WO2014168108A1 - Resin composition containing fluorine compound, molded body, wavelength dispersion adjustment agent, and method for adjusting wavelength dispersion of resin - Google Patents

Abstract

The present invention prepares a resin composition that can add a compound having a fluorine skeleton without losing mechanical properties by means of adding, to a non-epoxy resin, an epoxy compound and a non-epoxy compound having a 9,9-bisarylfluorine skeleton represented by formula (1). [In the formula: ring Z indicates an aromatic hydrocarbon ring; R¹ and R² indicate a substituent group; X indicates the group -[(OR³)n-Y] (in the formula: Y indicates a hydroxyl group, a mercapto group, or a (meth)acryloyloxy group; R³ indicates an alkylene group; and n indicates an integer that is at least 0) or an amino group; k indicates an integer from 0 to 4; m indicates an integer that is at least 0; and p indicates an integer that is at least 1.]

Description

Resin composition and molded product containing fluorene compound, wavelength dispersion adjusting agent and resin wavelength dispersion adjusting method

The present invention relates to a resin composition containing a compound having a fluorene skeleton (9,9-bisarylfluorene skeleton), a molded product thereof, a wavelength dispersion adjusting agent, and a resin wavelength dispersion adjusting method.

A compound having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) is known to have excellent functions such as a high refractive index and high heat resistance. As a method for expressing the excellent function of such a fluorene skeleton in a resin and making it moldable, fluorene compounds having a reactive group (hydroxyl group, amino group, etc.), such as 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, Japanese Unexamined Patent Application Publication No. 2002-284864 (Patent Document 1) discloses a molding material composed of a polyester resin having a 9,9-bisphenylfluorene skeleton. Japanese Patent Laid-Open No. 2002-284834 (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 or 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (bisphenoxyethanol) is used as a 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.

Also, attempts are being made to add the fluorene compound directly to the resin without polymerizing it. For example, JP-A-2005-162785 (Patent Document 3) discloses a resin composition comprising 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 a polycarbonate resin. And that the refractive index has increased.

JP 2011-8017 A (Patent Document 4) discloses an optical resin composition composed of a transparent resin and a fluorene compound having a 9,9-bisarylfluorene skeleton. And this document describes that the birefringence can be reduced without impairing the mechanical properties and heat resistance of the transparent resin, and in a specific example, the fluorene-containing polyester resin is compared with 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.

Japanese Patent Laid-Open No. 2011-21083 (Patent Document 5) 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. Are listed. In the examples of this document, 1 to 5% by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene was added to the α-crystal (melting point: 168 ° C.) poly-L lactic acid and melted. Kneading 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 2012-211252 A (Patent Document 6) discloses a film containing a cellulose derivative (such as cellulose triacetate) and a fluorene compound having a 9,9-bisarylfluorene skeleton (such as bisphenoxyethanol fluorene). ing. And in the Example of this document, it is described that the retardation value of the stretched film containing cellulose triacetate and bisphenoxyethanol fluorene was 0 or a negative value.

JP 2002-284864 A (Claims, Examples) JP 2002-284834 A (Claims, Examples) Japanese Patent Laying-Open No. 2005-162785 (Claims and Examples) JP 2011-8017 A (Claims, Examples) Japanese Patent Laying-Open No. 2011-21083 (Claims and Examples) JP 2012-211252 A (Claims, Examples)

An object of the present invention is to provide a novel resin composition containing a compound (non-epoxy compound) having a fluorene skeleton (9,9-bisarylfluorene skeleton), a molded article formed with this resin composition, and a wavelength dispersion regulator. Another object of the present invention is to provide a resin wavelength dispersion adjusting method.

Another object of the present invention is to provide a resin composition to which a compound having a fluorene skeleton can be added without impairing mechanical strength, a molded article formed with this resin composition, a wavelength dispersion adjusting agent, and a resin wavelength dispersion adjusting method. Is to provide.

Still another object of the present invention is to provide a resin composition capable of adjusting or controlling wavelength dispersibility, a molded article formed from the resin composition, a wavelength dispersion adjusting agent, and a resin wavelength dispersion adjusting method.

As described above, although several techniques for adding a compound having a fluorene skeleton to a resin have been reported, by adding to a specific resin, the refractive index is improved, the birefringence is reduced, the crystal structure is improved. The change from α-crystal to β-crystal and plasticizer effect are only seen, and the current situation is that the development has not been made yet.

On the other hand, the present inventors surprisingly have a compound in which a compound having a fluorene skeleton has a reverse wavelength dispersibility (or negative wavelength dispersibility, a phase difference (or birefringence) that increases as the wavelength increases) with respect to the resin. ) Can be imparted (or expressed).

Under such circumstances, the present inventors have intensively studied to solve the above problems, and as a result, non-epoxy compounds having a 9,9-bisarylfluorene skeleton and epoxy compounds with respect to resins (especially thermoplastic resins). When added in combination, it is possible to suppress a decrease in mechanical properties due to the addition of a non-epoxy compound having a 9,9-bisarylfluorene skeleton, which is a low molecular weight compound, and to adjust (or control) the wavelength dispersion of the resin. ) [For example, the wavelength dispersion of the resin can be reduced (or adjusted to low wavelength dispersion)], and the present invention has been completed.

That is, the resin composition of the present invention includes a non-epoxy resin, a non-epoxy compound having a 9,9-bisarylfluorene skeleton, and an epoxy compound.

The non-epoxy 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, 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 an integer of 1 or more] .

In particular, the non-epoxy 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 It 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 May be 2 and p may be 1 to 3.

Non-epoxy compounds having a 9,9-bisarylfluorene skeleton typically include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, and 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 It may be at least one selected from (alkyl-hydroxyalkoxyphenyl) fluorene, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene, and 9,9-bis (hydroxyalkoxynaphthyl) fluorene.

The non-epoxy resin may be a thermoplastic resin, and in particular, may be at least one selected from a cyclic olefin resin, a methacrylic resin, an aromatic polycarbonate resin, an aromatic polyester resin, and a cellulose derivative.

The epoxy compound may particularly contain at least a polyfunctional epoxy compound.

In the resin composition of the present invention, the ratio of each component to 100 parts by weight of the non-epoxy resin is, for example, that the ratio of the non-epoxy compound having a 9,9-bisarylfluorene skeleton is about 0.5 to 50 parts by weight. The ratio of the epoxy compound may be about 0.1 to 30 parts by weight.

In the resin composition of the present invention, the proportion of the epoxy compound may be, for example, about 1 to 100 parts by weight with respect to 100 parts by weight of the non-epoxy compound having a 9,9-bisarylfluorene skeleton. .

The present invention also includes a molded body formed from the resin composition. Such a molded article may be an optical molded article [such as an optical film (such as a retardation film)]. 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 invention, the wavelength dispersion of the non-epoxy resin is adjusted or controlled by adding a non-epoxy compound having a 9,9-bisarylfluorene skeleton to the non-epoxy resin in combination with the epoxy compound ( For example, the wavelength dispersion can be reduced).

Therefore, the present invention relates to an additive for adjusting or controlling (for example, reducing) the wavelength dispersion of a non-epoxy resin, and a non-epoxy compound having an 9,9-bisarylfluorene skeleton and an epoxy compound Are also included (for example, a wavelength dispersion reducing agent). Further, in the present invention, such a wavelength dispersion adjusting agent (for example, a wavelength dispersion reducing agent) is added to the non-epoxy resin to adjust or control (for example, reduce) the wavelength dispersion of the non-epoxy resin. Also included is a method of adjusting the wavelength dispersion of the resin. In addition, in such a regulator and method, the ratio of each component and the use ratio with respect to resin are the same as in the resin composition.

The wavelength range for adjusting the dispersibility is not particularly limited. For example, the visible light range is about 300 to 800 nm (for example, 350 to 770 nm), preferably about 400 to 750 nm (for example, 400 to 700 nm). Also good.

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. Further, 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 compound (non-epoxy compound) having a fluorene skeleton (9,9-bisarylfluorene skeleton). Such a resin composition has resin characteristics according to the type of resin (non-epoxy resin), and also conventionally known effects obtained by adding a compound having a fluorene skeleton (improvement of refractive index, reduction of birefringence) , Improvement of stretchability, etc.) can be obtained. Surprisingly, such a resin composition contains a compound having a fluorene skeleton which is a low molecule, but does not impair the mechanical properties, in particular, a compound having only a fluorene skeleton. Compared with the case of containing, the mechanical properties can be further improved or improved, so that it is very useful.

In addition, as described above, the compound having a fluorene skeleton seems to be able to impart reverse wavelength dispersion to the resin. By combining such a compound having a fluorene skeleton and an epoxy compound, the wavelength dispersion is adjusted or Can be controlled. For example, the addition of a compound having a fluorene skeleton imparts reverse wavelength dispersibility to the resin, but when combined with an epoxy compound, the wavelength dispersibility becomes uniform, or a low wavelength dispersible resin (composition Product) can be easily obtained.

The resin composition of the present invention comprises a non-epoxy resin (hereinafter sometimes referred to simply as a resin) and a non-epoxy compound having a 9,9-bisarylfluorene skeleton (hereinafter sometimes referred to as a fluorene compound). And an epoxy compound.

[resin]
As the resin, a wide range of resins can be used (or applied), and any of a thermoplastic resin and a curable resin (thermal or photo-curable resin) may be used.

Examples of the thermoplastic resin include olefin resin {eg, chain olefin resin [ethylene resin (eg, polyethylene), propylene resin (eg, polypropylene), polymethylpentene, etc.], cyclic olefin resin, etc.}, halogen-containing resin) Vinyl resins (polyvinyl chloride, fluororesins, etc.), vinyl resins (eg, polyvinyl alcohol, acrylonitrile resins), acrylic resins (eg, methacrylic resins such as polymethyl methacrylate), styrene resins [eg, styrene Monomers or copolymers of polystyrene monomers (polystyrene, styrene-α-methylstyrene copolymer, etc.), copolymers of styrene monomers and copolymerizable monomers (styrene-acrylonitrile copolymers ( AS resin), styrene- (meth) acrylic acid ester copolymer Styrene-methyl methacrylate copolymer, etc.), styrene-maleic anhydride copolymer, etc.]], polycarbonate resin (eg, aromatic polycarbonate resin, etc.), polythiocarbonate resin, polyester resin [eg, aliphatic polyester resin, etc. (Polylactic acid, etc.), aromatic polyester resin, etc.], polyacetal resin, polyamide resin (for example, aliphatic polyamide resin such as polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 612, polyamide 6/66; Aromatic polyamide resins such as polyamide MXD), polyphenylene ether resins, polysulfone resins, polyphenylene sulfide resins, polyimide resins, polyether ketone resins, cellulose derivatives, and thermoplastic elastomers. And so on.

Resins may be used alone or in combination of two or more.

The molecular weight of the thermoplastic 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 in terms of polystyrene by a conventional method such as gel permeation chromatography (GPC).

Examples of the curable resin (thermal or photocurable resin, non-epoxy curable resin) include acrylic resin (thermal or photocurable acrylic resin), phenol resin, amino resin (urea resin, melamine resin, etc.). ), Furan resins, unsaturated polyester resins, thermosetting urethane resins, silicone resins, thermosetting polyimide resins, diallyl phthalate resins, vinyl ester resins, and the like. The curable resins may be used alone or in combination of two or more. The curable resin may contain a curing agent, a curing accelerator, or the like depending on the type.

Resins may be used alone or in combination of two or more.

The resin (thermoplastic resin or curable resin) may be either a crystalline resin or an amorphous resin.

In addition, the resin may be a resin having a positive wavelength dispersion or a resin having a negative wavelength dispersion (reverse wavelength dispersion).

The resin may typically be a thermoplastic resin. In particular, the resin may be a resin having excellent transparency, for example, a cyclic olefin resin, a methacrylic resin, an aromatic polycarbonate resin, an aromatic polyester resin, a cellulose derivative, or the like.

Hereinafter, these resins will be described in detail.

(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. In addition, the cyclic olefin includes a substituent such as a hydrocarbon group [eg, an alkyl group (eg, a C _1-10 alkyl group such as a methyl group, preferably a C _1-5 alkyl group), a cycloalkyl group (eg, cyclohexyl group). 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, cyclohexenyl group, etc.), alkylidene group (eg, 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 such as), 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 (eg, 5-phenyl-2-norbornene), norbornene having a polar group (eg, 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 [for example , 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 ] A C _6-25 tricycloalkadiene such as undeca-3,8-diene, etc.]}, a polycyclic olefin having four or more rings {eg, a tetracyclic olefin [eg, tetracycloalkene (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 . C _7-30 tetracycloalkene such as 1 ^7,10 ] -3-dodecene), etc.], pentacyclic olefin [eg C _10-35 pentacycloalkadiene such as tricyclopentadiene, etc. ), 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 (eg, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 2-methyl-1-pentene). 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1 C _2-20 alkenes such as -hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 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 include cyclic olefin copolymers {eg, cyclic olefins (eg, cyclic olefins containing at least norbornenes) and copolymerizable monomers [eg, chain olefins (eg, C ₂₋ 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 {eg, norbornene having a polar group [eg, acyloxynorbornene (eg, 5-methoxycarbonyl-2 An alkoxycarbonyl group such as norbornene or 5-methyl-5-methoxycarbonyl-2-norbornene (eg, norbornene substituted with a C _1-10 alkoxycarbonyl group, preferably a C _1-4 alkoxycarbonyl group), etc.] } And a copolymerizable monomer [for example, a copolymerizable monomer [for example, a copolymerizable monomer containing at least a chain olefin (eg, 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.

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

(Methacrylic resin)
Examples of the methacrylic resin (methacrylic resin or methacrylate resin) include resins having at least a methacrylic acid ester as a polymerization component. Usually, the methacrylic resin is an alkyl methacrylate [for example, an alkyl methacrylate ester (for example, a C _1-20 alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, Preferably, a resin having a polymerization component of C _1-12 alkyl methacrylate, more preferably C _1-6 alkyl methacrylate, particularly C _1-4 alkyl methacrylate) and the like. The alkyl methacrylates may be used alone or in combination of two or more.

Specific methacrylic resins include alkyl methacrylates (especially alkyl methacrylates containing at least methyl methacrylate) homopolymers or copolymers, alkyl methacrylates (particularly alkyl methacrylates containing at least methyl methacrylate) and copolymers. And a copolymer with a functional monomer.

The copolymerizable monomer is not particularly limited as long as it is copolymerizable. For example, a (meth) acrylic monomer {for example, (meth) acrylic acid, alkyl acrylate (for example, methyl acrylate, ethyl acrylate) C _1-10 alkyl acrylates such as propyl acrylate and butyl acrylate), alicyclic (meth) acrylates (eg, (meth) acrylic acid C _5-10 cycloalkyl esters such as cyclohexyl (meth) acrylate; Decalinyl (meth) acrylate, norbornyl (meth) acrylate, bornyl (meth) acrylate, bi to tetracycloalkyl (meth) acrylate such as adamantyl (meth) acrylate, etc.], hydroxyalkyl (meth) acrylate [for example, (meth) acrylic Acid hydroxyethyl etc. (Meth) acrylic acid hydroxyalkyl C _2-6 alkyl], 3 or more (meth) acrylate compound having an acryloyloxy group [for example, an alkane diol di (meth) acrylate (e.g., ethylene glycol di (meth) acrylate, diethylene glycol di ( (Meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc.), alkanetriol di to tri (meth) acrylate (for example, trimethylolethane tri (meth) acrylate, trimethylolpropane tri ( Meth) acrylates), polyols such as alkanetetraol di to tetra (meth) acrylates (pentaerythritol tetra (meth) acrylate etc.), poly (meth) acrylates, polyols Alkylene oxide (e.g., C _2-4 alkylene oxides such as ethylene oxide) and poly adducts (meth) acrylate, etc.]}, (meth) acrylonitrile, styrene monomers (styrene, etc.), vinyl ester monomers (Vinyl acetate etc.), unsaturated carboxylic acid or its anhydride (maleic anhydride, maleic acid, fumaric acid etc.) etc. can be illustrated. The copolymerizable monomers may be used alone or in combination of two or more.

Preferred methacrylic resins include resins having methyl methacrylate as a polymerization component, such as polymethyl methacrylate, copolymers having methyl methacrylate as a polymerization component [for example, copolymers of methyl methacrylate and alkyl methacrylate esters. (For example, methyl methacrylate-methacrylic acid C _2-8 alkyl ester copolymer) and the like]. In the copolymer containing methyl methacrylate as a polymerization component, the proportion of methyl methacrylate is determined based on the total amount of monomers [methyl methacrylate and other monomers (methacrylic acid C _2-8 alkyl ester, copolymerizable monomer). Body etc.)], for example, about 55 to 99.9% by weight, preferably 60% or more (for example, about 65 to 99% by weight), more preferably 70% or more (for example, 75%). Or about 95% by weight).

(Aromatic polycarbonate resin)
Examples of the aromatic polycarbonate resin include resins having an aromatic diol and a carbonate-forming compound as polymerization components.

Examples of the aromatic diol include bisphenols and dihydroxyarene (hydroquinone, resorcinol, etc.). Examples of bisphenols include dihydroxyarenes [eg, di ( _{hydroxyC 6-10} arenes) such as 4,4′-dihydroxybiphenyl], bis (hydroxyphenyl) alkanes [eg, bis (4-hydroxyphenyl) methane 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis ( 4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2 Bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane Bis (hydroxy) such as 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) diphenylmethane Phenyl) C _1-10 alkanes, preferably bis (hydroxyphenyl) C _1-8 alkanes], bis (hydroxyphenylaryl) alkanes [eg 2,2-bis (4-hydroxy-3,3′- biphenyl) propane and bis (hydroxy _{biphenylyl) C 1-10} alkanes, preferably bis (arsenate B carboxymethyl _{biphenylyl) C 1-8} alkanes, bis (hydroxyphenyl) cycloalkane [e.g., 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis ( Bis (hydroxyphenyl) C _4-10 cycloalkane such as 3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane , Preferably bis (hydroxyphenyl) C _5-8 cycloalkane], bis (hydroxyphenyl) ethers (eg, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyl) Diphenyl ether), bis (hydroxyphenyl) sulfones ( For example, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, 4,4′-dihydroxy-3,3′-diphenyldiphenylsulfone), bis (hydroxyphenyl) Sulfoxides (for example, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfoxide, etc.), bis ( Hydroxyphenyl) sulfides (for example, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide) Bis (hydroxyphenyl-alkyl) array [For example, bis (hydroxyphenyl-C _1-4 alkyl) C _6-10 arenes such as 4,4 ′-(o, m or p-phenylenediisopropylidene) diphenol, preferably bis (hydroxyphenyl- C _1-4 alkyl) benzene] and the like.

Among these aromatic diols, in particular, bis (hydroxyphenyl) alkanes [especially bis (hydroxyphenyl) C _1-4 alkanes such as 2,2-bis (4-hydroxyphenyl) propane], bis (hydroxyphenyl) Bisphenols such as -alkyl) arenes [bis (hydroxyphenyl-C _1-4 alkyl) benzene etc.] are preferred. Aromatic diols may be used alone or in combination of two or more.

Examples of the carbonate-forming compound include carbonates such as phosgene (phosgene, diphosgene, triphosgene, etc.), carbonates [eg, dialkyl carbonate (dimethyl carbonate, diethyl carbonate, etc.), diaryl carbonate (diphenyl carbonate, dinaphthyl carbonate, etc.). Diesters] and the like. Among these, phosgene, diphenyl carbonate and the like may be preferably used. The carbonate-forming compounds may be used alone or in combination of two or more.

The aromatic polycarbonate resin may be used alone or in combination of two or more.

(Aromatic polyester resin)
Examples of aromatic polyester resins include polyalkylene arylate resins, polyarylate resins [for example, aromatic dicarboxylic acids (such as terephthalic acid) and aromatic diols (biphenol, bisphenol A, xylylene glycol, alkylene oxide adducts thereof, etc.) And the like)], and liquid crystalline polyester resins.

Examples of the polyalkylene arylate resin include polyalkylene terephthalate resin [for example, polyalkylene terephthalate (eg, poly C _2-4 alkylene terephthalate such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate), alkylene terephthalate unit (polyalkylene terephthalate unit) ), Polyalkylene naphthalate resin [for example, polyalkylene naphthalate (for example, poly C _2-4 alkylene naphthalate such as polyethylene naphthalate), alkylene naphthalate unit (polyalkylene naphthalate unit) Having a copolyester], polycycloalkane dialkylene terephthalate resin [for example, polycycloalkanedia Sharp emission terephthalate (e.g., poly cyclohexane dimethylene terephthalate), such as a copolyester having cycloalkandienyl alkylene terephthalate units (poly cycloalkane alkylene terephthalate unit), and the like.

In the copolyester, the copolymer component includes, for example, a diol component [eg, alkane diol (eg, C _2-6 alkane diol such as ethylene glycol, propylene glycol, butane diol, hexane diol), polyalkane diol (eg, diethylene glycol). Di-hexaC _2-4 alkanediols such as polytetramethylene glycol), alicyclic diols (eg 1,4-cyclohexanedimethanol etc.), aromatic diols (eg C _2-4 alkylenes of bisphenols) Oxide adducts, etc.)], dicarboxylic acid components {eg aliphatic dicarboxylic acids (eg C _4-12 alkane dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid), aromatic dicarboxylic acids [eg asymmetric aromatics] Zika Rubonic acid (eg phthalic acid, isophthalic acid etc.), diphenyldicarboxylic acid etc.]}, hydroxycarboxylic acid component (eg hydroxybenzoic acid etc.) and the like. The copolymerization components may be used alone or in combination of two or more.

In the copolyester, the proportion of alkylene arylate units (alkylene terephthalate units, alkylene naphthalate units, etc.) may be, for example, 40% by weight or more, preferably 50% by weight or more.

The aromatic polyester resin may be crystalline or non-crystalline.

The aromatic polyester resin may have a linear structure or a branched structure.

Aromatic polyester resins may be used alone or in combination of two or more.

(Cellulose derivative)
The cellulose derivative is not particularly limited, and various cellulose derivatives such as cellulose ester, cellulose carbamate (for example, cellulose phenyl carbamate), cellulose ether and the like can be used.

Examples of the cellulose ester include cellulose acetate such as cellulose diacetate (DAC) and cellulose triacetate (TAC); cellulose C _3-5 acylate such as cellulose propionate and cellulose butyrate; cellulose acetate propionate (CAP), And cellulose acylate such as cellulose acetate C _3-5 acylate such as cellulose acetate butyrate (CAB).

Examples of the cellulose ether include alkyl celluloses (eg, C _1-4 alkyl celluloses such as methyl cellulose and ethyl cellulose), hydroxyalkyl celluloses (eg, hydroxy C ₂₋ such as hydroxyethyl cellulose (HEC) and hydroxypropyl cellulose (HPC)). _4- alkyl cellulose), hydroxyalkylalkyl cellulose (eg, hydroxy C _2-4 alkyl C _1-4 alkyl cellulose such as hydroxypropylmethyl cellulose), carboxyalkyl cellulose (such as carboxymethyl cellulose (CMC)), alkyl-carboxyalkyl cellulose (Such as methyl carboxymethyl cellulose)], derivatives thereof [for example, carboxymethyl cellulose sodium CMC salts (such as alkali metal salts)].

Among these cellulose derivatives, cellulose esters and cellulose ethers are preferable, and cellulose esters (cellulose acylates) such as cellulose acetate and cellulose acetate C _3-4 acylate are particularly preferable. More specifically, cellulose esters such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate may be suitably used as the cellulose derivative.

The cellulose derivatives may be used alone or in combination of two or more.

[Fluorene compound]
The fluorene compound only needs to have a 9,9-bisarylfluorene skeleton, such as a compound having no reactive group [for example, 9,9-bisarylfluorene (for example, 9,9-bisphenylfluorene), etc. 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 non-epoxy reactive groups such as a hydroxyl group, a mercapto group, a carboxyl group, an amino group, and a (meth) acryloyloxy group. 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, 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 an integer of 1 or more] .

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. Condensed bicyclic to tetracyclic hydrocarbons such as 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 ter C _6-10 arene ring such as biphenyl ring, terphenyl ring or 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 C _1-12 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-8 alkyl group, particularly a C _1-1 such as a methyl group). ₄ alkyl group) and the like. When k is plural (2 to 4), the types of the plural groups R ¹ may be the same or different from each other. Moreover, the kind of group R < ¹ > substituted by the different benzene ring may be the same or different. 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.) Hydrocarbon groups such as _6-10 aryl groups), aralkyl groups (C _6-10 aryl-C _1-4 alkyl groups such as benzyl and phenethyl groups); alkoxy groups (C ₁ such as methoxy groups and 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 group) And a dialkylamino group such as an amino group).

Preferred groups R ² include hydrocarbon groups [eg, alkyl groups (eg, C _1-6 alkyl groups), cycloalkyl groups (eg, C _5-8 cycloalkyl groups), aryl groups (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. When the group R ² is an aryl group, the group R ² may form the ring assembly hydrocarbon ring together with the ring Z.

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 type of the group R ² may be the same or different. The number of substitutions m can be selected according to the type of the ring Z, and may be, for example, 0 to 8, preferably 0 to 4 (eg, 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. A group, preferably a C _2-4 alkylene group, and more preferably a C _2-3 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 types of the groups R ³ may be the same or different, and may be usually the same.

The number (addition mole number) n of oxyalkylene groups (OR ³ ) may be 0 or more (for example, 0 to 20), for example, 0 to 15 (for example, 1 to 12), preferably 0 to 10 ( For example, it may be 1 to 6), more preferably 0 to 4 (eg 1 to 4), particularly 0 to 2 (eg 0 to 1). 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), 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, and it may be substituted at an appropriate substitution position on the ring Z. For example, when the ring Z is a benzene ring, the group X may be substituted at the 2-6 position of the phenyl group, and may preferably be substituted 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 5th and 6th positions of the ring.

Specific fluorene compounds (or compounds represented by the above 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, and the like mercapto group, or (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 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].

The 9,9-bis (hydroxynaphthyl) fluorenes correspond to the 9,9-bis (hydroxyphenyl) fluorenes, and are compounds in which the 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] fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene such as 9,9-bis (hydroxy _{C 2-4} alkoxyphenyl) fluorene}, 9,9-bis (alkyl - hydroxy alkoxyphenyl) Fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 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) 9,9-bis (hydroxyalkoxynaphthyl) fluorenes such as 9,9-bis (hydroxyC _2-4 alkoxynaphthyl) fluorene} such as) -2-naphthyl] fluorene.

Among these fluorene compounds, in particular, 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene [for example, 9,9-bis (mono or di C _1-4 alkyl- Hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [eg, 9,9-bis (mono or diC _6-10 aryl-hydroxyphenyl) fluorene], 9,9-bis (di or A compound in which n is 0 in the above formula (1A) such as trihydroxyphenyl) fluorene and 9,9-bis (hydroxynaphthyl) fluorene; 9,9-bis (hydroxyalkoxyphenyl) fluorene {eg, 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 A} compound in which n is 1 or more (for example, 1 to 4, preferably 1 to 2, more preferably 1) in the above formula (1A) such as -4alkoxynaphthyl) fluorene} is preferable. In particular, 9,9-bis (hydroxyalkoxyphenyl) fluorene such as 9,9-bis (hydroxyethoxyphenyl) fluorene may be used from the standpoint that the effect of homogenizing wavelength dispersion by the epoxy compound appears remarkably.

Fluorene compounds may be used alone or in combination of two or more.

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

The ratio of the fluorene compound can be selected, for example, from the range of about 0.1 parts by weight or more (for example, 0.2 to 200 parts by weight) with respect to 100 parts by weight of the resin. It may be 0.5 to 80 parts by weight, more preferably about 1 to 50 parts by weight, usually 0.5 to 50 parts by weight (for example, 0.5 to 40 parts by weight, preferably 0.7 to 30 parts by weight). Parts, more preferably 1 to 20 parts by weight, particularly 2 to 18 parts by weight, particularly preferably 3 to 15 parts by weight). In particular, since the effect of homogenizing the wavelength dispersion by the epoxy compound appears remarkably, the ratio of the fluorene compound is 5 to 15 parts by weight (particularly 8 to 13 parts by weight) with respect to 100 parts by weight of the resin. Good.

In the present invention, the proportion of the fluorene compound used is 20 parts by weight or less (for example, 0.1 to 18 parts by weight), preferably 15 parts by weight or less (for example, 0.2 to 12 parts by weight) with respect to 100 parts by weight of the resin. Part), 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 the present invention, the resin properties can often be maintained or improved at a high level even if a relatively large proportion of the fluorene compound is added. Therefore, the proportion of the fluorene compound used 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 resin. It may be 30 parts by weight or more (for example, 30 to 70 parts by weight).

[Epoxy compound]
The epoxy compound (or epoxy resin) can be roughly classified into a monofunctional epoxy compound (monofunctional epoxy compound) and a polyfunctional epoxy compound (polyfunctional epoxy compound). Examples of monofunctional epoxy compounds include glycidyl ethers (monoglycidyl ether) [eg, alkyl glycidyl ether (eg, 2-ethylhexyl glycidyl ether), alkenyl glycidyl ether (eg, allyl glycidyl ether), aryl glycidyl ether, etc. (Eg, phenyl glycidyl ether, pt-butylphenyl glycidyl ether, etc.), glycidyl ethers of alkylene oxide adducts corresponding to these compounds (eg, glycidyl ethers of alkylene oxide adducts of phenol), etc.], alkene oxides (For example, octylene oxide, styrene oxide, etc.). Monofunctional epoxy compounds may be used alone or in combination of two or more.

Examples of the polyfunctional epoxy compound include diglycidyl ether, alkanediol diglycidyl ether (for example, C _2-10 alkane such as butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether). Diol diglycidyl ether), polyalkane diol diglycidyl ether (eg, poly C _2-4 alkane diaudiglycidyl ether such as polypropylene glycol diglycidyl ether), cycloalkane dialkanol diglycidyl ether (eg cyclohexane dimethanol diglycidyl ether) C _4-10 cycloalkanedi-C _1-4 alkanol diglycidyl ether)), aliphatic polyol poly having 3 or more hydroxyl groups Glycidyl ethers [for example, di- or triglycidyls of C _3-10 alkanetri- or _tetraols such as di- to hexa-glycidyl ethers of alkane tri to hexaols (eg trimethylolpropane di or triglycidyl ethers, glycerin di or triglycidyl ethers) Ether), etc.], bisphenol type epoxy resin (reaction product of the above-mentioned bisphenols such as bisphenol A type epoxy resin and bisphenol F type epoxy resin and epichlorohydrin), brominated bisphenol type epoxy resin, phenol type epoxy resin (Phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc.), glycol type epoxy resin [for example, bisphenols (bisphenol A etc.) or its hydrogenated alkyl A reaction product of a lenoxide adduct and epichlorohydrin], a dicyclopentadiene type epoxy resin, a poly (glycidyloxyphenyl) alkane [for example, 1,1,2,2-tetrakis (4-glycidyloxyphenyl) ethane, Tri- or tetra (glycidyloxyphenyl) C _1-4 alkane such as 1,1,1-tris (glycidyloxyphenyl) methane], a glycidyl ether compound having a naphthalene skeleton [for example, 1,5-di (glycidyloxy) naphthalene 1,6-di (glycidyloxy) naphthalene, 2,6-di (glycidyloxy) naphthalene, 2,7-di (glycidyloxy) naphthalene, 2,7-di (2-methyl-2,3-epoxypropyl) Oxy) naphthalene, 2,2'-diglycidyloxybinaphthalene, etc. (Glycidyloxy) naphthalene, bis (2-glycidyl Jill oxy naphthyl) diglycidyl sulfopropyl such as bis (glycidyloxy naphthyl) C _1-6 alkanes such as methane, binding these di (glycidyloxy) naphthalenes directly or Tetraglycidyl ether (eg bis [2,7-di (glycidyloxy) naphthyl] methane etc.) linked via a linking group (eg alkylene group such as methylene group, ethylene group or alkylidene group)], Glycidyl ether type epoxy compounds such as glycidyl ether compounds having a xanthene skeleton (for example, 9-phenyl-2,7-diglycidyloxy-1,3,4,5,6,8-hexamethylxanthene); glycidyl ester type Epoxy compounds [eg aromatic dica Boric acid (such as phthalic acid) or a hydrogenated product thereof (tetrahydrophthalic acid, hexahydrophthalic acid, etc.) and epichlorohydrin, dimer acid glycidyl ester, etc.]; glycidylamine type epoxy compound (eg, diglycidyl) Aniline, tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, N, N-diglycidyl-4-glycidyloxyaniline, etc.); alkenylcycloalkene dioxide (eg, vinylcyclohexenedioxide, etc.);

Also, the polyfunctional epoxy compound (particularly, glycidyl ether type epoxy compound) includes an epoxy compound having a fluorene skeleton (polyfunctional epoxy compound). Examples of the epoxy compound having a fluorene skeleton include a compound represented by the following formula (1B) (that is, a compound in which Y is a glycidyloxy group in X of the formula (1)).

(In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1)).

Specific epoxy compounds having a fluorene skeleton (or a compound represented by the formula (1B)) include 9,9-bis (glycidyloxyaryl) fluorenes [or 9,9-bis (glycidyloxyaryl) fluorenes. Compounds having a skeleton, such as 9,9-bis (glycidyloxyphenyl) fluorenes, 9,9-bis (glycidyloxynaphthyl) fluorenes], 9,9-bis (glycidyloxy (poly) alkoxyaryl) fluorenes [Or a compound having a 9,9-bis (glycidyloxy (poly) alkoxyaryl) fluorene skeleton, such as 9,9-bis (glycidyloxy (poly) alkoxyphenyl) fluorenes, 9,9-bis (glycidyloxy ( Poly) alkoxynaphthyl) fluorenes] and the like

9,9-bis (glycidyloxyphenyl) fluorenes include, for example, 9,9-bis (glycidyloxyphenyl) fluorene [eg, 9,9-bis (4-glycidyloxyphenyl) fluorene], 9,9- Bis (alkyl-glycidyloxyphenyl) fluorene [eg, 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dimethylphenyl) fluorene, etc. 9,9-bis (mono- or di-C _1-4 alkyl-glycidyloxyphenyl) fluorene], 9,9-bis (aryl-glycidyloxyphenyl) fluorene [for example, 9,9-bis (4-glycidyloxy- 9,9-bis such as 3-phenylphenyl) fluorene (mono- or _{di-C 6-10} ants Ru-glycidyloxyphenyl) fluorene], 9,9-bis (polyglycidyloxyphenyl) fluorene [eg, 9,9-bis (3,4-diglycidyloxyphenyl) fluorene, 9,9-bis (2,4 9,9-bis (di- or triglycidyloxyphenyl) fluorene such as -diglycidyloxyphenyl) fluorene].

The 9,9-bis (glycidyloxynaphthyl) fluorenes correspond to the 9,9-bis (glycidyloxyphenyl) fluorenes and are compounds in which a phenyl group is substituted with a naphthyl group, such as 9,9- Bis (glycidyloxynaphthyl) fluorene [eg, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, 9,9-bis (5-glycidyloxy-1-naphthyl) fluorene] and the like.

9,9-bis (glycidyloxy (poly) alkoxyphenyl) fluorenes include, for example, 9,9-bis (glycidyloxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- (2-glycidyloxyethoxy) ) Phenyl] fluorene, 9,9-bis [4- (2-glycidyloxypropoxy) phenyl] fluorene and other 9,9-bis (glycidyloxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (alkyl) -Glycidyloxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- (2-glycidyloxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-glycidyloxypropoxy) -3 -Methylphenyl] fluorene, 9,9-bis [4- (2-glycidyloxy) 9,9-bis (mono or di C _1-4 alkyl-glycidyloxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (aryl-glycidyloxy) such as ethoxy) -3,5-dimethylphenyl] fluorene Alkoxyphenyl) fluorene {eg, 9,9-bis [4- (2-glycidyloxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-glycidyloxypropoxy) -3-phenylphenyl ] 9,9-bis (glycidyloxyalkoxyphenyl) fluorenes such as 9,9-bis (mono or diC _6-10 aryl-glycidyloxy C _2-4 alkoxyphenyl) fluorene} such as fluorene (formula (1B In which n is 1); 9,9-bis (glycidyloxydial) Coxiphenyl) fluorene {eg, 9,9-bis (glycidyloxydiC _2-4 alkoxyphenyl) fluorene} such as 9,9-bis {4- [2- (2-glycidyloxyethoxy) ethoxy] phenyl} fluorene} 9,9-bis (glycidyloxypolyalkoxyphenyl) fluorenes (compounds wherein n is 2 or more in the formula (1B)), and the like.

The 9,9-bis (glycidyloxy (poly) alkoxynaphthyl) fluorenes correspond to the 9,9-bis (glycidyloxy (poly) alkoxyphenyl) fluorenes, and the phenyl group is substituted with a naphthyl group. Compounds such as 9,9-bis (glycidyloxyalkoxynaphthyl) fluorene {eg 9,9-bis [6- (2-glycidyloxyethoxy) -2-naphthyl] fluorene, 9,9-bis [6- ( such as 2-hydroxypropoxy) -2-naphthyl] 9,9-bis (glycidyloxy _{C 2-4} alkoxy naphthyl) fluorene} 9,9-bis (glycidyloxy alkoxy naphthyl) fluorene such as a fluorene are included.

The multifunctional epoxy compounds may be used alone or in combination of two or more.

The epoxy compounds may be used alone or in combination of two or more.

Of these, polyfunctional epoxy compounds may be suitably used. Therefore, the epoxy compound may contain at least a polyfunctional epoxy compound. In this case, an epoxy compound may be comprised only with a polyfunctional epoxy compound, and may combine a polyfunctional epoxy compound and a monofunctional epoxy compound. When combining a polyfunctional epoxy compound and a monofunctional epoxy compound, these ratios are the former / the latter (weight ratio) = 99.5 / 0.5 to 10/90 (for example, 99/1 to 15/85), Preferably, it may be about 98/2 to 20/80 (for example, 97/3 to 25/75), more preferably about 95/5 to 30/70 (for example, 95/5 to 35/65). It may be about 99/1 to 40/60 (for example, 95/5 to 50/50).

The epoxy compound may be solid or liquid at normal temperature (eg, about 15 to 25 ° C.). The viscosity (25 ° C.) of the liquid epoxy compound may be, for example, 1 to 6000 mPa · s, preferably 10 to 4000 mPa · s, more preferably about 50 to 2000 mPa · s, and 1000 mPa · s or less. An epoxy compound having a low viscosity of [for example, 1 to 500 mPa · s, preferably 300 mPa · s or less (eg 50 to 200 mPa · s), more preferably 150 mPa · s or less (eg 70 to 140 mPa · s)] May be used.

The proportion of the epoxy compound can be selected from the range of, for example, about 0.05 parts by weight or more (for example, 0.07 to 100 parts by weight) with respect to 100 parts by weight of the resin. It may be about 0.3 to 50 parts by weight, more preferably about 0.5 to 40 parts by weight, usually 0.1 to 30 parts by weight (eg, 0.3 to 25 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 0.7 to 15 parts by weight, particularly 0.8 to 10 parts by weight, particularly preferably 1 to 5 parts by weight.

The ratio of the epoxy compound is, for example, 0.1 to 200 parts by weight (eg 0.5 to 150 parts by weight), preferably 1 to 100 parts by weight (eg 2 to 2 parts by weight) with respect to 100 parts by weight of the fluorene compound. 80 parts by weight), more preferably 3 to 60 parts by weight, particularly about 5 to 40 parts by weight, usually 1 to 100 parts by weight (eg 2 to 80 parts by weight, preferably 3 to 50 parts by weight, More preferably, it may be about 5 to 30 parts by weight, particularly 8 to 25 parts by weight.

The resin composition of the present invention may contain other additives {additives that are neither a fluorene compound nor an epoxy compound, for example, a filler or a reinforcing agent, a colorant (dye pigment), a conductive agent, if necessary. Flame retardants, plasticizers, lubricants, stabilizers [antioxidants (hindered phenol antioxidants, phosphorus antioxidants, etc.), UV absorbers, heat stabilizers, etc.], curing agents (epoxy compounds or epoxy resins) Curing agents, etc.), curing accelerators, 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, the ratio of another additive can be suitably selected according to the kind. For example, the proportion of the stabilizer is about 0.001 to 10 parts by weight, preferably 0.01 to 7 parts by weight, more preferably about 0.05 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Also good.

The resin composition can be obtained by mixing a resin, a fluorene compound, and an epoxy compound [further, with other components (such as other additives) as necessary]. The mixing method is not particularly limited, and may be mixed by, for example, melt kneading or may be mixed by dissolving each component in a solvent.

The present invention also includes a molded body formed of such a resin composition. The shape of such a molded body is not particularly limited, and can be appropriately selected depending on the application. For example, a two-dimensional structure (film shape, sheet shape, plate shape, etc.), a three-dimensional structure (tubular, rod shape, tube) Shape, hollow shape, etc.).

In particular, the resin composition of the present invention is often excellent in optical properties, and an optical material or an 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 various 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.

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

Such a film (such as an optical film) is formed 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. Can be manufactured.

The film may be a stretched film. Such a stretched film may be either a uniaxially stretched film or a 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 thickness of the stretched film may be, for example, about 1 to 150 μm, preferably 3 to 120 μm, and more preferably about 5 to 100 μm.

Such a stretched film can be obtained by subjecting a film after film formation (or an unstretched film) to a stretching treatment. 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.

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.

(Yield point strength, elongation at break)
A tensile test was performed using an autograph (load cell: 1 kN) manufactured by Shimadzu Corporation. A sample having a width of about 7.5 mm and a length of 5 cm was used, the distance between chucks was 20 mm, and the tensile speed was 10 mm / min.

(Tear strength)
A tear test was performed using a digital Elmendorf tear tester SA-WP (manufactured by Toyo Seiki Seisakusho). The sample used was a 75 mm × 63 mm rectangular sample (conforming to JISK7128-2) with a 20 mm cut in the center, and the obtained results were converted to tear strength per 30 μm.

(Evaluation of phase difference and chromatic dispersion characteristics)
The retardation of the film was measured with a high-speed retardation measuring device RE-100 manufactured by Otsuka Electronics Co., Ltd. Moreover, (the retardation value at each wavelength and _{N 400, N 589, N 700} ) in evaluating the wavelength dispersion, the 400 nm, 589 nm, measurement of retardation values of 700 nm.

(Haze, total light transmittance)
The total light transmittance and haze were measured with Suga Test Instruments Co., Ltd. Haze Meter HZ-2.

(Reference Example 1)
100 parts by weight of cellulose triacetate (manufactured by Daicel Corporation, LT55, hereinafter referred to as TAC), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEF) ) 11 parts by weight, stabilizer [hindered phenol antioxidant (BASF Japan, IRGANOX1010) and phosphorus antioxidant (Sumitomo Chemical Co., Ltd., SUMILIZER GP)] Using KZW15 / 30 MG) manufactured by Technobel, melt-kneading was performed at a cylinder temperature of 210 to 290 ° C. to obtain a pellet-shaped resin composition. In addition, the ratio of hindered phenolic antioxidant was 2000 ppm with respect to the total amount of TAC and BPEF, and the ratio of phosphorus antioxidant was 1000 ppm with respect to the total amount of TAC and BPEF. In addition, the resin composition was transparent and was mixed uniformly.

The obtained resin composition was melt-pressed (hot pressed) using a press molding machine to obtain a film (unstretched film).

And various characteristics were measured using the obtained film.

First, the tear strength of the film was 0.11 N, the yield strength was 71.6 MPa, and the elongation at break was 9.9%.

In the film, the phase difference (N ₄₀₀ ) at a wavelength of ₄₀₀ nm is 0.12 nm, the phase difference (N ₅₈₉ ) at a wavelength of ₅₈₉ nm is 0.21 nm, and the phase difference (N ₇₀₀ ) at a wavelength of 700 nm is 0.24 nm. shows a wavelength dispersion _{(N 400 / N 589 = 0.57} , N 700 / N 589 = 1.14).

Furthermore, the haze of the film was 0.9, and the total light transmittance was 92%.

(Example 1)
In Reference Example 1, a resin composition was obtained in the same manner as in Reference Example 1 except that 1.6 parts by weight of an epoxy compound (trimethylolpropane triglycidyl ether) was further melt-kneaded. In addition, the resin composition was transparent and was mixed uniformly.

Then, in the same manner as in Reference Example 1, films were prepared and various characteristics were evaluated.

First, in the film, the tear strength is 0.13 N, the yield point strength is 79.8 MPa, the elongation at break is 11.2%, and it is confirmed that the mechanical properties are greatly improved compared to Reference Example 1. did.

In the film, the phase difference (N ₄₀₀ ) at a wavelength of ₄₀₀ nm is 0.16 nm, the phase difference (N ₅₈₉ ) at a wavelength of ₅₈₉ nm is 0.15 nm, the phase difference (N ₇₀₀ ) at a wavelength of 700 nm is 0.15 nm, and flat (N ₄₀₀ / N ₅₈₉ = 1.07, N ₇₀₀ / N ₅₈₉ = 1.00).

From this result, it was found that the wavelength dispersion can be suppressed by adding an epoxy compound as compared with Reference Example 1.

Furthermore, in the film, the haze was 0.6 and the total light transmittance was 92%.

From this result, it was found that even when an epoxy compound was added, transparency was not impaired (rather, transparency was improved).

(Example 2)
Reference Example 1 and Reference Example 1 except that 2.0 parts by weight of 9,9-bis (4-glycidyloxyphenyl) fluorene (Osaka Gas Chemical Co., Ltd.) were melt-kneaded as an epoxy compound. Similarly, a resin composition was obtained. In addition, the resin composition was transparent and was mixed uniformly.

Then, in the same manner as in Reference Example 1, films were prepared and various characteristics were evaluated.

First, in the film, the tear strength is 0.12 N, the yield point strength is 77.4 MPa, and the elongation at break is 12.9%, confirming that the mechanical properties are greatly improved as compared with Reference Example 1. did.

In the film, the retardation (N ₄₀₀ ) at a wavelength of ₄₀₀ nm is 0.21 nm, the retardation (N ₅₈₉ ) at a wavelength of ₅₈₉ nm is 0.20 nm, the retardation (N ₇₀₀ ) at a wavelength of 700 nm is 0.20 nm, and the film is flat. (N ₄₀₀ / N ₅₈₉ = 1.05, N ₇₀₀ / N ₅₈₉ = 1.00).

From this result, it was found that the wavelength dispersion can be suppressed by adding an epoxy compound as compared with Reference Example 1.

Furthermore, in the film, the haze was 1.2 and the total light transmittance was 92%.

From this result, it was found that even when an epoxy compound was added, the transparency was not greatly impaired.

(Reference Example 2)
Reference Example 1 except that 11 parts by weight of BPEF was replaced with 18 parts by weight of 6,6-bis (9-fluorenylidene) -di (2-naphthol) (Osaka Gas Chemical Co., Ltd., hereinafter referred to as BNF). In the same manner as in Example 1, a film (unstretched film) was obtained. The cylinder temperature was 210 to 280 ° C. And various characteristics were measured using the obtained film.

First, the tear strength of the film was 0.38 N, the yield strength was 63.7 MPa, and the elongation at break was 2.8%.

Further, the obtained film was measured for a phase difference, a phase difference at a wavelength of 400 nm _{(N 400)} is 4.70Nm, the phase difference at a wavelength of 589 nm _{(N 589)} is 5.08Nm, the phase difference at a wavelength 700 nm (N ₇₀₀ ) was 5.18 nm, and showed reverse wavelength dispersion (N ₄₀₀ / N ₅₈₉ = 0.93, N ₇₀₀ / N ₅₈₉ = 1.02).

Furthermore, the haze of the film was 0.9, and the total light transmittance was 92%.

(Example 3)
In Reference Example 2, a resin composition was obtained in the same manner as in Reference Example 2 except that 1.6 parts by weight of an epoxy compound (trimethylolpropane triglycidyl ether) was further melt-kneaded. In addition, the resin composition was transparent and was mixed uniformly.

Then, in the same manner as in Reference Example 1, films were prepared and various characteristics were evaluated.

First, in the film, the tear strength is 0.58 N, the yield point strength is 67.4 MPa, the elongation at break is 5.7%, and it is confirmed that the mechanical properties are greatly improved compared to Reference Example 2. did.

In the film, the phase difference (N ₄₀₀ ) at a wavelength of ₄₀₀ nm is 4.43 nm, the phase difference (N ₅₉₈ ) at a wavelength of 589 nm is 4.59 nm, the phase difference (N ₇₀₀ ) at a wavelength of 700 nm is 4.63 nm, and is flat. (N ₄₀₀ / N ₅₈₉ = 0.96, N ₇₀₀ / N ₅₈₉ = 1.01).

Furthermore, in the film, the haze was 0.6 and the total light transmittance was 92%.

From this result, it was found that even when an epoxy compound was added, transparency was not impaired (rather, transparency was improved).

(Reference Example 3)
In Reference Example 1, 11 parts by weight of BPEF was replaced with 18 parts by weight of 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene (Osaka Gas Chemical Co., Ltd., hereinafter referred to as BOPPEF). Except for the above, a film (unstretched film) was obtained in the same manner as in Reference Example 1. The cylinder temperature was 210 to 280 ° C. And various characteristics were measured using the obtained film.

And various characteristics were measured using the obtained film.

First, the tear strength of the film was 0.41 N, the yield strength was 68.0 MPa, and the elongation at break was 4.5%.

Further, when the retardation of the obtained film was measured, the retardation at a wavelength of 400 nm (N ₄₀₀ ) was 4.66 nm, the retardation at a wavelength of 589 nm (N ₅₈₉ ) was 5.79 nm, and the retardation at a wavelength of 700 nm (N ₇₀₀ ) was 6.07 nm, and showed reverse wavelength dispersion (N ₄₀₀ / N ₅₈₉ = 0.81, N ₇₀₀ / N ₅₈₉ = 1.02).

Furthermore, the haze of the film was 0.9, and the total light transmittance was 92%.

Example 4
In Reference Example 3, a resin composition was obtained in the same manner as in Reference Example 3, except that 1.6 parts by weight of an epoxy compound (trimethylolpropane triglycidyl ether) was further melt-kneaded. In addition, the resin composition was transparent and was mixed uniformly.

Then, in the same manner as in Reference Example 1, films were prepared and various characteristics were evaluated.

First, in the film, the tear strength is 0.56 N, the yield point strength is 70.8 MPa, the elongation at break is 4.9%, and it is confirmed that the mechanical properties are greatly improved compared to Reference Example 3. did.

In the film, the phase difference (N ₄₀₀ ) at a wavelength of ₄₀₀ nm is 5.39 nm, the phase difference (N ₅₉₈ ) at a wavelength of 589 nm is 6.60 nm, and the phase difference (N ₇₀₀ ) at a wavelength of 700 nm is 6.9 nm. shows a wavelength dispersion _{(N 400 / N 589 = 0.82} , N 700 / N 589 = 1.04).

Furthermore, in the film, the haze was 0.6 and the total light transmittance was 92%.

From this result, it was found that even when an epoxy compound was added, transparency was not impaired (rather, transparency was improved).

Since the resin composition of the present invention contains a combination of a fluorene compound and an epoxy compound, it can impart excellent properties derived from the fluorene compound to the resin without impairing mechanical properties. Further, the wavelength dispersion of the resin can be adjusted (for example, the wavelength dispersion of the resin can be reduced) by a combination of a fluorene compound and an epoxy compound.

Therefore, the resin composition of the present invention is excellent in, for example, high refractive index, high heat resistance, high transparency, excellent moldability (such as high melt fluidity), although it depends on the type of resin constituting the resin composition. It has characteristics.

Such a resin composition is particularly useful for constructing (or forming) a molded product for optical use (optical molded product) because it is often excellent in optical properties. Examples of the optical molded body formed (configured) with such a resin composition include optical films and optical lenses.

As an optical film, in addition to a phase film (or a retardation plate), a polarizing film (and a polarizing element and a polarizing plate protective film constituting the polarizing film), an alignment film (alignment film), a viewing angle expansion (compensation) film, a diffusion plate (Film), 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, electrode substrate film, color filter substrate film, barrier film, color filter layer, black matrix layer, adhesive layer or release layer between optical films, etc. Can be mentioned. 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 (15)

1. A resin composition comprising a non-epoxy resin, a non-epoxy compound having a 9,9-bisarylfluorene skeleton, and an epoxy compound.
2. The resin composition according to claim 1, wherein the non-epoxy 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, 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 an integer of 1 or more]
3. The resin composition according to claim 1 or 2, wherein the non-epoxy 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)).
4. 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 _2-4 alkylene group, n is 0 to 2, and p is 1 to 3.
5. Non-epoxy compounds having a 9,9-bisarylfluorene skeleton include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, and 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-hydroxyalkoxy) The resin according to any one of claims 1 to 4, which is at least one selected from phenyl) fluorene, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene, and 9,9-bis (hydroxyalkoxynaphthyl) fluorene. Composition.
6. 6. The resin composition according to claim 1, wherein the non-epoxy resin is a thermoplastic resin.
7. 7. The resin composition according to claim 1, wherein the non-epoxy resin is at least one selected from a cyclic olefin resin, a methacrylic resin, an aromatic polycarbonate resin, an aromatic polyester resin, and a cellulose derivative.
8. The resin composition according to any one of claims 1 to 7, wherein the epoxy compound comprises a polyfunctional epoxy compound.
9. The proportion of the non-epoxy compound having a 9,9-bisarylfluorene skeleton is 0.5 to 50 parts by weight and the proportion of the epoxy compound is 0.1 to 30 parts by weight with respect to 100 parts by weight of the non-epoxy resin. The resin composition according to any one of claims 1 to 8.
10. 10. The resin composition according to claim 1, wherein the ratio of the epoxy compound is 1 to 100 parts by weight with respect to 100 parts by weight of the non-epoxy compound having a 9,9-bisarylfluorene skeleton.
11. A molded body formed of the resin composition according to any one of claims 1 to 10.
12. The molded article according to claim 11, which is an optical molded article.
13. The molded article according to claim 11 or 12, which is an optical film.
14. A wavelength dispersion reducing agent composed of a non-epoxy compound having an 9,9-bisarylfluorene skeleton and an epoxy compound, which is an additive for reducing the wavelength dispersion of a non-epoxy resin.
15. A method for reducing the wavelength dispersibility of a non-epoxy resin by adding the wavelength dispersibility reducing agent according to claim 14 to the non-epoxy resin.