ethylene resins (eg, polyethylene), propylene resins (eg, polypropylene), polymethylpentene, etc.), halogen-containing vinyl resins (polyvinyl chloride, Fluorinated resin, etc.), acrylic resin, styrene resin, polycarbonate resin (eg, aromatic polycarbonate resin), polythiocarbonate resin, polyester resin [eg, aliphatic polyester resin (eg, polylactic acid), aromatic polyester resin ( For example, polyalkylene arylate resins such as polyethylene terephthalate and polyethylene naphthalate)], polyacetal resins, polyamide resins (for example, polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyester, Aliphatic polyamide resins such as amide 612 and polyamide 6/66; aromatic polyamide resins such as polyamide MXD), polyphenylene ether resins, polysulfone resins, polyphenylene sulfide resins, polyimide resins, polyether ketone resins, thermoplastic elastomers, etc. Resin etc. are mentioned. The resins may be used alone or in combination of two or more.

  The ratio of the other resin is, for example, 1 to 1000 parts by weight, preferably 3 to 500 parts by weight (for example, 4 to 300 parts by weight), more preferably 5 to 100 parts with respect to 100 parts by weight of the cyclic olefin resin. The amount may be about 1 part by weight, and usually about 1 to 100 parts by weight (for example, 2 to 80 parts by weight, preferably 3 to 50 parts by weight).

  Further, the resin composition may contain various additives [for example, fillers or reinforcing agents, colorants (dye pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet rays). Absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents, carbon materials, etc.] Good. These additives may be used alone or in combination of two or more.

  In addition, a resin composition can be obtained by mixing a cyclic olefin resin, a fluorene compound, and [and other components (additives etc. as needed)]. 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.

[Molded body]
The molded body formed with the said resin composition is also contained in this invention. The shape of the molded body is not particularly limited and can be appropriately selected depending on the application. For example, a two-dimensional structure (film shape, sheet shape, plate shape, etc.), a three-dimensional structure (tubular, rod-shaped, tubular shape, hollow) Etc.).

  In particular, the resin composition of the present invention is often excellent in various optical properties, has high transparency, and has a high refractive index, low birefringence and / or low Abbe number, or an optical material or optical molded body ( In particular, an optical film, an optical lens, etc.) may be suitably formed.

  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.

  In particular, the resin composition of the present invention is often excellent in optical properties, and is useful for forming a film (particularly an optical film). Therefore, the present invention also includes a film (such as an optical film) formed from the resin composition. A film (such as an optical film) can be produced by forming (or molding) the resin composition using a conventional film forming method, casting method (solvent casting method), melt extrusion method, calendar method, or the like.

  The thickness of the film can be selected from the range of about 1 to 1000 μm depending on the application, and may be, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably about 10 to 120 μm.

  The film may be a stretched film (uniaxially stretched film or biaxially stretched film). The stretching ratio may be about 1.05 to 10 times (for example, 1.1 to 5 times) in each direction in uniaxial stretching or biaxial stretching, and is usually 1.1 to 3 times (for example, 1. 2 to 2.5 times). In the case of biaxial stretching, it may be equal stretching or partial stretching. In the case of uniaxial stretching, longitudinal stretching or lateral stretching may be used. The stretching method is not particularly limited. In the case of uniaxial stretching, a wet stretching method or a dry stretching method may be used. In the case of biaxial stretching, a tenter method (also referred to as a flat method), a tube method, or the like may be used. Good.

  The stretched film may have a thickness of, for example, 1 to 150 μm, preferably 3 to 120 μm, and more preferably about 5 to 100 μm.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples, various characteristics were measured as follows.

(Tensile strength)
A sample (thickness 0.2 mm, width 5 mm, length 50 mm) is prepared from the stretched film, and a tensile tester (Tensilon RTC-1250 (A & D)) is used in this sample, and the distance between chucks is set to 20 mm. The strength until the sample was cut at a tensile speed of 2 mm / min was measured.

(Dynamic viscoelasticity)
A sample (thickness 0.2 mm, width 1-2 mm, length 50 mm) was prepared from the stretched film, and a dynamic viscoelasticity tester (Rheogel E4000 (UBM)) was used for this sample, and the uniaxial tension mode was used. The storage elastic modulus (E ′) at room temperature (25 ° C.) was measured at (100 Hz).

(Birefringence)
With respect to the stretched film, birefringence (Δn / λ) increased per unit magnification at the time of stretching was measured at a wavelength of 546 nm by using a polarizing microscope (manufactured by NIKON, OPTIPHOT-POL) by offsetting the polarization with a compensator. .

(Refractive index and Abbe number)
About the unstretched film (thickness 2 mm), the refractive index was measured at a wavelength of 589 nm using an Abbe refractometer (manufactured by Atago Co., Ltd.). Moreover, the Abbe number was calculated based on the refractive index measured with C line (656 nm), D line (589 nm), and F line (486 nm).

Example 1
After melting a cyclic olefin copolymer (manufactured by JSR Corporation, Arton 4531F) with Laboplastmill, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene (biscresol fluorene, Osaka Gas Chemical Co., Ltd.) (Hereinafter referred to as “BCF”) at 250 ° C. (0 wt%, 1 wt%) or 240 ° C. (5 wt%, 10 wt%) so that the ratio shown in Table 1 is obtained. Obtained. In addition, the resin composition was transparent and mixed uniformly in any ratio.

  The obtained resin composition was dried at 120 ° C. and then hot-pressed at 220 ° C. (0 weight, 1 part by weight) or 230 ° C. (5% by weight, 10% by weight) to prepare a sheet. Further, the obtained sheet was heat-treated at 150 ° C., and then thermally stretched in a silicone oil bath at a stretching temperature of 180 ° C. and a stretching ratio of 1.2 times to obtain a stretched film.

  Various characteristics were measured using the obtained stretched film.

  The results are shown in Table 1. In Table 1, for comparison, the result of the BCF ratio of 0% by weight is also shown.

  As is clear from the results in Table 1, it was found that adding BCF to the cyclic olefin copolymer improves the mechanical strength. By adding BCF to the cyclic olefin resin, birefringence is reduced. Declined.

(Example 2)
Example 1 except that 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEF) was used instead of BCF in Example 1. Measured in the same manner as above. The mixing temperature was 250 ° C., and the hot press temperature was 220 ° C. (0 weight, 1 part by weight) or 230 ° C. (5% by weight, 10% by weight, 30% by weight).

  The results are shown in Table 2.

  As is apparent from the results in Table 2, even when BPEF was added to the cyclic olefin copolymer, the mechanical strength was improved and the birefringence was also reduced.

(Example 3)
The resin was a cyclic olefin copolymer (manufactured by Mitsui Chemicals, Apel APL5014DP), BCF was kneaded at the blending ratio shown in Table 3, and the refractive index was measured. The mixing temperature was 250 ° C. and the hot press temperature was 250 ° C. The results are shown in Table 3.

  As is apparent from Table 3, the Abbe number can be reduced by adding a fluorene compound.

  The resin composition of the present invention is composed of a cyclic olefin resin. In addition to the properties of the cyclic olefin resin itself, the resin composition has excellent properties such as high refractive index, high strength, low birefringence, low Abbe number, and high transparency. It has the characteristics. Such a resin composition can be suitably used particularly for an optical lens, an optical film, an optical sheet, a pickup lens, a hologram, a liquid crystal film, an organic EL film, and the like. In addition, the resin composition of the present invention includes paints, antistatic agents, inks, adhesives, pressure-sensitive adhesives, resin fillers, charging trays, conductive sheets, protective films (protective films such as electronic devices and liquid crystal members), electric Electronic materials (carrier transport agents, light emitters, organic photoreceptors, thermal recording materials, hologram recording materials), electrical / electronic components or equipment (optical discs, inkjet printers, digital paper, organic semiconductor lasers, dye-sensitized solar cells, It can be suitably used for resins for EMI shield films, photochromic materials, organic EL elements, color filters, etc.), resins for mechanical parts or equipment (automobiles, aerospace materials, sensors, sliding members, etc.), and the like.

  In particular, since the resin composition of the present invention is excellent in optical properties, it is useful for constituting (or forming) a molded article for optical use (optical molded article). Examples of the optical molded body formed (configured) with such a resin composition include an optical film and an optical lens. The resin composition can form a molded product having a low Abbe number (for example, a lens), and the molded product having a low Abbe number can be combined with a molded product having a high Abbe number (for example, a lens) to disperse light. An optical component with small distortion, extremely small aberration, improved resolution, and no color blur can be formed.

  As an optical film, a polarizing film (and a polarizing element and a polarizing plate protective film constituting it), a retardation film, an alignment film (alignment film), a viewing angle expansion (compensation) film, a diffusion plate (film), a prism sheet, Light guide plate, brightness enhancement film, near infrared absorption film, reflection film, antireflection (AR) film, reflection reduction (LR) film, antiglare (AG) film, transparent conductive (ITO) film, anisotropic conductive film (ACF) ), Electromagnetic wave shielding (EMI) film, film for electrode substrate, film for color filter substrate, barrier film, color filter layer, black matrix layer, adhesive layer or release layer between optical films. In particular, the film of the present invention is useful as an optical film for use in an apparatus display. Specific examples of the display member (or display) including the optical film of the present invention include FPD devices such as personal computer monitors, televisions, mobile phones, car navigation systems, and touch panels (for example, , LCD, PDP, etc.).

Claims (9)

A resin composition comprising a cyclic olefin copolymer having a polar group and a compound having a 9,9-bisarylfluorene skeleton, wherein the ratio of the compound having the 9,9-bisarylfluorene skeleton is the cyclic The resin composition which is 0.1-20 weight part with respect to 100 weight part of olefin copolymers . The resin composition according to claim 1, wherein the compound having a 9,9-bisarylfluorene skeleton is a compound represented by the following formula (1).

[Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is a group — [(OR ³ ) nY] (wherein Y is a hydroxyl group, a mercapto group, glycidyl An oxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is an integer of 0 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is 1 or more. Indicates an integer. ] The resin composition according to claim 1 or 2, wherein the compound having a 9,9-bisarylfluorene skeleton is a compound represented by the following formula (1A).

(In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1).) Ring Z is a benzene ring or naphthalene ring, R ¹ is an alkyl group, k is 0 to 1, R ² is an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group, m is 0 to 2, and R ³ is C The resin composition according to claim 2 or 3, wherein a _2-4 alkylene group, n is 0 to 2, and p is 1 to 3.   Compounds having a 9,9-bisarylfluorene skeleton include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene, 9,9-bis (di- or trihydroxyphenyl) fluorene, 9,9-bis (hydroxynaphthyl) fluorene, 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyalkoxyphenyl) fluorene The resin composition according to claim 1, wherein the resin composition is at least one selected from 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene and 9,9-bis (hydroxyalkoxynaphthyl) fluorene. . The molded object formed with the resin composition in any one of Claims 1-5 . The molded article according to claim 6, which is an optical molded article. The molded article according to claim 6 or 7, which is an optical film. Molded body according to any one of a stretched film according to claim 6-8.