JP2008290294A - Transparent resin molding and its manufacturing process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin molding having high transparency and refractive index. <P>SOLUTION: The transparent resin molding having a high refractive index is prepared by solidifying a transparent resin composition containing aromatic rings in a fluidized state in a magnetic field, wherein the aromatic rings are oriented in the resin. The aromatic rings may be fluorene rings. The transparent resin composition may be composed of a transparent resin prepared by using a fluorene derivative. The molding is useful for a lens and an optical material, as it combines a refractive index and transparency both at a high level without deteriorating the characteristics inherent in the resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a molded article made of a transparent resin composition having a high refractive index suitable for various optical materials and lenses, and a method for producing the same.

  Conventionally, inorganic materials such as glass and transparent resins have been used as materials that require transparency, such as various optical materials and lenses. Among them, in recent years, the use of a transparent resin excellent in moldability and mechanical properties has been actively used, but depending on the application, a high refractive index is also required in addition to transparency. As a method for improving the refractive index of a resin composition, for example, a technique of dispersing metal oxide fine particles having a large refractive index in a resin is widely known. As the refractive index increases, the transparency is lowered and coloration is likely to occur.

  As another method for improving the refractive index of the resin composition, “Photo / Electronic Functional Organic Material Handbook” (Non-Patent Document 1) includes introduction of an aromatic ring, introduction of sulfur (S) atoms, fluorine (F ) Techniques such as introduction of halogen atoms other than atoms are disclosed. In this document, it is described that a high refractive index of about 1.7 can be achieved by these methods, but in the case of introducing an S atom, which is considered to have the greatest effect of increasing the refractive index, the yellow color inherent to the S atom is obtained. It was easy to color and was unsuitable for practical use because of the unusual odor of S atoms during processing such as cutting and polishing of the molded body. In addition, the introduction of halogen atoms other than F atoms is easy to be colored, and it is difficult to increase the refractive index of 1.6 or more. Therefore, practically, increasing the refractive index of the resin composition has been limited to introduction of an aromatic ring. However, even if an aromatic ring is introduced, it is the limit that a refractive index of about 1.6 can be achieved, and a method for further increasing the refractive index has been demanded.

  On the other hand, “AIST TODAY” (Non-Patent Document 2) requires alignment technology at the molecular level in order to improve the performance of organic optoelectronic materials including optical materials. Examples include diamagnetic interactions of aromatic compounds. The alignment technique of organic nanocrystals mentioned in the above is shown. However, in this document, although the orientation technique is described, its specific material and practicality are not disclosed.

  WO 2004/030807 (Patent Document 1) discloses a method of orienting an aggregate of objects having a uniaxial anisotropic diamagnetic susceptibility by applying an external magnetic field that varies with time. Yes. This document uses a liquid crystal material such as a high-molecular liquid crystal or a low-molecular liquid crystal, a melt or solution of a high-molecular or low-molecular material such as polyethylene terephthalate, polyethylene oxide, isotactic polypropylene, isotactic polystyrene, or cellulose. The production of molded articles with improved magnetic, electrical, thermal and mechanical properties is described. However, this document does not mention refractive index and transparency.

Furthermore, in Japanese Patent Application Laid-Open No. 2002-146063 (Patent Document 2), an organic alkali metal salt is added to a polycarbonate (PC) or polyethylene terephthalate (PET), which is an amorphous polymer, and then melted. A method for producing a molded body by crystal orientation is disclosed. This document describes that the molded body obtained by this method can be used as an optical material having transparency and a large intrinsic birefringence value. However, in this molded body, crystallization of polycarbonate or polyester is promoted, but the transparency decreases with crystallization. Further, birefringence is defined as a difference between the refractive index n0 of ordinary light and the refractive index ne of extraordinary light (see Non-Patent Document 1, etc.), and is a physical quantity different from the refractive index. That is, Patent Document 2 does not describe improvement of the refractive index due to magnetic field orientation of molecules.
WO 2004/030807 (claims 1 and 12-14, page 7, line 14 to page 8, line 15) JP 2002-146063 A (Claim 1, paragraph [0003]) "Optical / Electronic Functional Organic Materials Handbook", Volume III Materials / Chapter 3 Optical Materials, Asakura Shoten, 1995 "AIST TODAY", Vol. 5, No. 4, pp. 12-15, 2005

  Accordingly, an object of the present invention is to provide a resin molded body having high transparency and refractive index and a method for producing the same.

  Another object of the present invention is to provide a transparent resin molded article having high heat resistance and dimensional stability and low birefringence, and a method for producing the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors applied a magnetic field to a transparent resin composition containing an aromatic ring and oriented the aromatic ring in response to the direction of the magnetic field, whereby the original characteristics of the resin The present inventors have found that both transparency and refractive index can be increased without lowering the thickness, and the present invention has been completed.

  That is, the molded article of the present invention is a molded article composed of a transparent resin composition containing an aromatic ring, and the aromatic ring is oriented by applying a magnetic field. The aromatic ring may be a fluorene ring. The said transparent resin composition may be comprised with the transparent resin obtained using the fluorene derivative represented by Formula (1).

(In the formula, ring Z ¹ and ring Z ² are aromatic hydrocarbon rings, R ^1a , R ^1b and R ² are the same or different and each represents a substituent. K1 and k2 are the same or different and represent an integer of 0 to 4; M represents 0 or an integer of 1 or more, and n represents an integer of 1 or more).

  This molded article has a high degree of orientation of aromatic rings, and for example, the intensity of the fluorescence spectrum emitted when irradiated with ultraviolet rays is smaller than that before application of a magnetic field.

  The present invention also includes a method for producing the molded body, which includes a step of solidifying the fluidized transparent resin composition while applying a magnetic field. This production method may be a method of solidifying a solution containing a transparent resin composition by removing a solvent, or a method of solidifying a molten or softened transparent resin composition by cooling.

  The present invention also includes a method of increasing the refractive index of the transparent resin composition by applying a magnetic field to the transparent resin composition containing an aromatic ring and orienting the aromatic ring.

  Furthermore, the present invention includes a transparent resin composition containing a fluorene ring, which can improve the refractive index by applying a magnetic field.

  In the present invention, by applying a magnetic field to a transparent resin composition containing an aromatic ring, both transparency and refractive index can be improved without impairing the properties of the resin. Furthermore, by using a fluorene ring as the aromatic ring, the heat resistance and dimensional stability can be improved, and the birefringence can be lowered.

[Transparent resin composition]
The molded body of the present invention is composed of a transparent resin composition containing an aromatic ring, and the aromatic ring is oriented by applying a magnetic field.

As the aromatic ring, for example, in addition to a monocyclic aromatic ring such as a benzene ring, condensed polycyclic aromatic rings (for example, indene ring, naphthalene ring, anthracene ring, fluorene ring, phenanthrene ring, pyrene ring, coronene ring, pentacene ring, etc. C _10-30 condensed 2- to 7-ring aromatic rings, etc.). These aromatic rings are condensed polycyclic heterocycles in which a part of the chemical structure of the aromatic ring is substituted with a heteroatom such as nitrogen, oxygen, or sulfur, such as a carbazole ring, phenoxazine ring, or phenothiazine ring. May be. Further, these aromatic rings may be derivatives having a substituent such as an alkyl group. These aromatic rings can be used alone or in combination of two or more. Of these aromatic rings, a C _10-20 condensed 2- to 4-cyclic aromatic ring, particularly a fluorene ring, is preferable from the viewpoint of excellent optical characteristics, heat resistance, dimensional stability, and the like.

  In the present invention, the aromatic ring can be oriented by applying a magnetic field to the aromatic ring by utilizing the characteristic that these aromatic rings have responsiveness to the magnetic field. The presence form of the aromatic ring in the resin composition (molded product) may be a form in which a low molecular compound having an aromatic ring is dispersed in the resin, but the mechanical properties of the resin composition can be improved. Therefore, a form in which the aromatic ring is present as a structural unit in the polymer is preferable. When the aromatic ring is a structural unit of the polymer, it is preferable to have an aromatic ring in the side chain portion of the polymer from the point that the magnetic field is easy to respond, from the point that the transparency and mechanical properties of the polymer can be improved, The main chain of the polymer preferably has an aromatic ring.

  In this invention, it is preferable that especially transparent resin composition fat is comprised with the transparent resin obtained using the fluorene derivative represented by Formula (1).

(In the formula, ring Z ¹ and ring Z ² are aromatic hydrocarbon rings, R ^1a , R ^1b and R ² are the same or different and each represents a substituent. K1 and k2 are the same or different and represent an integer of 0 to 4; M represents 0 or an integer of 1 or more, and n represents an integer of 1 or more).

In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z ¹ and the ring Z ² include a benzene ring and a condensed polycyclic hydrocarbon ring. The condensed polycyclic hydrocarbon corresponding to the condensed polycyclic hydrocarbon ring includes a condensed bicyclic hydrocarbon (for example, C _8-20 condensed bicyclic hydrocarbon such as indene and naphthalene, preferably C _10-16. Condensed bicyclic hydrocarbons) and condensed tricyclic hydrocarbons (for example, anthracene, phenanthrene, etc.) and the like. Preferable condensed polycyclic hydrocarbons include benzene and condensed polycyclic aromatic hydrocarbons (naphthalene, anthracene, etc.), and benzene and naphthalene are particularly preferable. Ring Z ¹ and ring Z ² may be the same or different from each other. Usually, ring Z ¹ and ring Z ² may be the same ring.

The substituents represented by the groups R ^1a and R ^1b are not particularly limited, and may be a cyano group, a hydrocarbon group (for example, an alkyl group or the like), and is usually an alkyl group in many cases. Examples of the alkyl group include C _1-6 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 _1-4 alkyl group, particularly a methyl group). . The groups R ^1a and R ^1b may be different from each other or the same. When k1 (or k2) is 2 or more, the groups R ^1a (or R ^1b ) may be different or the same in the same benzene ring. Note that the bonding position (substitution position) of the group R ^1a (or R ^1b ) with respect to the benzene ring constituting the fluorene skeleton is not particularly limited. Preferred substitution numbers k1 and k2 are 0 or 1, in particular 0. The substitution numbers k1 and k2 may be different but are usually the same.

Examples of the substituent R ² for substituting the ring Z ¹ and the ring Z ² (hereinafter collectively referred to as ring Z) include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group). C _1-20 alkyl group such as s-butyl group and t-butyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group, etc., cycloalkyl group (cyclopentyl group, cyclohexyl) A C _5-10 cycloalkyl group such as a group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 cycloalkyl group, etc., an aryl group [eg, a phenyl group, an alkylphenyl group (methylphenyl group ( or tolyl group, 2-methylphenyl group, and 3-methylphenyl group), a dimethylphenyl group (xylyl), etc.), C such as a naphthyl group _-10 aryl group, preferably a _{C 6-8} aryl group, especially a phenyl 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); Alkoxy group (C _1-4 alkoxy group such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group, etc.); Acyl group (C _1-6 acyl group such as acetyl group, etc.) Alkoxycarbonyl groups (C _1-4 alkoxycarbonyl groups such as methoxycarbonyl groups); halogen atoms (fluorine atoms, chlorine atoms, etc.); nitro groups; cyano groups and the like. Preferred substituents R ² are an alkyl group (eg, C _1-6 alkyl group), a cycloalkyl group (eg, C _5-8 cycloalkyl group), an aryl group (eg, C _6-10 aryl group), an aralkyl group. (For example, a C _6-8 aryl-C _1-2 alkyl group), and a C _1-4 alkyl group, a C _1-4 alkoxy group, and a C _6-8 aryl group are particularly preferable. The substituent R ² may be substituted on the benzene ring alone or in combination of two or more in the same ring (ring Z ¹ or ring Z ² ). Further, the substituents R ² substituted on the different rings Z ¹ and Z ² may be the same or different from each other, and may usually be the same. Incidentally, the substitution position of the substituent R ² is not particularly limited, depending on the substitution position of the hydroxyl group, may be substituted on proper position of substitution.

The substitution number m of the substituent R ² can be appropriately selected according to the number of condensed rings of the condensed hydrocarbon, and is not particularly limited, and is, for example, 0 to 12, preferably 0 to 8 (for example, 1 to 6), and Preferably, it may be about 0-4. In particular, when ring Z is a condensed bicyclic hydrocarbon ring (such as a naphthalene ring), the preferred substitution number m depends on the substitution number n of the hydroxyl group, but is preferably 0 to 4, more preferably 0 to 2, particularly 0 to 1 (particularly 0). The number of substitutions m may be the same or different in each of the rings Z ¹ and Z ² and is usually the same in many cases.

The substitution number n of the hydroxyl group may be 1 or more, and may be, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1. The number n of hydroxyl group substitutions may be the same or different in each of the rings Z ¹ and Z ² , and is usually the same in many cases. The substitution position of the hydroxyl group is not particularly limited as long as it is substituted at an appropriate substitution position of ring Z. In particular, in the condensed polycyclic hydrocarbon, the hydroxyl group is often substituted at least with a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of fluorene.

Preferred fluorene derivatives include, for example, 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (C _1-4 alkylhydroxyphenyl) fluorene, 9,9-bis (hydroxyarylphenyl) fluorene (or 9,9). 9-bis (arylhydroxyphenyl) fluorene), 9,9-bis (hydroxynaphthyl) fluorenes {for example, 9,9-bis [6- (2-hydroxynaphthyl)] fluorene (or 6,6- (9- Substituents such as fluorenylidene) -di (2-naphthol)), 9,9-bis [1- (5-hydroxynaphthyl)] fluorene (or 5,5- (9-fluorenylidene) -di (1-naphthol)) 9,9-bis (hydroxynaphthyl) fluorene} which may have

  In addition, these fluorene derivatives may be further modified, for example, a hydroxyl group may be added by an alkylene oxide such as ethylene oxide. Further, in the case of a curable resin, the fluorene derivative may be a glycidyl ether of 9,9-bis (hydroxyphenyl) fluorene (such as diglycidyl ether or tetraglycidyl ether) or 9,9 as a polyfunctional (meth) acrylate. -(Meth) acrylates of bis (hydroxyphenyl) fluorenes may be used. In the case of a polyamide resin or a polyimide resin, the hydroxyl group of the fluorene derivative may be an amino group.

  The transparent resin obtained by using these fluorene derivatives is not particularly limited, and a conventional thermoplastic resin or thermosetting resin (or photocurable resin) can be used. Examples of the thermoplastic resin include acrylic resins, polycarbonate resins, polyester resins, polyamide resins, and polyimide resins. These thermoplastic resins may be used alone or in combination of two or more.

  Examples of thermosetting resins include phenolic resins, unsaturated polyester resins, epoxy resins, thermosetting polyurethane resins, thermosetting polyimide resins, vinyl ester resins (epoxy resins and (meth) acrylic acid or derivatives thereof). And a resin obtained by reaction of polyhydric phenols with glycidyl (meth) acrylate, and the like. In addition, the thermosetting resin (or photocurable resin) includes a polyfunctional (meth) acrylate [(meth) acrylate of the 9,9-bis (hydroxyphenyl) fluorenes, (poly) urethane (meth) acrylate]. , (Poly) ester (meth) acrylate, epoxy (meth) acrylate, etc.], vinyl ether (divinyl ether obtained by reaction of diol component and acetylene, etc.) and the like. Thermosetting resins may be used alone or in combination of two or more.

  Further, the thermosetting resin may contain an initiator, a reactive diluent, a curing agent, a curing accelerator, and the like depending on the type of the thermosetting resin (or photocurable resin). For example, the resin composition containing the epoxy resin or urethane resin may contain an amine-based curing agent or the like, and the resin composition containing the unsaturated polyester resin or vinyl ester resin may contain an initiator (peroxide resin). Oxides, etc.), polymerizable monomers (reactive diluents such as (meth) acrylic acid esters and styrene) and the like.

  Of these resins, the radical polymerization resin usually has a fluorene derivative in the side chain, and the condensation resin often has a fluorene derivative in the main chain. Among these resins, polyester resin, polycarbonate resin, polyurethane resin (thermoplastic or thermosetting polyurethane resin), acrylic resin [polyfunctional (meth) acrylate, etc. Including a curable or photocurable resin], an epoxy resin, a polyimide resin (thermoplastic or thermosetting polyimide resin) and the like are preferable.

(1) Polyester resin A polyester resin containing a fluorene derivative as a polymerization component is a polyol component such as the fluorene derivative having at least a hydroxyl group (the 9,9-bis (hydroxyphenyl) fluorene or an alkylene oxide adduct thereof, In particular, 9,9-bis (monohydroxyphenyl) fluorenes or diol components such as alkylene oxide adducts thereof) and a dicarboxylic acid component can be obtained, and polyester resins include saturated or unsaturated polyesters. In addition to a resin, a polyarylate resin using an aromatic dicarboxylic acid as a polymerization component is also included.

The polyol component (particularly the diol component) of the polyester resin may be configured by combining the fluorene derivative and another diol component. Examples of such diol components (or diols) include alkylene glycols (eg, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, decane. Linear or branched C _2-12 alkylene glycols such as diols), (poly) oxyalkylene glycols (eg di to tetra C _2-4 alkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, etc.) Alicyclic diols (for example, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane and its alkylene oxide adducts 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane etc.)), aromatic diols (eg, biphenol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bisphenol AD, Examples thereof include bisphenol F and their alkylene oxide ( _C2-3 alkylene oxide) adducts (such as 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane) and xylylene glycol). These diols may be used alone or in combination of two or more.

Preferred diols are linear or branched C _2-10 alkylene glycols, particularly C _2-6 alkylene glycols (eg, linear or branched chain such as ethylene glycol, propylene glycol, 1,4-butanediol). C _2-4 alkylene glycol). As the diol, at least ethylene glycol is often used. When such diols (for example, ethylene glycol) are used, the polymerization reactivity can be enhanced and flexibility can be imparted to the resin.

  The ratio (molar ratio) between the fluorene derivative and the diol is, for example, the former / the latter = 100/0 to 50/50, preferably 100/0 to 75/25 (for example, 100/0 to 70/30). More preferably, it may be about 100/0 to 90/10 (for example, 100/0 to 80/20).

  A polyol such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol may be used in combination with the diol component as necessary.

  Examples of the dicarboxylic acid component constituting the polyester resin include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and derivatives capable of forming esters thereof [for example, acid anhydrides; acid halides (acid chlorides, etc.); Lower alkyl esters (such as C1-2 alkyl esters)] and the like. These dicarboxylic acids can be used alone or in combination of two or more.

Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, and other saturated C _3-20 aliphatic dicarboxylic acids. Acids (preferably saturated C _3-14 aliphatic dicarboxylic acids, etc.); unsaturated C _4-20 aliphatic dicarboxylic acids (preferably unsaturated C _4-14 aliphatics, such as maleic acid, fumaric acid, citraconic acid, mesaconic acid) Dicarboxylic acid and the like); derivatives of these that can form esters. In the unsaturated polyester resin, the ratio of the aliphatic unsaturated dicarboxylic acid (maleic acid or its acid anhydride) is, for example, 10 to 100 mol%, preferably 30 to 100 mol%, based on the entire dicarboxylic acid component. More preferably, it may be about 50 to 100 mol% (for example, 75 to 100 mol%).

Examples of the alicyclic dicarboxylic acid include saturated alicyclic dicarboxylic acids (cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, cycloheptane dicarboxylic acid, etc. C _3-10 cycloalkane-dicarboxylic acid), unsaturated alicyclic dicarboxylic acid (C _3-10 cycloalkene-dicarboxylic acid such as 1,2-cyclohexene dicarboxylic acid, 1,3-cyclohexene dicarboxylic acid, etc.); Cyclic alkane dicarboxylic acids (di- or tricyclo C _7-10 alkane-dicarboxylic acids such as bornane dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid), polycyclic alkene dicarboxylic acids (bornene dicarboxylic acid, norbornene dicarboxylic acid, etc. di- or tricyclic C _7-10 A Ken - dicarboxylic acid), etc. These esters can form derivatives can be exemplified.

Aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, etc.), 4,4'-diphenyldicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, 4 , 4′-diphenylmethane dicarboxylic acid, aromatic C _8-16 dicarboxylic acid such as 4,4′-diphenyl ketone dicarboxylic acid; and ester-forming derivatives thereof.

  The dicarboxylic acid may be used in combination with a polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid, if necessary.

The dicarboxylic acid component is usually at least one selected from aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, in particular, aliphatic dicarboxylic acids (saturated aliphatic dicarboxylic acids or derivatives capable of forming esters thereof, particularly adipic acid, Saturated C _3-14 aliphatic dicarboxylic acids such as suberic acid and sebacic acid) and alicyclic dicarboxylic acids (C _5-10 cycloalkane dicarboxylic acids such as cyclohexane dicarboxylic acid) are preferred.

  In the polyarylate-based resin, a dicarboxylic acid component containing at least an aromatic dicarboxylic acid is used, and the aromatic dicarboxylic acid may be used in combination with another dicarboxylic acid (aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid). Good. The ratio of the aromatic dicarboxylic acid to the other dicarboxylic acid is, for example, the former / the latter (molar ratio) = 100/0 to 10/90, preferably 100/0 to 30/70, more preferably 100/0 to 50. It may be about / 50.

  In the polyester resin, the ratio (molar ratio) between the dicarboxylic acid component and the polyol component (fluorene derivative, other diol component, etc.) is usually the former / the latter = 1.5 / 1 to 0.7 / 1, preferably It may be about 1.2 / 1 to 0.8 / 1 (particularly 1.1 / 1 to 0.9 / 1).

The weight average molecular weight Mw (polystyrene conversion) of the polyester resin is not particularly limited, and is, for example, 100 to 50 × 10 ⁴ , preferably 500 to 30 × 10 ⁴ (for example, 1000 to 20 × 10 ⁴ ), and more preferably 3000. About 30 × 10 ⁴ . In the case of an unsaturated polyester resin, the molecular weight per double bond may be 300 to 1000, preferably 350 to 800, and more preferably about 400 to 700. The terminal group of the polyester resin may be a hydroxyl group or a carboxyl group, and may be protected by a protecting group as necessary.

  The polyester resin is prepared by a conventional method, for example, a direct polymerization method (direct esterification method) or a transesterification method, and a polyol component (particularly a diol component) composed of a fluorene compound having a hydroxyl group and the dicarboxylic acid component. Can be produced by a condensation reaction.

(2) Polycarbonate-based resin As a polycarbonate-based resin containing a compound having a fluorene skeleton as a polymerization component, according to a conventional method, for example, at least the fluorene derivative (particularly 9,9-bis (monohydroxyphenyl) fluorene or its) A reaction between a polyol component (particularly a diol component) and phosgene composed of an alkylene oxide adduct or the like (phosgene method), or a polyol component composed of the fluorene compound having a hydroxyl group (diol component) and a carbonate ester And polycarbonate resins obtained by the above reaction (transesterification method).

  The polyol component (diol component) may be composed of a fluorene derivative alone, and a fluorene derivative and other diols (the diols exemplified in the section of the polyester resin, particularly aromatic diols and alicyclic diols) You may comprise. Other diols can be used alone or in combination of two or more. Among other diols, aromatic diols such as bisphenols such as bisphenol A, AD, and F are particularly preferable. The ratio between the fluorene derivative and the diol can be selected from the same range as in the case of the polyester resin.

The molecular weight of the polycarbonate resin is not particularly limited. For example, the weight average molecular weight is 1 × 10 ^{3 to} 100 × 10 ⁴ (for example, 1 × 10 ^{4 to} 100 × 10 ⁴ ), preferably 5 × 10 ³ to 50 × 10 ^4. (For example, 1 × 10 ⁴ to 50 × 10 ⁴ ), more preferably about 1 × 10 ^{4 to} 25 × 10 ⁴ (for example, 1 × 10 ⁴ to 10 × 10 ⁴ ).

(3) Polyurethane resin Polyol component (diol component) constituting a polyurethane resin containing a fluorene derivative as a polymerization component is a fluorene derivative having a hydroxyl group (9,9-bis (monohydroxyphenyl) fluorenes or alkylene thereof. Oxide adducts and the like) may be used alone or in combination with the diols exemplified in the section of the polyester resin together with the fluorene derivative. Furthermore, a diol component containing the fluorene derivative as a structural unit, for example, a polyester diol produced by a reaction of a diol component composed of 9,9-bis (monohydroxyphenyl) fluorene and a dicarboxylic acid component, 9,9- Polyether diol produced by the reaction of a diol component composed of bis (monohydroxyphenyl) fluorenes and an alkylene oxide can also be used as the diol component of the polyurethane resin. A diol component can also be used individually or in combination of 2 or more types. If necessary, the diol component may be used in combination with a polyol component such as triol.

  In the polyol component (diol component), the content of the fluorene derivative is, for example, 10 to 100 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol, based on the entire polyol component (diol component). % May be sufficient.

Examples of the diisocyanate compound constituting the polyurethane resin include aromatic diisocyanates [paraphenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), naphthalene diisocyanate (NDI), bis ( Isocyanatophenyl) methane (MDI), toluidine diisocyanate (TODI), 1,2-bis (isocyanatophenyl) ethane, 1,3-bis (isocyanatophenyl) propane, 1,4-bis (isocyanatophenyl) butane , Polymeric MDI, etc.], alicyclic diisocyanates [cyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc.], fat Diisocyanate diisocyanate compounds such as [hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI), etc.] and the like. These diisocyanate compounds can be used alone or in combination of two or more. If necessary, these diisocyanate compounds may be polyisocyanate compounds (for example, aliphatic triisocyanates such as 1,6,11-undecane triisocyanate methyloctane and 1,3,6-hexamethylene triisocyanate; bicycloheptane triisocyanate). Triisocyanate compounds such as alicyclic triisocyanates, etc.), monoisocyanate compounds (C _1-6 alkyl isocyanates such as methyl isocyanate; C _5-6 cycloalkyl isocyanates such as cycloalkyl isocyanate; C _6- such as phenyl isocyanate) ₁₀ aryl isocyanate and the like). The isocyanate compound includes derivatives such as multimers and modified products of the polyisocyanate compound.

  The polyurethane-based resin is used in a conventional manner, for example, 0.7 to 2.5 mol, preferably 0.8 to 2.2 mol, more preferably 0.9 to 2 mol per mol of the polyol component (diol component). It can be obtained by using it at a ratio of about 2 mol and urethanizing it. In addition, when a diisocyanate component of about 0.7 to 1.1 mol is used with respect to 1 mol of a diol component, a thermoplastic resin can be obtained, and an excess mol (for example, about 1.5 to 2.2 mol) is obtained. When a diisocyanate component is used, a thermosetting resin having a free isocyanate group at the terminal can be obtained.

(4) Acrylic resin An acrylic resin monomer (a (meth) acrylic monomer having a fluorene skeleton) is obtained by a reaction between the hydroxyl group-containing fluorene derivative and a carboxyl group-containing polymerizable monomer. May be obtained. As the polymerizable monomer having a carboxyl group, an unsaturated monocarboxylic acid, particularly (meth) acrylic acid, can be used, and cinnamic acid, crotonic acid, sorbic acid, maleic acid monoalkyl esters (monomethyl malate, etc.) Etc. may be used. Further, reactive derivatives such as acid chloride and C _1-2 alkyl ester may be used in place of the unsaturated carboxylic acid. These monomers may be used alone or in combination of two or more.

The acrylic resin is a homopolymer or copolymer of the (meth) acrylic monomer having the fluorene skeleton, and a copolymer of the (meth) acrylic monomer having the fluorene skeleton and another copolymerizable monomer. It may be a polymer. Examples of the copolymerizable monomer include carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (meth) acrylic acid esters [(meth) such as methyl (meth) acrylate Acrylic acid C _1-6 alkyl ester, etc.]; vinyl cyanides such as (meth) acrylonitrile; aromatic vinyl monomers such as styrene; vinyl carboxylic acid esters such as vinyl acetate; α-olefins such as ethylene and propylene Examples can be given. These copolymerizable monomers can be used alone or in combination of two or more.

  In addition, a monomer having a plurality of (meth) acryloyl groups [for example, (meth) acrylates of the 9,9-bis (hydroxyphenyl) fluorenes exemplified above (di (meth) acrylate, tetra (meth) acrylate, etc.)] Etc.] itself may be used as an acrylic resin (that is, thermosetting acrylic resin, oligomer (resin precursor)).

(5) Epoxy resin An epoxy resin (a monomer of an epoxy resin having a fluorene skeleton) may be obtained by a reaction between the fluorene derivative having a hydroxyl group and epichlorohydrin. Furthermore, the epoxy resin composition of an epoxy resin and the said fluorene derivative may be sufficient. Examples of the epoxy resin include glycidyl ether type epoxy resins [for example, epi-bis type epoxy resins; phenol type epoxy resins; brominated epoxy resins; glycol type epoxy resins (for example, bisphenols (bisphenol A, etc.) or hydrogenated products thereof] Reaction product of alkylene oxide adduct and epichlorohydrin); epoxy resin having alicyclic skeleton such as diglycidyl ether of alicyclic diol, dicyclopentadiene type epoxy resin; poly (glycidyloxyphenyl) alkane; Epoxy resins having a naphthalene skeleton (for example, diglycidyloxynaphthalenes such as bis (glycidyloxynaphthyl) C _1-6 alkanes), these di (glycidyloxy) naphthalenes are directly bonded or linking groups (for example, methylene group, ethylene Group etc. A glycidyl ether having a condensed ring skeleton such as an epoxy resin having a xanthene skeleton], a glycidyl amine type epoxy resin (for example, tetraglycidyl diaminodiphenylmethane, triglycidyl) linked via an alkylene group or an alkylidene group) Paraaminophenol, etc.), glycidyl ester type epoxy resins (for example, aromatic dicarboxylic acids (phthalic acid etc.) or hydrogenated products thereof (tetrahydrophthalic acid, hexahydrophthalic acid etc.) and epichlorohydrin, dimer acid Glycidyl esters), fluorene-containing epoxy compounds (fluorene-based epoxy resins) [for example, bisphenoxyethanol fluorenediglycidyl ether, bisphenol fluorenediglycidyl ether, etc. Fluorenes having phenolic hydroxyl groups as exemplified above or polyglycidyl ethers of adducts thereof with alkylene oxide], nitrogen-containing epoxy compounds (for example, triglycidyl isocyanurate, epoxy resin having hydantoin skeleton, N, N-diglycidyl-4 -Glycidyloxyaniline, etc.), peracetic acid-oxidized epoxy compounds, silicon-containing epoxy compounds, and the like.

(6) Polyimide resin (thermoplastic or thermosetting polyimide resin)
The polyamine component (diamine component) constituting the polyimide resin is a fluorene compound having an amino group [9,9-bis (aminophenyl) fluorenes such as 9,9-bis (monoaminophenyl) fluorenes in particular]. May be used alone or in combination with a diamine component. Examples of the diamine component include chain C _2-14 aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, and dodecanediamine; Cyclic C _6-14 amines such as isophoronediamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4-amino-3-methyldicyclohexyl) methane; metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, etc. C _6-20 aromatic diamine; C _{7 - 14} aromatic aliphatic diamines such as m- xylylenediamine, diamino phenyl ether, 2,2-bis (3,4 Bis (di-aminophenyl) alkanes such aminophenyl) propane can be exemplified. Diamines can be used alone or in combination of two or more.

  The ratio between the fluorene compound having an amino group and the diamine is the former / the latter (molar ratio) = 100/0 to 5/95, preferably 90/10 to 10/90, more preferably 80/20 to 20/80. Degree.

  Examples of the raw material polycarboxylic acids include tetracarboxylic acids or derivatives thereof, such as pyromellitic acid or anhydrides thereof, biphenyltetracarboxylic acid or anhydrides thereof, benzophenone tetracarboxylic acid or anhydrides thereof, and 2,2-bis (3 , 4-Dicarboxyphenyl) propane and other bis (dicarboxyphenyl) alkanes or anhydrides thereof, bis (carboxyphenyl) fluoroalkanes such as 2,2-bis (3,4-carboxyphenyl) hexafluoropropane, bismaleimide Etc. can be exemplified. These polycarboxylic acids can be used alone or in combination of two or more.

  In addition to the above-mentioned transparent resin, the transparent resin composition includes conventional additives such as stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), mold release agents, flame retardants, and bluing depending on the application. Agents, fluorescent brighteners, colorants, antistatic agents, antibacterial agents, lubricants, fillers, and the like. Furthermore, other transparent resins not having an aromatic ring may be included as long as the transparency and refractive index are not lowered.

[Molded body and manufacturing method thereof]
The molded body of the present invention can be obtained by applying a magnetic field to the transparent resin composition and orienting the aromatic ring. Specifically, the fluidized transparent resin composition is solidified while applying the magnetic field. Can be obtained through a step (hereinafter sometimes referred to as “application / solidification step”).

  Since the aromatic ring is a functional group having a high magnetic susceptibility, it has the property of responding to a magnetic field and orienting regularly (constant direction) along the magnetic field. In the present invention, by utilizing this property of the aromatic ring, the refractive index of the transparent resin is improved by orienting the aromatic ring by applying a magnetic field, but the orientation of the molecule (compound such as a resin) having the aromatic ring is improved. The ease depends on the fluidity of the molecule, and it is necessary to make the fluidity high. That is, it is preferable that the transparent resin composition at the time of applying a magnetic field is in a fluid state from the viewpoint of securing a degree of freedom for movement of molecules having an aromatic ring.

  The fluid state may be a solution state in which the transparent resin composition is dissolved or dispersed in a solvent, or may be a state in which the transparent resin composition is heated or melted or softened. Furthermore, when the transparent resin composition is a heat or photocurable resin, the fluid state may be a liquid state before curing. The application / solidification step may be performed on the resin composition that is the raw material before molding depending on the target molded body, but in order to maintain the orientation of the aromatic ring by the magnetic field, the process of manufacturing the molded body It is preferable to carry out as a solidification step in step 1 or a step on the obtained molded body (a step of solidifying again by heating and applying a magnetic field).

  Examples of the method for applying a magnetic field include a method for applying a magnetic field using a magnet such as a permanent magnet, an electromagnet, or a superconducting magnet. As a method using these magnets, for example, a static magnetic field (a magnetic field in which the magnitude of the magnetic field does not fluctuate over time) may be applied using a permanent magnet, or a dynamic magnetic field ( A method of applying a magnetic field in which the magnitude of the magnetic field periodically varies with time may be used. Among these methods, the method of applying a static magnetic field using a permanent magnet is preferable from the viewpoint of simplicity.

  Examples of permanent magnets include rare earth magnets such as neodymium magnets and samarium cobalt magnets, cast magnets such as alnico magnets, and ferrite magnets. Among these magnets, rare earth magnets such as neodymium magnets and cast magnets such as alnico magnets are preferable from the viewpoint of application efficiency.

  In the present invention, the applied magnetic field strength (residual magnetic flux density) is preferably, for example, 30 T (Tesla) or less from the viewpoint of industrial properties such as equipment. It may be about 01 to 10T, preferably 0.1 to 5T, more preferably about 0.3 to 3T (particularly 0.5 to 2T). The magnetic field strength means a magnetic flux density that remains even after the magnetic field is removed after the magnetic material is magnetized by an external magnetic field.

  A specific application method using a permanent magnet is, for example, that two plate-like permanent magnets are arranged so that the north and south poles face each other, and a transparent resin composition is formed in a magnetic field generated between the two magnets. It may be a method of fixing an object. The distance between the two magnets can be appropriately selected according to the magnetic field strength of the magnet, the size of the resin composition, and the like, and is, for example, about 1 to 100 mm, preferably 3 to 50 mm, and more preferably about 5 to 30 mm. The application time of the magnetic field is not particularly limited as long as the magnetic field is applied at the time of solidification of the resin. Usually, from the point of simplicity, the application of the magnetic field is started before the start of the flow state, and after the solidification is completed. Stop applying the magnetic field.

  As a method for producing a molded product, a conventional method (resin molding method, wet resin molding method using a solvent) can be selected according to the type of resin, for example, coating or casting method, casting method, extrusion molding. Methods, injection molding methods, injection compression molding methods, compression molding methods, transfer molding methods, blow molding methods, pressure molding methods, casting molding methods and the like can be used.

  As described above, the application / solidification step can be provided as various steps depending on the type of molding method. For example, a wet resin molding method (for example, a solution in which a resin composition is dissolved or dispersed in a solvent is applied). In the casting method or the like, the drying process for removing the solvent may be the application / solidification process. In the case of the wet resin molding method, it is only necessary to apply a magnetic field in a state where the solvent and the resin composition are mixed until the solvent is distilled off and the resin composition is completely solidified.

  In this case, usable solvents are conventional solvents such as hydrocarbons (aliphatic hydrocarbons such as pentane and hexane, alicyclic hydrocarbons such as cyclohexane, toluene, and the like depending on the type of transparent resin. Aromatic hydrocarbons such as xylene), halogenated solvents (haloalkanes such as dichloromethane, haloarenes such as monochlorobenzene), alcohols (such as alkyl alcohols such as methanol, ethanol, propanol), diols (ethylene glycol, Alkanediols such as propylene glycol, (poly) oxyalkylene glycols such as diethylene glycol and polyoxyethylene glycol), ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran), S (Acetic esters such as ethyl acetate), ketones (dialkyl ketones such as acetone and ethyl methyl ketone, cyclic ketones such as cyclopentanone and cyclohexanone), glycol ether esters (ethylene glycol monomethyl ether acetate) , Propylene glycol monomethyl ether acetate, cellosolve acetate, etc.), cellosolves (such as methyl cellosolve, ethyl cellosolve), carbitols (such as carbitol), etc. can be used. These solvents may be used alone or in combination of two or more.

  The proportion of the solvent may be in a range that does not impair the moldability, and the solid content concentration of the resin composition is, for example, 1 to 50% by weight, preferably 3 to 40% by weight, more preferably 5 to 30% by weight ( In particular, the ratio may be about 10 to 30% by weight.

  Such a solution is used for a coating or casting method, a casting method, or the like among the above-described molding methods, and is usually molded into a sheet by coating or casting on a substrate. As a casting or coating method, a conventional method such as a spin coating method, a dipping method, or a casting method can be used. Examples of the substrate include paper, cloth, plastic film, glass, quartz, ceramics, and metal.

  The applied liquid resin composition may be dried by heating or may be naturally dried. The temperature in the case of heating can be suitably selected according to the kind of solvent to be used, and is usually a temperature not higher than the boiling point of the solvent, for example, about 50 to 120 ° C., preferably about 60 to 100 ° C. The drying time is, for example, about 10 seconds to 30 minutes, preferably about 30 seconds to 20 minutes, and more preferably about 1 to 15 minutes. Thus, a highly transparent sheet | seat is obtained by peeling the solidified transparent resin composition from a base material after drying.

  When the resin composition is melted or softened by a resin molding method such as extrusion molding or injection molding, the application / solidification process may be a solidification process by cooling the melted resin composition. That is, an application / solidification step may be incorporated as one step of melt molding. Furthermore, as described above, when a thermoplastic resin is used, a magnetic field may be applied to the molded body obtained by reheating and melting or softening the obtained molded body. In this case, the molded body is once completed. Then, an application / solidification step is provided. In these application / solidification steps, the heating temperature is not particularly limited as long as the resin composition can be melted or softened. For example, the heating temperature may be near the glass transition temperature of the transparent resin, for example, the glass transition temperature of the transparent resin. When Tg is set, for example, Tg to Tg + 250 ° C., preferably Tg + 30 ° C. to Tg + 200 ° C., and more preferably about Tg + 50 ° C. to Tg + 150 ° C. In particular, in order to maintain the state of orientation by the magnetic field, the application of the magnetic field was continuously performed from the state of high fluidity to the state of complete solidification, and the solidified state (for example, the compact was cooled to room temperature). The application of the magnetic field is preferably stopped in the state).

  In the case where the transparent resin is a heat or photocurable resin, for example, methods such as casting, compression molding, injection molding and the like can be used in addition to the application or casting method similar to the above-described solution. The application / solidification step in the heat or photocurable resin may be provided as a curing step by irradiation with heat or light. That is, while irradiating heat or light to cure the liquid curable resin composition, a magnetic field may be applied to orient the aromatic ring of the resin composition.

  In the obtained molded body, the orientation state of the aromatic ring is, for example, when the compound having an aromatic ring emits light (usually fluorescence), the fluorescence spectrum of the molded body to which a magnetic field is applied and the magnetic field is applied. It can be evaluated by comparing with the fluorescence spectrum of the molded product without. This evaluation is possible because the light absorption and emission characteristics of the aromatic ring compound have anisotropy inside the molecule, and macroscopically in a random state where the aromatic ring compound is not oriented. While the anisotropy of individual molecules is canceled, when the aromatic ring compound is oriented, it becomes macroscopically anisotropic. As a result, a remarkable difference in fluorescence intensity occurs between the state where the aromatic ring is not oriented and the state where the aromatic ring is oriented.

  With regard to the degree of orientation of the molded article of the present invention, for example, in the fluorescence spectrum, the intensity of the fluorescence spectrum emitted when irradiated with ultraviolet rays (for example, ultraviolet rays having a wavelength of 330 nm) is greatly reduced compared to before the magnetic field is applied. Specifically, the fluorescence spectrum after application of the magnetic field is reduced by, for example, 30% or more, preferably 50% or more, compared to the fluorescence spectrum before application of the magnetic field.

  Since the aromatic ring is oriented in a certain direction, the molded article of the present invention has high transparency and refractive index. Although the refractive index of a molded object changes according to the kind of resin, it is 1.56 or more (for example, about 1.56-1.7), Preferably it is 1.57-1.69, More preferably, it is 1. It is about 60 to 1.68 (particularly 1.61 to 1.67). Furthermore, in the present invention, the refractive index is increased by applying a magnetic field, and is, for example, 0.001 or more, preferably 0.005 to 0.1, more preferably 0.01 to 0.08 (particularly compared to the application). 0.02 to 0.05).

  The light transmittance of the molded article of the present invention is 70% or more (about 70 to 99%), preferably 75% or more (for example, about 75 to 95%), more preferably 80% or more under the condition of a thickness of 2 mm. (For example, about 80 to 90%).

  Since the molded article of the present invention has excellent characteristics (particularly transparent, high optical characteristics such as high refractive index and low birefringence), an optical lens, an optical film, an optical sheet, an optical disk, and a pickup It can be suitably used for lenses, holograms, liquid crystal films, organic EL (electroluminescence) films, and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
Fluorene ester resin (trade name “OKP4”, refractive index 1.61 manufactured by Osaka Gas Chemical Co., Ltd.) was dissolved in cyclohexanone to prepare a 15 wt% solution. The prepared coating solution was applied on a quartz substrate (25 × 25 mm) by spin coating (2500 rpm), then held in a magnetic field using a permanent magnet and heated and dried at 80 ° C. for 10 minutes. A thin film molded body having a thickness of about 1.5 μm was prepared.

  In addition, the magnetic field using a permanent magnet is in a magnetic field generated by facing two square neodymium magnets (length 40 mm × width 40 mm × 10 mm) having a magnetic field strength of about 1.3 T with their surfaces facing each other at intervals of up to 10 m. A thin film coated on the substrate was set and applied with a magnetic field.

Comparative Example 1
A thin film compact was produced in the same manner as in Example 1 except that it was not applied in a magnetic field.

(Evaluation of orientation)
The degree of orientation was evaluated based on the intensity of the fluorescence spectrum. That is, when the OKP4 resin is irradiated with ultraviolet rays, fluorescence derived from the fluorene ring is emitted. The intensity of the fluorescence at this time reflects the degree of orientation of the fluorene ring. When the fluorene ring is oriented, the intensity of the fluorescence changes. In FIG. 1, the fluorescence spectrum which the molded object produced in Example 1 and the comparative example 1 emitted by the ultraviolet irradiation was shown. As an excitation spectrum for emitting fluorescence, ultraviolet rays having a wavelength of 275 nm were irradiated. In Comparative Example 1 and Example 1 which are considered not to have molecular orientation in the film, the fluorescence intensity clearly changed, and in Example 1, it was shown that the fluorene ring was oriented.

(Evaluation of refractive index)
The value of the refractive index was obtained by interferometry. That is, it calculated | required from the interference fringe of 600 nm vicinity among the interference fringes seen in the transparent region (330-800 nm) of an electronic absorption spectrum. The obtained refractive index was 1.65 in Example 1 and 1.55 in Comparative Example 1. Thus, it was clearly shown that the refractive index is improved by applying the magnetic field.

3 is a chart showing fluorescence spectra in molded articles of Example 1 and Comparative Example 1. 3 is a chart showing electron absorption spectra in molded articles of Example 1 and Comparative Example 1.

Claims (9)

  A molded article composed of a transparent resin composition containing an aromatic ring, wherein the aromatic ring is oriented by applying a magnetic field.   The molded article according to claim 1, wherein the aromatic ring is a fluorene ring. The molded product according to claim 1 or 2, wherein the transparent resin composition is composed of a transparent resin obtained by using the fluorene derivative represented by the formula (1).

(In the formula, ring Z ¹ and ring Z ² are aromatic hydrocarbon rings, R ^1a , R ^1b and R ² are the same or different and each represents a substituent. K1 and k2 are the same or different and represent an integer of 0 to 4; M is 0 or an integer of 1 or more, and n is an integer of 1 or more)   The molded product according to any one of claims 1 to 3, wherein the intensity of a fluorescence spectrum emitted when irradiated with ultraviolet rays is smaller than that before application of a magnetic field.   The manufacturing method of the molded object in any one of Claims 1-4 including the process of solidifying the transparent resin composition of a fluid state, applying a magnetic field.   The manufacturing method of Claim 5 which solidifies the solution containing a transparent resin composition by removal of a solvent.   The production method according to claim 5, wherein the transparent resin composition melted or softened by heating is solidified by cooling.   A method of increasing the refractive index of a transparent resin composition by applying a magnetic field to a transparent resin composition containing an aromatic ring and orienting the aromatic ring.   A transparent resin composition for optical use, comprising a fluorene ring, wherein the refractive index can be improved by applying a magnetic field.

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