JP5749927B2 - Polyarylate resin having fluorene skeleton - Google Patents

Description

  The present invention relates to a novel polyarylate having a specific fluorene skeleton (specifically, a 9,9-bis (fused polycyclic aryl) fluorene skeleton).

  Bisphenol compounds having a fluorene skeleton are known to have properties such as high heat resistance, and polyarylates using such bisphenol compounds have also been developed.

  For example, JP-A-2000-79768 (Patent Document 1) discloses 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl) as a heat-resistant protective lubricating layer of a thermal transfer recording sheet. It has been disclosed that polyarylate containing -4-hydroxyphenyl) fluorene or the like as a bisphenol compound is contained. However, the glass transition temperature (Tg) of the polyarylate obtained in this document is 288 ° C. at the maximum, which is not sufficient in terms of heat resistance. Further, the polyarylate of this document has a relatively high refractive index, but it is desired to develop a polyarylate having an improved refractive index and excellent optical characteristics.

  Attempts have also been made to obtain polyallylate having higher heat resistance using a bisphenol compound containing a halogen atom in the fluorene skeleton. JP 2002-145998 A (Patent Document 2) discloses 9,9-bis (4-hydroxy-3-chloro-5-methylphenyl) fluorene, 9,9-bis (4-hydroxy-) as bisphenol compounds. Polyarylate using 3,5-dibromophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene and the like is disclosed. JP-A-2006-89541 (Patent Document 3) discloses 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromo). Poly having a skeleton derived from a halogen-containing bisphenol such as phenyl) fluorene and a skeleton derived from at least two dicarboxylic acids selected from 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and terephthalic acid Arylate is disclosed.

  In these documents, highly heat-resistant polyarylate having a glass transition temperature exceeding 300 ° C. is obtained. However, such polyarylate contains halogen, is easily colored, and may cause environmental problems.

  JP-A 2007-99741 (Patent Document 4) discloses a bisnaphthol compound having a fluorene skeleton such as 9,9-bis (hydroxynaphthyl) fluorene. And although this literature describes that such a bisnaphthol compound can be used as a resin raw material, it does not describe at all about the details.

JP 2000-79768 A (claims, paragraph [0022], examples) JP 2002-145998 A (Claims, Examples) JP 2006-89541 A (Claims, Examples) JP 2007-99741 A (claim, paragraph [0064])

  Accordingly, an object of the present invention is to provide a novel polyarylate having a condensed polycyclic arylfluorene skeleton (particularly a naphthylfluorene skeleton).

  Another object of the present invention is to provide a halogen-free polyarylate capable of satisfying both high heat resistance and high refractive index even without having a halogen atom.

  Still another object of the present invention is to provide a polyarylate excellent in solubility in a solvent despite having high heat resistance and high refractive index.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a specific fluorenediol compound having a condensed polycyclic arene (particularly naphthalene) skeleton [9,9-bis (hydroxy condensed polycyclic) as a diol component. A novel polyarylate can be obtained by combining such a fluorenediol compound with an aromatic dicarboxylic acid component, and using such a compound. Even though the polymer chain or polymer skeleton has substantially no halogen, it has high heat resistance and a high refractive index, and it is surprisingly versatile despite having such characteristics. The present invention was completed by finding that it can be dissolved in other solvents (for example, tetrahydrofuran) and is excellent in practicality. .

  That is, the polyarylate of the present invention is a diol component containing a compound (a) having a 9,9-bis (hydroxy-fused polycyclic aryl) fluorene skeleton (for example, 9,9-bis (hydroxynaphthyl) fluorenes). A polyarylate having A) and a dicarboxylic acid component (B) containing an aromatic dicarboxylic acid component as polymerization components. In particular, the compound (a) may be a compound having no halogen.

  The polyarylate of the present invention has characteristics such as high heat resistance and a high refractive index even without halogen (or halogen atom). For example, halogen (or halogen atom) is contained in the polymer skeleton. It may be a polymer (polyarylate) having a refractive index at a temperature of 25 ° C., a wavelength of 589 nm of 1.68 or more, and a glass transition temperature of 300 ° C. or more.

  The polyarylate of the present invention may have a relatively low molecular weight (for example, a number average molecular weight of 30000 or less) from the viewpoint of handling properties.

  In a typical polyarylate of the present invention, the compound (a) is 9,9-bis (hydroxynaphthyl) fluorene, and the aromatic dicarboxylic acid component is a benzenedicarboxylic acid component, a naphthalenedicarboxylic acid component, and Contains at least one selected from biphenyldicarboxylic acid components, has no halogen in the polymer backbone, has a refractive index of 1.7 or higher at a temperature of 25 ° C. and a wavelength of 589 nm, and has a glass transition temperature of 310 ° C. or higher. And polyarylate having a number average molecular weight of 25000 or less.

  The present invention also includes a method for producing the polyarylate by reacting the diol component (A) and the dicarboxylic acid component (B). In this method, a dicarboxylic acid halide may be used as the dicarboxylic acid component (B), and solution polymerization may be performed in the presence of a base (for example, a tertiary amine such as pyridine). The usage-amount of a base may be about 1-10 molar equivalent with respect to 1 mol of hydroxyl groups of the said diol component (A), for example.

  The present invention also includes a molded body (for example, an optical film) formed of the polyester resin. Such a molded body may be a stretched film.

  In the present specification, unless otherwise specified, the “dicarboxylic acid component” includes not only dicarboxylic acids but also ester-forming derivatives of dicarboxylic acids (for example, lower alkyl esters, acid halides, acid anhydrides, etc.). Used to include.

  In the present invention, a novel polyarylate having a condensed polycyclic aryl fluorene skeleton (particularly a naphthyl fluorene skeleton) can be obtained by using a specific fluorenediol compound. Such a novel polyarylate can achieve both high heat resistance and high refractive index, and in particular, such characteristics can be obtained even if the polymer chain or polymer skeleton has no halogen, that is, halogen-free polyarylate. This can also be realized with arylate. Furthermore, the polyarylate of the present invention is excellent in solubility in a solvent (solvent solubility) and practicality despite having high heat resistance and high refractive index. Such a polyarylate of the present invention has high heat resistance and excellent optical properties (for example, high refractive index, low birefringence, etc.), and thus molded articles such as films (particularly optical films). Is suitable for forming.

[Polyarylate]
The polyarylate (aromatic polyester resin) of the present invention is a resin having a specific diol component and a specific dicarboxylic acid component as polymerization components [or a skeleton (or residue) derived from a specific diol component and a specific dicarboxylic acid component. A resin having a skeleton (or a residue) derived therefrom.

(Diol component)
The diol component (sometimes referred to as diol component (A)) is a compound having a 9,9-bis (hydroxy-fused polycyclic aryl) fluorene skeleton (compound (a), diol having a fluorene skeleton, etc.) At least. As long as such a compound (a) has a 9,9-bis (hydroxy-fused polycyclic aryl) fluorene skeleton, it is substituted with fluorene or a condensed polycyclic aryl group substituted at the 9-position of fluorene. It may have a group (such as a substituent described later).

  Such a compound (a) may typically be a compound represented by the following formula (1).

(In the formula, ring Z represents a condensed polycyclic arene ring, R ¹ represents a substituent, R ² represents a substituent, m is an integer of 0 to 4, and n is an integer of 0 or more.)
In the above formula (1), examples of the condensed polycyclic arene (or condensed polycyclic aromatic hydrocarbon) ring represented by ring Z include a condensed bicyclic arene ring (for example, an indene ring, a naphthalene ring, etc.) C _8-20 fused bicyclic arene rings, preferably C _10-16 fused bicyclic arene rings), fused tricyclic arene rings (eg, anthracene ring, phenanthrene ring, etc.) Examples include arene rings. Preferred examples of the condensed polycyclic arene ring include a naphthalene ring and an anthracene ring, and a naphthalene ring is particularly preferable. The two rings Z may be the same or different rings, and may usually be the same ring.

Examples of the group R ¹ include a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [eg, alkyl group, aryl group (C _6-10 aryl group such as phenyl group), etc.] Non-reactive substituents such as, for example, are often groups that are not halogen atoms such as alkyl groups. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, such as _{C 1-12} alkyl group _{(e.g., C 1-8} alkyl groups, especially methyl groups, such as t- butyl group _{C 1- 4} alkyl group) and the like. In addition, when m is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number m is 0 to 1, in particular 0. In the two benzene rings constituting the fluorene, the substitution number m may be the same as or different from each other.

  In addition, in the said Formula (1), the substituted position of a hydroxy group is not specifically limited, What is necessary is just to substitute to the appropriate substituted position of the ring Z. In particular, in the condensed polycyclic arene ring Z, the hydroxy group is at least substituted with a hydrocarbon ring different from the hydrocarbon ring bonded to the 9th position of fluorene (for example, the 5th and 6th positions of the naphthalene ring). There are many cases.

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, Preferably a C _1-8 alkyl group, more preferably a C _1-6 alkyl group, etc.), a cycloalkyl group (C _5-8 cycloalkyl group such as a cyclohexyl group, preferably a C _5-6 cycloalkyl group, etc.) An aryl group (for example, a C _6-14 aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, preferably a C _6-10 aryl group, more preferably a C _6-8 aryl group), an aralkyl group ( a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group) hydrocarbon group such as; alkoxy group (methoxy group, an ethoxy group _{C 1-8} alkoxy group, such as preferably _{C 1-6} alkoxy groups), _{C 6,} such as _{C 5-10,} such as cycloalkyl group), an aryloxy group (phenoxy group such as cycloalkoxy group (hexyloxy group cycloheteroalkyl _-10 aryloxy group), aralkyloxy group (for example, C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group) and the like -OR ³ [wherein R ³ represents a hydrocarbon group (above-mentioned) An exemplary hydrocarbon group). An alkylthio group (a C _1-8 alkylthio group such as a methylthio group or an ethylthio group, preferably a C _1-6 alkylthio group), a cycloalkylthio group (such as a C _5-10 cycloalkylthio group such as a cyclohexylthio group), A group —SR ³ (wherein R _{6 is an} arylthio group (C _6-10 arylthio group such as a thiophenoxy group)), an aralkylthio group (eg, a C _6-10 aryl-C _1-4 alkylthio group such as a benzylthio group) ³ is the same as above.); Acyl group (C _1-6 acyl group such as 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) Dialkylamino groups such as amino groups) and the like.

Preferred group R ² is a group that is not a halogen atom, such as a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (For example, a C _6-10 aryl group), an aralkyl group (for example, a C _6-8 aryl-C _1-2 alkyl group), an alkoxy group (C _1-4 alkoxy group, etc.), and the like. In particular, R ² is preferably 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.

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

  The representative compound (a) (or the compound represented by the formula (1)) includes a halogen-free compound such as 9,9-bis (hydroxynaphthyl) fluorene [for example, 9,9-bis ( 9,9-bis (hydroxynaphthyl) fluorenes (or 9-fluorenylidene-dinaphthols) such as 6-hydroxy-2-naphthyl) fluorene, 9,9-bis (5-hydroxy-1-naphthyl) fluorene, etc.] Is included.

  These compounds (a) may be used alone or in combination of two or more.

In addition, a diol component may be comprised only with a compound (a), and if it is a range which does not impair the effect of this invention, it may contain the aromatic diol component (the aromatic diol component which is not a compound (a)). Good. Examples of the aromatic diol component include dihydroxyarene (hydroquinone, resorcinol and the like), biphenols (biphenol and the like), bisphenols (for example, bis (hydroxyphenyl) C _1-10 alkane such as bisphenol A), compound (a A diol having a fluorene skeleton [e.g., 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene (e.g., 9,9-bis (4-hydroxy-3-) And the like wherein the ring Z is a benzene ring in the above formula (1) such as 9,9-bis (C _1-4 alkyl-hydroxyphenyl) fluorene such as methylphenyl) fluorene]. The aromatic diol components may be used alone or in combination of two or more.

  When the aromatic diol component is used in combination, the ratio of the compound (a) to the aromatic diol component is, for example, the former / the latter (molar ratio) = 99.9 / 0.1-50 / 50, preferably 99.5. /0.5 to 60/40, more preferably about 99/1 to 70/30 (for example, 97/3 to 80/20).

Further, the diol component may contain a non-aromatic diol component as long as it does not impair the effects of the present invention. Such non-aromatic diol components include aliphatic diols [for example, alkanediols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol). , 1,3-butanediol, 1,4-pentanediol, 1,5-pentanediol, 1,3-pentanediol, C _2-10 alkanediol such as neopentyl glycol, preferably C _2-6 alkanediol, More preferably, C _2-4 alkanediol), polyalkanediol (eg, di- or tri-C _2-4 alkanediol such as diethylene glycol, dipropylene glycol, triethylene glycol, etc.), etc.], alicyclic diol [eg, cyclohexane Alkanediol (eg cyclohexanedi) C _5-8 cycloalkanediols such as all), di (hydroxyalkyl) cycloalkanes (eg, di (hydroxyC _1-4 alkyl) C _5-8 cycloalkanes such as cyclohexanedimethanol, etc.)], aromatic aliphatic Diols [for example, di (hydroxyC _1-4 alkyl) C _6-10 arenes such as 1,4-benzenedimethanol and 1,3-benzenedimethanol] and the like. These non-aromatic diol components may be used alone or in combination of two or more.

  When the non-aromatic diol component is used, the ratio of the compound (a) to the non-aromatic diol component is, for example, the former / the latter (molar ratio) = 99.9 / 0.1 to 70/30, preferably 99 It may be about 8 / 0.2 to 80/20, more preferably about 99.5 / 0.5 to 90/10 (for example, 99/1 to 95/5).

  In the diol component, the ratio of the compound (a) is, for example, 50 mol% or more (for example, about 60 to 100 mol%), preferably 70 mol% or more (for example, 80 to 100 mol%) with respect to the entire diol component. Degree), more preferably 90 mol% or more (for example, about 95 to 100 mol%).

  If necessary, in addition to the diol component, a polyol component having 3 or more hydroxyl groups [alkane polyol (eg, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, etc.)] may be added in a small amount [eg, diol 10 mol% or less (for example, 0.01 to 8 mol%, preferably 0.05 to 5 mol%, more preferably about 0.1 to 3 mol%) based on the total amount of the component and the polyol component] May be.

  The diol component (and the polyol component) may usually be a compound that does not have halogen or does not introduce halogen into polyarylate.

  The diol component used in the reaction may be an ester (eg, diol acetate) or the like in addition to the diol, depending on the polymerization method.

(Dicarboxylic acid component)
The dicarboxylic acid component (sometimes referred to as dicarboxylic acid component (B)) contains at least an aromatic dicarboxylic acid component.

  Examples of the aromatic dicarboxylic acid component include aromatic dicarboxylic acids and ester-forming derivatives of aromatic dicarboxylic acids.

Examples of the aromatic dicarboxylic acid include arene dicarboxylic acids [eg, benzene dicarboxylic acid (terephthalic acid, isophthalic acid, phthalic acid; C _1-4 alkylbenzene dicarboxylic acid such as methyl terephthalic acid, 4-methylisophthalic acid, etc.), naphthalene, etc. Dicarboxylic acids (for example, 2 in different rings such as 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, etc. Naphthalene dicarboxylic acid having two carboxyl groups; naphthalene dicarboxylic acid having two carboxyl groups in the same ring such as 1,2-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid), anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, etc. C _6-14 arene-dicarboxylic acid, preferably C _6-12 arene-dicarboxylic acid, more preferably C _6-10 arene-dicarboxylic acid and the like], arylarene dicarboxylic acid [for example, biphenyl dicarboxylic acid (2,2′- C _6-10 aryl C _6-10 arene dicarboxylic acid] such as biphenyl dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, etc.], diaryl alkane dicarboxylic acid [for example, diphenyl alkane dicarboxylic acid (eg, 4,4′-diphenylmethane) DiC _6-10 aryl C _1-6 alkane-dicarboxylic acid] such as diphenyl C _1-4 alkane-dicarboxylic acid such as dicarboxylic acid], diaryl ketone dicarboxylic acid [eg, diphenyl ketone dicarboxylic acid (4,4′- Diphenyl ketone dicarboxylic acid, etc. Di _{C 6-10} aryl ketones, such as - dicarboxylic acid, dicarboxylic acid {e.g. having a fluorene skeleton, 9,9-bis (carboxyalkyl) fluorene [e.g., 9,9-bis 9 such as (carboxymethyl) fluorene, 9-bis (carboxyC _1-4 alkyl) fluorene and the like], 9,9-bis (carboxyaryl) fluorene [for example, 9,9-bis (carboxyC) such as 9,9-bis (4-carboxyphenyl) fluorene. _6-10 aryl) fluorene], dicarboxyfluorene (eg, 2,7-dicarboxyfluorene), 9,9-dialkyl-dicarboxyfluorene (eg, 2,7-dicarboxy-9,9-dimethylfluorene) _{9,9-C 1-10} alkyl - dicarboxylate fluorene) and the like} ani It is.

Examples of the ester-forming derivative include esters {eg, alkyl esters [eg, lower alkyl esters such as methyl ester, ethyl ester (eg, C _1-4 alkyl ester, particularly C _1-2 alkyl ester], etc.}}. , Acid halides (acid chlorides, etc.), acid anhydrides, etc. The ester-forming derivatives may be monoesters (half esters) or diesters, monoacid halides or dihalides, and aromatic dicarboxylic acids. The acid component can be selected depending on the production method of polyarylate, but an acid halide of an aromatic dicarboxylic acid may be used in a solution polymerization method, an interfacial polymerization method, or the like.

  The aromatic dicarboxylic acid components may be used alone or in combination of two or more.

  Typical dicarboxylic acid components include benzene dicarboxylic acid components (terephthalic acid component, isophthalic acid component, etc.), naphthalene dicarboxylic acid components, biphenyl dicarboxylic acid components, and the like.

  In addition, the aromatic dicarboxylic acid component may particularly include a polycyclic aromatic dicarboxylic acid component. When the aromatic dicarboxylic acid component is composed of a polycyclic aromatic dicarboxylic acid component, the combination with the compound (a) can increase the refractive index of the polyarylate and further improve the optical properties of the polyarylate.

Examples of the polycyclic aromatic dicarboxylic acid component include polycyclic aromatic dicarboxylic acids and ester-forming derivatives thereof (such as the derivatives exemplified above). As the polycyclic aromatic dicarboxylic acid, among the aromatic dicarboxylic acids, a condensed polycyclic aromatic dicarboxylic acid (for example, naphthalenedicarboxylic acid, anthracene dicarboxylic acid, dicarboxyfluorene (full orange carboxylic acid), 9,9- Condensed polycyclic C _10-24 arene-dicarboxylic acid such as dialkyl-dicarboxyfluorene, preferably condensed polycyclic C _10-16 arene-dicarboxylic acid, more preferably condensed polycyclic C _10-14 arene-dicarboxylic acid ), Arylarene dicarboxylic acids (eg, biphenyl dicarboxylic acid), diarylalkane dicarboxylic acids (eg, 4,4′-diphenylmethane dicarboxylic acid), diaryl ketone dicarboxylic acids (eg, diphenyl ketone dicarboxylic acid), 9,9-bis (carboxyl) Alkyl) full Examples include olene and 9,9-bis (carboxyaryl) fluorene.

  These polycyclic aromatic dicarboxylic acid components may be used alone or in combination of two or more.

A preferable polycyclic aromatic dicarboxylic acid component is a condensed polycyclic aromatic dicarboxylic acid component (for example, a condensed polycyclic C _10-16 arene-dicarboxylic acid) component, and a naphthalenedicarboxylic acid component is particularly preferable.

  The ratio of the polycyclic aromatic dicarboxylic acid component is, for example, 10 mol% or more (for example, about 15 to 100 mol%), preferably 20 mol% or more (for example, 25 to 25 mol%) with respect to the entire aromatic dicarboxylic acid component. About 100 mol%), more preferably 30 mol% or more (for example, about 35 to 100 mol%), particularly about 40 to 100 mol% (for example, 45 to 100 mol%), usually 40 to 100 mol%. It may be about mol%.

The dicarboxylic acid component may contain a non-aromatic dicarboxylic acid component as long as the effects of the present invention are not impaired. Such non-aromatic dicarboxylic acid components include aliphatic dicarboxylic acid components [for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid. , Saturated aliphatic dicarboxylic acid components (eg, alkane dicarboxylic acid components such as C _2-12 alkanedicarboxylic acid components) such as dodecanedicarboxylic acid, and ester-forming derivatives thereof (such as those exemplified above)], alicyclic Dicarboxylic acids [eg, cycloalkane dicarboxylic acids (eg, C _5-10 cycloalkane-dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid), di- or tricycloalkane dicarboxylic acids (eg, decalin dicarboxylic acid, norbornane dicarboxylic acid, Adamantanedicarboxylic acid, tri Black like decanedicarboxylic acid), such as a saturated alicyclic dicarboxylic acid component such as ester-forming derivatives thereof (such as the exemplary derivative)] and the like. These non-aromatic dicarboxylic acid components may be used alone or in combination of two or more.

  When the non-aromatic dicarboxylic acid component is used, the ratio of the aromatic dicarboxylic acid component to the non-aromatic dicarboxylic acid component is, for example, the former / the latter (molar ratio) = 99.9 / 0.1 to 70/30, Preferably, it may be about 99.8 / 0.2 to 80/20, more preferably about 99.5 / 0.5 to 90/10 (for example, 99/1 to 95/5).

  In the dicarboxylic acid component, the ratio of the aromatic dicarboxylic acid component is, for example, 50 mol% or more (for example, about 60 to 100 mol%), preferably 70 mol% or more (for example, 80 to 80%) with respect to the entire dicarboxylic acid component. About 100 mol%), more preferably 90 mol% or more (for example, about 95 to 100 mol%).

If necessary, in addition to the dicarboxylic acid component, other acid components (carboxylic acid components) may be combined. Examples of such acid components include unsaturated carboxylic acid components {eg, unsaturated aliphatic dicarboxylic acids (eg, C _2-10 alkene-dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid), unsaturated fats, etc. Cyclic dicarboxylic acids [cycloalkane dicarboxylic acids (eg C _5-10 cycloalkene-dicarboxylic acids such as cyclohexene dicarboxylic acid), di- or tricycloalkene dicarboxylic acids (eg norbornene dicarboxylic acid etc.)], ester formation of these Etc.} and polycarboxylic acid components having 3 or more carboxyl groups (for example, aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid, ester-forming derivatives thereof, etc.). These other acid components may be used alone or in combination of two or more.

  In addition, when using another acid component, the usage-amount of another acid component is a small amount [For example, 10 mol% or less (for example, 0.01-8 mol% with respect to the total amount of a dicarboxylic acid component and another acid component) , Preferably 0.05 to 5 mol%, more preferably about 0.1 to 3 mol%)].

  The dicarboxylic acid component (and other acid components) is usually a compound that does not have halogen or does not introduce halogen into polyarylate (that is, does not include halogen derived from the acid halide group of the dicarboxylic acid component). Also good.

(Resin characteristics and manufacturing method)
The polyarylate of the present invention is a resin having the diol component (A) and the dicarboxylic acid component (B) as polymerization components (or the dicarboxylic acid component (A) and the diol component (B) are polymerized), Typically, it is a resin having at least a unit (repeating unit) represented by the following formula (2).

(In the formula, L represents a residue of an aromatic dicarboxylic acid component (a group obtained by removing a carboxyl group or an ester-forming group (ester group, acid halide group, etc.) from an aromatic dicarboxylic acid component), Z, R ¹ , R ² , m and n are the same as above.)
Such polyarylate is excellent in various properties (particularly optical properties). For example, since the polyarylate of the present invention has a 9,9-bis (hydroxy-fused polycyclic aryl) fluorene skeleton, it has a very high refractive index and high heat resistance.

  The refractive index of the polyarylate of the present invention is, for example, at a temperature of 25 ° C. and a wavelength of 589 nm, 1.65 or more (for example, about 1.67 to 1.85), preferably 1.68 or more (for example, 1.69 to 1.8), more preferably 1.7 or more (for example, about 1.71 to 1.75). In particular, by selecting the type of dicarboxylic acid component (for example, composed of an aromatic dicarboxylic acid component such as a polycyclic aromatic dicarboxylic acid component), the refractive index at a wavelength of 589 nm is 1.72 or more (for example, 1 .72 to 1.8, preferably about 1.73 to 1.75).

  The glass transition temperature (Tg) of the polyarylate of the present invention is, for example, 280 ° C. or higher (eg, 290 to 450 ° C.), preferably 300 ° C. or higher (eg, 305 to 400 ° C.), more preferably 310 ° C. or higher. (For example, about 310-380 degreeC) may be sufficient, and it can also be 320 degreeC or more (for example, about 325-400 degreeC, Preferably it is 330-380 degreeC, More preferably, it is about 335-360 degreeC).

  The polyarylate of the present invention usually does not have (substantially) halogen (halogen atom) in the polymer skeleton (or in the polymer chain). The polyarylate of the present invention has such high heat resistance and high refractive index as described above even if it does not contain such halogen.

  The number average molecular weight (Mn) of the polyarylate of the present invention can be selected from the range of, for example, about 5000 to 200000, for example, 6000 to 100,000, preferably 7000 to 80000, more preferably 8000 to 50000 (for example, 9000 to 40000). ) Degree. In addition, although the reason is not certain, the polyarylate of the present invention can be used as a polymer even if it has a relatively low molecular weight, while it is easy to increase the viscosity even in the molecular weight range of ordinary polymers. Therefore, in the present invention, the number average molecular weight is particularly 30000 or less (for example, 7000 to 28000), preferably 25000 or less (for example, 8000 to 24000), more preferably 23000 or less (for example, 9000 to 22000), particularly 20000 or less. You may use suitably the polyarylate (for example, about 10,000-20000). By adjusting to such a molecular weight, it is possible to obtain a polyarylate having characteristics such as high heat resistance and high refractive index without impairing handling properties. The molecular weight of the polymer can be adjusted by selecting the polymerization conditions (polymerization time, polymerization temperature, charge ratio of diol component and dicarboxylic acid component, etc.).

  Further, the molecular weight distribution (Mw / Mn) of the polyarylate of the present invention may be, for example, 1 to 10, preferably 1.2 to 8, and more preferably about 1.3 to 5.

  Furthermore, the polyarylate of the present invention is relatively excellent in solvent solubility despite having a rigid skeleton derived from the compound (a) and the aromatic dicarboxylic acid component. For example, the polyarylate of the present invention includes ethers (eg, tetrahydrofuran), hydrocarbons (aromatic hydrocarbons such as toluene), amides (eg, N, N-dimethylformamide), ketones (eg, , Cyclic ketones such as cyclopentanone and cyclohexanone), and halogen-based solvents (halogenated hydrocarbons such as methylene chloride and chloroform). Therefore, the polyarylate of the present invention is excellent in practicality while being a resin having characteristics such as high heat resistance and high refractive index.

  The polyarylate of the present invention can be produced by reacting (polymerizing or condensing) the diol component (A) and the dicarboxylic acid component (B). The polymerization method (manufacturing method) can be appropriately selected according to the type of dicarboxylic acid component to be used and the like, and is a conventional method such as a melt polymerization method (a method in which a diol component and a dicarboxylic acid component are polymerized under melt mixing). Examples thereof include a solution polymerization method and an interfacial polymerization method. Typical methods are a solution polymerization method and an interfacial polymerization method, and a preferred method is a solution polymerization method. In the solution polymerization method and interfacial polymerization method, a dicarboxylic acid halide (such as a dihalide) can be suitably used as the dicarboxylic acid component.

  In the reaction, the proportion of the diol component (A) and the dicarboxylic acid component (B) used may be a theoretical ratio or a stoichiometric ratio (that is, the former / the latter (molar ratio) = 1), depending on the polymerization method. If necessary (for example, for adjusting the molecular weight), the other may be used in excess. The ratio (molar ratio) between the diol component (A) and the dicarboxylic acid component (B) is generally the former / the latter (molar ratio) = 2/1 to 1/2, preferably including the case of excessive use. May be about 1.5 / 1 to 1 / 1.5, more preferably about 1.2 / 1 to 1 / 1.2 (for example, 1.1 / 1 to 1 / 1.1).

  In the reaction, the ratio (preparation ratio) of the compound (a) in the diol component (A) and the aromatic dicarboxylic acid component in the dicarboxylic acid component (B) is usually the same as the range described in the above-mentioned polyarylate. However, if necessary, an excess amount or a proportion less than the proportion in the polyarylate may be used. In addition, you may perform reaction in presence of a molecular weight modifier (for example, a monool component, a monocarboxylic acid component, etc.) as needed.

The reaction may be performed in the presence of a catalyst. The catalyst can be selected according to the polymerization method. In the melt polymerization method, a metal catalyst, for example, a metal compound containing an alkali metal (such as sodium), an alkaline earth metal (such as magnesium or barium), a transition metal (such as zinc, cadmium, lead, or cobalt) is used. As the metal compound, alkoxide, organic acid salt (acetate, propionate, etc.), inorganic acid salt (borate, carbonate, etc.), metal oxide and the like can be used. These catalysts can be used alone or in combination of two or more. In the solution polymerization method, the amount of the catalyst used is, for example, 0.01 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol, preferably 0.1 × 10 ⁻⁴ to 10 × 10, with respect to 1 mol of the dicarboxylic acid component. ^{About -4} mol may be sufficient.

  In the solution polymerization method and the interfacial polymerization method, the reaction can be performed in the presence of a base (basic catalyst, basic catalyst). Examples of the base include amines [eg, aliphatic amines (eg, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, dicyclohexylethylamine, N, N, N ′, N '-Tetramethylethylenediamine, 1-methylpiperidine, 1-ethylpiperidine, 1,2,2', 6,6'-pentamethylpiperidine, 1-methylpyrrolidine, 4-methylmorpholine, 2,6-dimethylpiperazine, etc. Aliphatic tertiary amine), aromatic amine (eg, aromatic tertiary amine such as N, N-dimethylaniline), heterocyclic amine (eg, pyridine, 4- (dimethylamino) pyridine, 4- Pyrrolidinopyridine, lutidine, collidine, imidazole, 1,5-dia Bicyclo [4.3.0] nonene, 1,8-diazabicyclo [5.4.0] undecene, etc.)], metal alkoxides (for example, alkali metal alkoxides such as sodium methoxide, potassium butoxide), quaternary ammonium water Oxides (tetraalkylammonium hydroxide such as tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide), organometallic compounds (such as butyllithium, phenyllithium, phenylmagnesium bromide, lithium diisopropylamide), organic acid salts (for example, Organic bases such as organic acid metal salts such as sodium acetate; carbonates or bicarbonates (for example, alkali or alkaline earth metal carbonates or bicarbonates such as potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate) , Hydroxides (alkali or alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide), hydrides (alkali or alkaline earth hydrides such as sodium hydride) And inorganic bases such as The bases may be used alone or in combination of two or more.

  Among these bases, amines {eg, tertiary amines [eg, aliphatic tertiary amines, heterocyclic amines (eg, pyridine)]} etc. can be suitably used in solution polymerization methods and the like. .

  The amount of the base used is, for example, 1 to 50 molar equivalents (for example, 1 to 30 molar equivalents), preferably 1 to 20 molar equivalents (for example, relative to 1 mol of the hydroxyl group of the diol component (A)). 1 to 10 molar equivalents), more preferably 1.1 to 8 molar equivalents (eg 1.2 to 7 molar equivalents), particularly 1.5 to 5 molar equivalents (eg 2 to 4 molar equivalents). May be.

  The reaction may be performed appropriately in the presence or absence of a solvent depending on the polymerization method (for example, in the solution polymerization method). Examples of the solvent include ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, anisole, etc.), aromatic solvents (aromatic carbonization such as benzene, toluene, and xylene). Hydrogens, anisole, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), sulfoxides (dimethylsulfoxide, etc.), halogenated solvents (halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc.), etc. Is mentioned. The solvents may be used alone or in combination of two or more.

  The amount of the solvent used is, for example, 0.3 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight (1 part by weight based on 1 part by weight of the diol component and the dicarboxylic acid component). For example, it may be about 2 to 10 parts by weight.

  The reaction may be performed in air or in an inert atmosphere (such as nitrogen or a rare gas), or may be performed under normal pressure, reduced pressure, or increased pressure. The reaction temperature can be selected according to the polymerization method. For example, in the solution polymerization method, it is about −20 ° C. to 150 ° C., preferably 0 to 120 ° C., more preferably about 20 to 100 ° C. (for example, 40 to 90 ° C.). You may go. Moreover, reaction time can be adjusted according to the kind of raw material, reaction temperature, the density | concentration in a solvent, etc., for example, 30 minutes-48 hours, 1-36 hours (for example, 1.5-24 hours), Preferably 2 About 18 hours (for example, 2.5 to 10 hours) may be sufficient.

  In addition, the reaction may be performed while stirring or may be performed while refluxing. In addition, although reaction is normally performed by mixing each component, you may perform mixing in steps.

  The product (polyarylate) can be separated and purified by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these.

[Molded body]
As described above, the polyarylate of the present invention has high heat resistance and excellent optical properties (high refractive index, high transparency, etc.). Furthermore, the polyarylate of the present invention is excellent in dispersibility of pigments and fillers. Therefore, the present invention also includes a molded article composed of the polyarylate (or a resin composition thereof, hereinafter referred to as polyarylate including the resin composition). The shape of the molded body is not particularly limited, and examples thereof include a two-dimensional structure (film shape, sheet shape, plate shape, etc.), a three-dimensional structure (tubular shape, rod shape, tube shape, hollow shape, etc.), and the like.

  Such a molded body should just be comprised with the said polyarylate, and may be comprised with the resin composition containing the said polyarylate. Such resin compositions include various additives [for example, fillers or reinforcing agents, colorants (dye pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat Stabilizers, mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents (silicone oil, silicone rubber, various plastic powders, various engineering plastics) Powder, etc.), heat resistance improvers (sulfur compounds, polysilanes, etc.), carbon materials, etc.]. These additives may be used alone or in combination of two or more.

  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, since the polyarylate of the present invention is excellent in various optical characteristics, it is useful for forming a film (particularly an optical film). Therefore, the present invention includes a film (optical film) formed of the polyarylate.

  The thickness of such a film can be selected according to the use from the range of about 1 to 1000 μm, 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 (optical film) can be produced by forming (or forming) the polyarylate using a conventional film forming method, casting method (solvent casting method), melt extrusion method, calendar method, or the like. .

  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 1.1 to 10 times (preferably 1.2 to 8 times, more preferably 1.5 to 6 times) in each direction in uniaxial stretching or biaxial stretching. It may be about 1 to 2.5 times (preferably 1.2 to 2.3 times, more preferably 1.5 to 2.2 times). In the case of biaxial stretching, even stretching (for example, 1.5 to 5 times in both longitudinal and transverse directions) is partially stretched (for example, 1.1 to 4 times in the longitudinal direction and 2 to 6 times in the transverse direction). Stretching). In the case of uniaxial stretching, the stretching may be longitudinal stretching (for example, 2.5 to 8 times stretching in the longitudinal direction) or lateral stretching (for example, 1.2 to 5 times stretching in the transverse direction).

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

  The 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, either 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) may be used. However, a tenter method that is excellent in uniformity of stretch thickness is preferable.

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

  In addition, the measurement and evaluation of the characteristic of resin were performed with the following method.

(Glass transition temperature (Tg))
Using a differential scanning calorimeter (DS Instruments TDS-Q2000, manufactured by TA Instruments), a sample was put in an aluminum pan, and Tg was measured in the range of 150 ° C to 400 ° C.

(Molecular weight)
Using gel permeation chromatography (GL Science, GL-7450), the sample was dissolved in tetrahydrofuran, and the molecular weight was measured in terms of polystyrene.

(Refractive index)
Using a multi-wavelength Abbe refractometer “DR-M2 / 1550” (manufactured by Atago Co., Ltd.), measurement was performed at a light source wavelength of 589 nm and a measurement temperature of 25 ° C.

(Solvent solubility)
After mixing with various solvents at a ratio of 25% by weight and stirring for 1 hour, the solubility was visually evaluated according to the following criteria.

○: Dissolved at room temperature ×: Not soluble at room temperature

Example 1
6,6- (9-Fluorenylidene) -di (2-naphthol) (or 9,9-bis (6-hydroxy-2-naphthyl) fluorene in a 1 L glass container equipped with a stirrer, a cooler, and a thermometer , 38.8 g (about 0.086 mol), tetrahydrofuran (THF) 200 mL, pyridine 34.0 g (about 0.43 mol, BNF 1 mol based on the description of JP 2007-99741 A) 5 molar equivalents) was added to obtain a homogeneous solution, and the container was replaced with argon (Ar), and then cooled until the internal temperature reached 1 ° C. Then, a solution prepared by dissolving 17.5 g (0.086 mol) of terephthalic acid dichloride in 100 mL of THF was slowly added dropwise over 30 minutes. After completion of the addition, the temperature was raised to 80 ° C. and refluxed for 4 hours to carry out the reaction. After the reaction, the reaction solution was returned to room temperature and allowed to stand overnight, and then the reaction solution was added to a 3 L beaker filled with 1.5 L of distilled water while slowly stirring, and then a 1N-HCl aqueous solution was further added to adjust the pH to 3 It was confirmed that

  The filtrate obtained by filtering the mixed solution in the beaker was washed with water, redissolved in THF, reprecipitated in 2 L of methanol, and filtered again. The filtrate was filtered and dried at 80 ° C. for 23 hours to obtain 48.2 g of the desired product in a yield of 96%. The product had a Tg of 340 ° C., a refractive index (nD25) of 1.72, and a number average molecular weight (Mn) of 18,708. Moreover, the property of the obtained polymer was white powder.

¹ H-NMR (ppm): 7.3 to 7.8 (m, 18H), 7.8 to 7.9 (d, 2H), 8.3 to 8.4 (s, 4H).

(Example 2)
In Example 1, 37.3 g (about 0.083 mol) of BNF instead of 38.3 g, 8.4 g (about 0.041 mol) of terephthalic acid dichloride instead of 17.5 g of terephthalic acid dichloride and isophthalic acid dichloride In the same manner as in Example 1 except that 8.4 g (about 0.041 mol) and 32.8 g (about 0.41 mol) of pyridine were used instead of 34.0 g, 45.9 g of the desired product was obtained. The yield was 96%. The product had a Tg of 319 ° C., a refractive index (nD25) of 1.71, and a number average molecular weight (Mn) of 13,823. Moreover, the property of the obtained polymer was white powder.

¹ H-NMR (ppm): 7.3 to 7.8 (m, 36H), 7.8 to 7.9 (d, 4H), 8.3 to 8.4 (s, 4H), 8.4 -8.5 (d, 2H), 9.0-9.1 (s, 1H).

(Example 3)
In Example 1, 27.3 g of 2,6-naphthalenedicarboxylic acid dichloride was substituted for a solution of 37.3 g (about 0.083 mol) of BNF instead of 38.3 g and 17.5 g of terephthalic acid dichloride in 100 mL of THF. (About 0.083 mol) dissolved in 200 mL of THF, except that 32.8 g (about 0.41 mol) of pyridine was used instead of 34.0 g, the reflux time was 5 hours, and the drying time was 26 hours. Produced 49.6 g of the desired product in a yield of 95% in the same manner as in Example 1. The product had a Tg of 312 ° C., a refractive index (n _D ²⁵ ) of 1.74, and a number average molecular weight (Mn) of 10,239. Moreover, the property of the obtained polymer was white powder.

¹ H-NMR (ppm): 7.3 to 7.8 (m, 20H), 8.0 to 8.2 (d, 2H), 8.3 to 8.4 (d, 2H), 8.8 -8.9 (s, 2H).

(Comparative Example 1)
In Example 1, 37.8 g (0.1 mol) of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene instead of 38.3 g of BNF, and 20.3 g of terephthalic acid dichloride instead of 17.5 g (0.1 mol), except that 39.5 g (0.5 mol) of pyridine was used instead of 34.0 g, in the same manner as in Example 1, 48.3 g of the desired product was obtained in a yield of 95%. Obtained. The product had a Tg of 289 ° C., a refractive index (nD25) of 1.64, and a number average molecular weight (Mn) of 16,267.

  The results are shown in Tables 1 and 2.

  The novel polyarylate of the present invention has excellent optical properties such as a high refractive index and high transparency, and is also excellent in various properties such as heat resistance. Therefore, the polyarylate (or the resin composition thereof) of the present invention can be suitably used for optical lenses, optical films, optical sheets, pickup lenses, holograms, liquid crystal films, organic EL films, and the like. In addition, the polyarylate (or resin composition thereof) of the present invention can be used for paints, antistatic agents, inks, adhesives, adhesives, resin fillers, charging trays, conductive sheets, protective films (electronic devices, liquid crystal members, etc.) Protective film, etc.), electrical / electronic materials (carrier transport agent, light emitter, organic photoreceptor, thermal recording material, hologram recording material), electrical / electronic components or equipment (optical disc, inkjet printer, digital paper, organic semiconductor laser, dye) Suitable for resins for sensitized solar cells, EMI shield films, photochromic materials, organic EL elements, color filters, etc.), resins for machine parts or equipment (automobiles, aerospace materials, sensors, sliding members, etc.), etc. Available.

  In particular, since the polyarylate of the present invention is excellent in optical properties, it is useful for constructing (or forming) a molded product for optical use (optical molded product). Examples of the molded article for optics formed (configured) with the polyarylate include an optical film.

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

Claims (9)

A polymer comprising a diol component (A) containing a compound (a) having a 9,9-bis (hydroxy-fused polycyclic aryl) fluorene skeleton and a dicarboxylic acid component (B) containing an aromatic dicarboxylic acid component as polymerization components Arylate, wherein the compound (a) is represented by the following formula (1):

(In the formula, ring Z represents a condensed bicyclic arene ring or a condensed tricyclic arene ring, R ¹ represents a cyano group, an alkyl group, an aryl group , R ² represents an alkyl group, a cycloalkyl group, an aryl group, An aralkyl group or an alkoxy group , m is an integer of 0 to 4, and n is an integer of 0 or more.)
A polyarylate in which the aromatic dicarboxylic acid component includes a condensed polycyclic C _10-16 arene-dicarboxylic acid or an ester-forming derivative thereof.   The polyarylate according to claim 1, wherein the compound (a) is a compound having no halogen atom.   The polyarylate according to claim 1, wherein the compound (a) is 9,9-bis (hydroxynaphthyl) fluorene, and the aromatic dicarboxylic acid component contains naphthalenedicarboxylic acid or an ester-forming derivative thereof.   The polyarylate according to any one of claims 1 to 3, which has no halogen atom in the polymer skeleton, has a refractive index of 1.68 or more at a temperature of 25 ° C, a wavelength of 589 nm, and a glass transition temperature of 300 ° C or more. .   The number average molecular weight is 30000 or less, Polyarylate in any one of Claims 1-4.   The compound (a) is 9,9-bis (hydroxynaphthyl) fluorene, the aromatic dicarboxylic acid component contains a naphthalenedicarboxylic acid component, has no halogen in the polymer skeleton, and has a temperature of 25 ° C. and a wavelength of 589 nm. The polyarylate according to claim 1, having a refractive index of 1.7 or more, a glass transition temperature of 310 ° C. or more, and a number average molecular weight of 25000 or less. 9,9-bis (hydroxymethyl condensed polycyclic aryl) compound having a fluorene skeleton (a) a diol component comprising (A), Ru by reacting a dicarboxylic acid component (B) containing an aromatic dicarboxylic acid component, poly A method for producing arylate, wherein the compound (a) is represented by the following formula (1):

(In the formula, ring Z represents a condensed bicyclic arene ring or a condensed tricyclic arene ring, R ¹ represents a cyano group, an alkyl group, an aryl group, R ² represents an alkyl group, a cycloalkyl group, an aryl group, An aralkyl group and an alkoxy group, m is an integer of 0 to 4, and n is an integer of 0 or more.) The aromatic dicarboxylic acid component is a condensed polycyclic C _10-16 arene. - containing dicarboxylic acid or an ester-forming derivative thereof, granulation how manufacturing of polyarylate of any of claims 1-6.   The production method according to claim 7, wherein a dicarboxylic acid halide is used as the dicarboxylic acid component (B) and solution polymerization is performed in the presence of a base.   The production method according to claim 7, wherein a dicarboxylic acid halide is used as the dicarboxylic acid component (B), and the interfacial polymerization is performed.