JP6549022B2 - Fluorene compound and resin composition containing the same - Google Patents

Description

  The present invention relates to a fluorene compound and a resin composition containing the same.

  In order to impart or improve properties such as thermal properties (heat resistance etc.), optical properties (high refractive index etc.) etc. in resins, resin raw materials etc., monomer components can be selected or reformed into resins Methods such as adding a compound are employed.

  For example, a compound having a fluorene skeleton has a high refractive index and has an excellent function in heat resistance and the like, and thus is used as a resin raw material, various additives, and the like. As such a compound, for example, a fluorene compound having a reactive group (hydroxyl group, amino group and the like), for example, bisphenol fluorene (BPF), biscresol fluorene (BCF), bisaminophenyl fluorene (BAF), bisphenoxyethanol Fluorene (BPEF) and the like are known.

As such a fluorene compound, a dicarboxylic acid having a fluorene skeleton is also being developed. For example, Patent Document 1, as a component of the photosensitive resin composition, bis _{(C 1-4} alkoxycarbonyl) -9,9-bis _{(C 1-4} alkoxycarbonyl _{-C 1-6} alkyl) fluorenes, Disclosed are dicarboxylic acid esters having a fluorene skeleton such as 9,9-bis [1,2-di (C _1-4 alkoxycarbonyl) ethyl] -fluorenes.

  However, since there are few synthesis examples of dicarboxylic acids having a fluorene skeleton, there are also few synthesis examples of dicarboxylic acid esters having a fluorene skeleton. For this reason, a resin composition using such a dicarboxylic acid ester having a fluorene skeleton is not sufficiently known.

JP, 2006-151833, A

  An object of the present invention is to provide a dicarboxylic acid ester having a fluorene skeleton suitable as an additive for resin and a resin composition using the same.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, in order to achieve the said objective, the present inventors discovered that the polyester which has a specific structure can provide outstanding characteristics, such as heat resistance improvement and fluidity | liquidity improvement, with respect to resin. Based on such findings, the present inventors conducted further studies to complete the present invention. That is, the present invention includes the following configurations.

  Item 1. The diol component and the general formula (1):

[Wherein, R ^1a and R ^1b are the same or different and each represents a substituent. R ^2a , R ^2b , R ^2c and R ^2d are the same or different and each represents a substituent. One of R ^3a and R ^3b is a hydrogen atom and the other is a carboxy group. One of R ^3c and R ^3d is a hydrogen atom and the other is a carboxy group. n1 and n2 are the same or different and each represents an integer of 0 to 4; m1 and m2 are the same or different, and represent an integer of 0-2. m3 and m4 are the same or different and each represents an integer of 0 to 3; ]
Polyester which makes a polymerization component the dicarboxylic acid component containing the fluorene compound represented by these.

  Item 2. The fluorene compound has a general formula (1A):

[Wherein, R ^3a , R ^3b , R ^3c and R ^3d are as defined above. ]
The polyester according to item 1, which is a fluorene compound represented by

  Item 3. The polyester according to Item 1 or 2, wherein the diol component comprises ethylene glycol.

  Item 4. General formulas (2A) to (2C):

[Wherein, R ^1a , R ^1b , R ^2a , R ^2b , R ^2c , R ^2d , n 1, n 2, m 1, m 2, m 3 and m 4 are as defined above. R ³ represents a divalent group. ]
Polyester having at least one repeating unit represented by

Item 5. Item 5. The polyester according to item 4, wherein R ³ is an ethylene group.

  Item 6. The additive for resin which consists of polyester in any one of claim | item 1 -5.

  Item 7. Item 7. The resin additive according to item 6, which is a resin heat resistance improver and / or a resin flowability improver.

  Item 8. Item 8. A resin composition containing a resin and the additive for resin according to item 6 or 7.

  Item 9. Item 9. The resin composition according to item 8, wherein the content of the additive for resin is 1 to 20 parts by weight with respect to 100 parts by weight of the resin.

  Item 10. Item 10. A molded article comprising the polyester according to any one of items 1 to 5 or the resin composition according to item 8 or 9.

  According to the present invention, novel polyesters having a specific structure can be provided. By adding this polyester to the resin, the heat resistance, fluidity, etc. of the resin can be improved.

  In the present specification, "containing" is a concept including any of "including", "consisting essentially of", and "consisting only of".

1. Polyester The polyester of the present invention comprises a diol component and a compound represented by the general formula (1):

[Wherein, R ^1a and R ^1b are the same or different and each represents a substituent. R ^2a , R ^2b , R ^2c and R ^2d are the same or different and each represents a substituent. One of R ^3a and R ^3b is a hydrogen atom and the other is a carboxy group. One of R ^3c and R ^3d is a hydrogen atom and the other is a carboxy group. n1 and n2 are the same or different and each represents an integer of 0 to 4; m1 and m2 are the same or different, and represent an integer of 0-2. m3 and m4 are the same or different and each represents an integer of 0 to 3; ]
And a dicarboxylic acid component containing a fluorene compound represented by the formula (hereinafter sometimes referred to as "fluorene compound (1)") as a polymerization component.

(1-1) Diol component As a diol component, an aliphatic diol component, an alicyclic diol component, an aromatic diol component etc. are mentioned, for example. The diol component may be used alone or in combination of two or more.

Examples of aliphatic diols constituting the aliphatic diol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol. Alkanediol such as butanediol, 1,4-pentanediol, 1,5-pentanediol, 1,3-pentanediol, neopentyl glycol (preferably C _2-10 alkanediol, more preferably C _2-6 alkanediol , more preferably C _2-4 alkane diol); diethylene glycol, dipropylene glycol, poly alkanediols and triethylene glycol (preferably include saturated aliphatic diols di- or tri-C _2-4 alkane diol), and the like. The aliphatic diols may be used alone or in combination of two or more.

The alicyclic diol constituting the alicyclic diol component includes, for example, cycloalkanediol, polycycloalkanediol, di (hydroxyalkyl) cycloalkane, di (hydroxyalkyl) polycycloalkane, and diol having a heterocycloalkane skeleton. Etc. Examples of cycloalkanediols include C _4-10 cycloalkanediols such as 1,4-cyclohexanediol, preferably C _5-8 cycloalkanediol, and the like. Examples of polycycloalkanediols include di- or tricycloalkanediols such as norbornane diol and adamantanediol, preferably di or tri C _4-10 cycloalkane diol, more preferably di or tri C _5-8 cycloalkane diol It can be mentioned. Examples of di (hydroxyalkyl) cycloalkanes include di (hydroxy C _1-4 alkyl) C _4-10 cycloalkanes such as 1,4-cyclohexanedimethanol, preferably di (hydroxy C _1-3 alkyl) C _{5 And -8} cycloalkane, more preferably di (hydroxy C _1-2 alkyl) C _5-6 cycloalkane and the like. Examples of di (hydroxyalkyl) polycycloalkanes include dicyclopentadiendimethanol (tricyclo [5.2.1.0 (2,6)] decanedimethanol), adamantane dimethanol, norbornane dimethanol and the like. Hydroxy C _1-4 alkyl) bi or tri C _4-10 cycloalkane, preferably di (hydroxy C _1-3 alkyl) bi or tri C _5-8 cycloalkane, more preferably di (hydroxy C _1-2 alkyl) The bi or tri _C5-6 cycloalkane etc. are mentioned. Examples of the diol having a heterocycloalkane skeleton include oxamono or polycycloalkanediol such as isosorbide; 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxa Diol (preferably di (hydroxyalkyl) tetraoxa spiro alkane, preferably di (hydroxy C _1-10 alkyl) tetraoxa spiro alkane) etc. which have oxaspiro ring frame | skeleton, such as spiro [5.5] undecane, etc. are mentioned. The alicyclic diols may be used alone or in combination of two or more.

As an aromatic diol which comprises an aromatic diol component, dihydroxy arene, bisphenols, an araliphatic diol etc. are mentioned, for example. Examples of dihydroxyarenes include hydroquinone and resorcinol. Examples of the aromatic aliphatic diol include di (hydroxyalkyl) arenes (preferably di (hydroxy C _1-4 alkyl) such as benzenedimethanol (1,4-benzenedimethanol, 1,3-benzenedimethanol, etc.) C _6-10 arene); alkylene oxide adducts of bisphenols and the like.

Examples of bisphenols include dihydroxyarenes such as 4,4′-dihydroxybiphenyl (preferably dihydroxy (C ₆ -10 arene)); bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxy) Phenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) ester Bread, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-, Bis (hydroxyphenyl) alkanes such as dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane and bis (4-hydroxyphenyl) diphenylmethane (preferably bis (hydroxyphenyl) ) C _1-10 alkanes, more preferably bis (hydroxyphenyl) C _1-8 alkanes); bis (hydroxyphenyl aryl) s such as 2, 2-bis (4-hydroxy-3,3'-biphenyl) propane alkanes (preferably bis (hydroxy _{biphenylyl) C 1-10} alkanes, more preferably Bis (hydroxy _{biphenylyl) C 1-8} alkanes); 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) Bis (hydroxyphenyl) cycloalkanes such as cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, etc. (preferably bis (hydroxyphenyl) C _4-10 cycloalkanes, more preferably bis _{(hydroxyphenyl) C 5-8} cycloalkane); 4,4'-dihydroxy diphenyl ether - ether, 4,4'-dihydroxy-3,3'-dimethyl diphenyl ether - bis such ether (Hydroxyphenyl) ethers; 4,4'-dihydroxydiphenyl sulfone Bis (hydroxyphenyl) sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfone; 4,4'-dihydroxydiphenyl sulfoxide Bis (hydroxyphenyl) sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, etc .; 4,4'-dihydroxydiphenyl sulfide Bis (hydroxyphenyl) sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide; 4,4 ′-(o- Phenylenediisopropylidene) diphenol, 4,4 '-(m-fu Two) diphenol, 4, 4 '- (p-phenylene-isopropylidene) bis diphenol such as (hydroxyphenyl - alkyl) arenes (preferably bis (hydroxyphenyl _{-C 1-4} alkyl) _{C 6 And -10} arene, more preferably bis (hydroxyphenyl-C _1-4 alkyl) benzene) and the like.

In addition, in the alkylene oxide adduct of bisphenol, _C2-6 alkylene oxides (Preferably _C2-3 alkylene oxide), such as ethylene oxide, a propylene oxide, a butylene oxide, etc. are mentioned as an alkylene oxide, for example. In addition, in the alkylene oxide adduct, the addition ratio of the alkylene oxide is, for example, 1 mole or more (eg, 1 to 10 moles), preferably 1 to 6 moles (eg, 1 mole) to 1 mole of hydroxy group of bisphenols. It may be about 1 to 5 mol, more preferably about 1 to 4 mol, particularly about 1 to 3 mol (e.g. 1 to 2 mol).

  Other than the aromatic diols constituting the aromatic diol component, fluorene-based diols can also be used. 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes [or compounds having a 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorene skeleton] as a fluorene diol, 9,9-bis (hydroxy) (Poly) alkoxynaphthyl) fluorenes [or compounds having a 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorene skeleton] and the like are included.

Examples of 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes include 9,9-bis (hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) phenyl] 9,9-bis (hydroxy _C2-4 alkoxyphenyl) fluorene} such as fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene, 9,9-bis (alkyl-hydroxyalkoxyphenyl) Fluorene {e.g. 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 9, 9, 9 such as 9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene 9-bis (mono or di C _1-4 alkyl-hydroxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- (2) 9,9-bis (mono or di C _6-10 aryl- such as -hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-phenylphenyl] fluorene and the like 9,9-bis (hydroxyalkoxyphenyl) fluorenes such as hydroxy C _2-4 alkoxyphenyl) fluorene}; 9,9-bis (hydroxydialkoxyphenyl) fluorene {eg, 9,9-bis {4- [2 - (2-hydroxyethoxy) ethoxy] phenyl} fluorene such as 9,9-bis (hydroxy-di C _-4 alkoxyphenyl) fluorene} etc. 9,9-bis (hydroxy polyalkoxy phenyl) includes fluorenes and the like.

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

Among these diols having a fluorene skeleton, in particular, 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes {eg, 9 such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and the like 9,9-bis (hydroxy (poly) _C2-4 alkoxyphenyl) fluorene}, 9,9-bis (hydroxy (poly) alkoxy-arylaryl) fluorenes {eg, 9,9-bis [4- (2-) Preferred is 9,9-bis (aryl-hydroxy (poly) _C2-4 alkoxyphenyl) fluorene} such as hydroxyethoxy) -3-phenylphenyl] fluorene.

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

  The diol component may typically be comprised of an aliphatic diol (especially ethylene glycol). The ratio of the aliphatic diol to the entire diol component may be, for example, 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, and particularly 70 mol% or more.

(1-2) Dicarboxylic Acid Component The dicarboxylic acid component has the general formula (1):

[Wherein, R ^1a , R ^1b , R ^2a , R ^2b , R ^2c , R ^2d , R ^3a , R ^3b , R ^3c , R ^3d , n 1, n 2, m 1, m 2, m 3 and m 4 are the same as above] is there. ]
And a fluorene compound represented by

In the general formula (1), R ^1a and R ^1b are substituents. Examples of this substituent include a hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group etc.), an alkoxy group, a cycloalkoxy group and the like. These substituents may or may not be substituted with other groups.

In the general formula (1), as the alkyl group represented by R ^1a and R ^1b , a C _1-8 alkyl group is preferable, and a C _1-4 alkyl group is preferable. A methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, t-butyl group etc. can be illustrated specifically ,. As a substituent of this alkyl group, it may have 1 to 4 pieces, such as the below-mentioned hydrocarbon group (a cycloalkyl group, an aryl group, an aralkyl group etc.) mentioned later, the below-mentioned alkoxy group, the below-mentioned cyclo alkoxy group etc., for example.

In the general formula (1), as the cycloalkyl group represented by R ^1a and R ^1b , a C _5-10 cycloalkyl group is preferable, a C _5-8 cycloalkyl group is more preferable, and a C _5-6 cycloalkyl group is more preferable. More preferable. Specifically, a cyclopentyl group, a cyclohexyl group etc. can be illustrated. As a substituent of this cycloalkyl group, it has, for example, 1 to 4 of the above-mentioned or below-mentioned hydrocarbon group (alkyl group, aryl group, aralkyl group etc.), below-mentioned alkoxy group, below-mentioned cycloalkoxy group etc. obtain.

As the aryl group represented by R ^1a and R ^1b in the general formula (1), a C _6-10 aryl group is preferable. Specifically, phenyl group, alkylphenyl group (alkyl: those mentioned above; tolyl group such as o-tolyl group, m-tolyl group, p-tolyl group, etc .; dimethylphenyl group such as xylyl group etc.), naphthyl group etc. Can be illustrated. As a substituent of this aryl group, for example, it has 1 to 4 of hydrocarbon group (alkyl group, cycloalkyl group, aralkyl group, etc. described above or below), alkoxy group described below, cycloalkoxy group described below, etc. obtain.

In the general formula (1), as the aralkyl group represented by R ^1a and R ^1b , a C _7-14 aralkyl group having the above-described aryl group and the above-described alkyl group is preferable. Specifically, a benzyl group, a phenethyl group etc. can be illustrated. The substituent of this aralkyl group may have, for example, 1 to 4 of the aforementioned hydrocarbon group (alkyl group, cycloalkyl group, aryl group etc.), an alkoxy group described later, a cycloalkoxy group mentioned later and the like.

In General Formula (1), as an alkoxy group shown by group ^R1a and ^R1b , _C1-8 alkoxy group is preferable and _C1-6 alkoxy group is more preferable. Specifically, methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group and the like can be exemplified. As a substituent of this alkoxy group, it can have 1 to 4 pieces, such as the above-mentioned hydrocarbon group (an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group etc.), the below-mentioned cyclo alkoxy group etc., for example.

As the cycloalkoxy group represented by R ^1a and R ^1b in General Formula (1), a C _5-10 cycloalkoxy group is preferable. Specifically, a cyclohexyloxy group etc. can be illustrated. As a substituent of this cycloalkoxy group, it can have 1 to 4 pieces, such as an above-described hydrocarbon group (an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group etc.), an above-mentioned alkoxy group etc., for example.

When n1 is plural (an integer of 2 to 4), plural R ^1a may be the same or different. Similarly, when n2 is plural (an integer of 2 to 4), plural R ^1b may be the same or different.

Further, R ^1a and R ^1b substituted on different benzene rings may be the same or different. Further, the bonding position (substituting position) of R ^1a and R ^1b is not particularly limited, and examples thereof include at least one of position 2 and position 7 of the fluorene ring.

In the general formula (1), n1 and n2 which are the substitution numbers of R ^1a and R ^1b may be the same or different, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, 0 or 1 More preferably, 0 is particularly preferred.

R ^{2a to} R ^2d are substituents. Examples of this substituent include a hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group etc.), an alkoxy group, a cycloalkoxy group and the like. These substituents may or may not be substituted with other groups. Examples of these substituents (hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group, etc.), alkoxy group, cycloalkoxy group, etc.) are as described above.

In addition, when m1 is plural (2), several R ^2a may be the same or different. Similarly, when m2 is plural (2), plural R ^2b may be the same or different. When m3 is plural (2 or 3), plural R ^2c may be the same or different. Furthermore, when m4 is plural (2 or 3), plural R ^2d may be the same or different.

Further, R ^{2a to} R ^2d substituted on different benzene rings may be the same or different. Further, the bonding position (substituting position) of R ^{2a to} R ^2d is not particularly limited, and, for example, at least one of positions 1, 2, 4, 6, 9 of the dibenzo [1,4] dioxin ring, etc. (The fluorene ring is usually bonded at the 3-position).

In the general formula (1), m1 and m2 which are the number of substitution of R ^2a and R ^2b may be the same or different, an integer of 0 to 2 is preferable, 0 or 1 is more preferable, and 0 is more preferable.

In the general formula (1), m3 and m4, which are the substitution numbers of R ^2c and R ^2d , may be the same or different, and an integer of 0 to 3 is preferable, an integer of 0 to 2 is more preferable, 0 or 1 is More preferably, 0 is particularly preferred.

One of R ^3a and R ^3b is a hydrogen atom and the other is a carboxy group. Also, one of R ^3c and R ^3d is a hydrogen atom and the other is a carboxy group. By employing such a fluorene compound, it is easier to form a linear polymer as the polyester of the present invention.

  As a fluorene compound (1) which satisfy | fills such conditions, General formula (1A):

[Wherein, R ^3a , R ^3b , R ^3c and R ^3d are as defined above. ]
The fluorene compound (Hereinafter, it may be called "fluorene compound (1A)") represented by these is preferable. Depending on the synthesis conditions, etc., the fluorene compound (1A)

Such isotopes may be included. Also, depending on the synthesis conditions, etc., it may be obtained as a mixture of these isotopes.

  The dicarboxylic acid component may be a dicarboxylic acid component consisting of the fluorene compound (1). The proportion of the fluorene compound (1) is, for example, 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, particularly 70 mol% or more based on the entire dicarboxylic acid component. Good.

In the present invention, the dicarboxylic acid component can also contain a dicarboxylic acid component other than the fluorene compound (1) within the range where the effects of the present invention are exhibited. As other dicarboxylic acid components, for example, monocyclic aromatic dicarboxylic acid components (C _6-10 arene dicarboxylic acid etc.), non-monocyclic aromatic dicarboxylic acid components (condensed polycyclic aromatic dicarboxylic acids, biphenyl dicarbons Acid, diphenyl alkanedicarboxylic acid, diphenyl ketone dicarboxylic acid), aliphatic dicarboxylic acid component (alkanedicarboxylic acid), alicyclic dicarboxylic acid component (cycloalkanedicarboxylic acid, di- or tricycloalkanedicarboxylic acid, etc.), etc. it can.

  However, the polyester of the present invention preferably comprises only a diol component and a dicarboxylic acid component consisting only of the fluorene compound (1). In this case, the polyester of the present invention has the general formulas (2A) to (2C):

[Wherein, R ^1a , R ^1b , R ^2a , R ^2b , R ^2c , R ^2d , n 1, n 2, m 1, m 2, m 3 and m 4 are as defined above. R ³ represents a divalent group. ]
And at least one repeating unit represented by Preferably, the polyester of the present invention comprises only at least one repeating unit represented by the general formulas (2A) to (2C).

In the general formulas (2A) to (2C), R ³ is a divalent group derived from a diol component. For example, when the diol component is an aliphatic diol component, R ³ is usually an alkylene group, and when ethylene glycol is employed as the diol component, R ³ is an ethylene group.

  The number of repeating units (polymerization degree) of the polyester of the present invention is not particularly limited, and is usually about 2 to 100, preferably about 3 to 50. The number average molecular weight of the polyester of the present invention is usually 500 to 50000, preferably about 700 to 30000. The number average molecular weight of the polyester of the present invention is measured by gel permeation chromatography (GPC).

2. Method for Producing Fluorene Compound (1) The method for producing fluorene compound (1) is not limited, and, for example, the following reaction formula:

[Wherein, R ^1a , R ^1b , R ^2a , R ^2b , R ^2c , R ^2d , R ^3a , R ^3b , R ^3c , R ^3d , n 1, n 2, m 1, m 2, m 3 and m 4 are the same as above] is there. One of R ^3a1 and R ^3b1 is a hydrogen atom and the other is a cyano group. One of R ^3c1 and R ^{3d 1} represents a hydrogen atom and the other represents a cyano group. X ¹ and X ² are the same or different and are halogen atoms. ]
Can be synthesized along the route shown by.

[Synthesis of Fluorene Compound (5)]
In the general formula (3), as R ^1a , R ^1b , R ^2c , R ^2d , n 1, n 2, m 3 and m 4, those described above can be adopted. Preferred embodiments are also the same.

  Examples of such a compound represented by the general formula (3) (hereinafter sometimes referred to as “compound (3)”) include

Compounds represented by and the like can be used, and known or commercially available compounds can be used. The compound (3) can be synthesized, for example, according to the method described in JP-A-2001-206862.

In the general formula (4), as R ^2a and m 1, those described above can be adopted. Preferred embodiments are also the same.

In the general formula (4), one of R ^3a1 and R ^3b1 is a hydrogen atom and the other is a cyano group.

In the general formula (4), X ¹ and X ² are a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably a fluorine atom. In addition, although X ¹ and X ² may be the same or different, the reaction is easier if the same.

  Examples of such a compound represented by the general formula (4) (hereinafter sometimes referred to as “compound (4)”) include

Etc. can be used, and known or commercially available compounds can be used.

  0.7-10 mol is preferable normally with respect to 1 mol of compounds (3), and, as for the usage-amount of a compound (4), 1.7-5 mol is more preferable.

The reaction is preferably carried out in the presence of a base. The base to be used is not particularly limited, and alkali metal salts such as potassium carbonate, sodium carbonate, potassium phosphate and sodium phosphate; alkaline earth metal salts such as calcium carbonate, magnesium carbonate and calcium phosphate; calcium hydride (CaH ₂ ) Alkaline earth metal hydrides such as ₂ ), amines such as diisopropylethylamine, tributylamine, morpholine, N-methylmorpholine and the like. Among these, from the viewpoint of reactivity, alkaline earth metal salts are preferable, and calcium carbonate is more preferable. These bases may be used alone or in combination of two or more.

  The amount of the base used is preferably in excess with respect to the compound (3) from the viewpoint of yield. Specifically, the amount of the base to be used is generally preferably 0.1 to 100 mol, and more preferably 1 to 10 mol, per 1 mol of compound (3).

  The compound (3), the compound (4) and the base may be added at once, or may be added stepwise several times.

  The reaction can usually be carried out in the presence of a solvent. As a solvent which can be used, for example, aromatic hydrocarbon solvents such as toluene, xylene and benzene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane and diisopropyl ether; ketone solvents such as acetone and methyl ethyl ketone; Amide solvents such as formamide and dimethylacetamide; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol and isopropyl alcohol; dimethyl sulfoxide and the like. These may be used alone or in combination of two or more. Among them, from the viewpoint of reactivity, amide solvents are preferable, and dimethylformamide is more preferable.

  The reaction is preferably performed under an inert gas (nitrogen gas, argon gas), and may be performed under reduced pressure. The reaction temperature may be usually 50 to 200 ° C, preferably 80 to 180 ° C. The reaction time can be such that the reaction proceeds sufficiently.

  The reaction mixture after completion of the reaction contains a solvent, a base, unreacted components, etc. in addition to the fluorene compound represented by the general formula (5) (hereinafter sometimes referred to as "fluorene compound (5)") Have Therefore, the fluorene compound (5) may be separated and purified from the reaction mixture after the reaction according to a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, etc. or separation means combining these. Good. In addition, since the reaction of the present invention easily proceeds ideally (quantitatively), the purity is sufficiently high even in separation by filtration or the like, but in order to further increase the purity, purification such as distillation or recrystallization may be performed . Further, in order to synthesize the fluorene compound (1) following the present reaction, the separation and purification may not be performed.

[Synthesis of Fluorene Compound (1)]
The hydrolysis conditions for synthesizing the fluorene compound (1) using the fluorene compound (5) are not particularly limited, and it is preferable to carry out in the presence of a strong acid or a strong base.

  As an acid which can be used, it is preferable that it is a strong acid, for example, hydrochloric acid, a sulfuric acid, nitric acid, p-toluenesulfonic acid, strongly acidic ion exchange resin etc. are mentioned. These may be used alone or in combination of two or more.

  As a base that can be used, a strong base is preferable. For example, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; alkali metal hydrides such as lithium hydride (LiH) and sodium hydride (NaH); methyl And alkyllithiums such as lithium, ethyllithium, n-butyllithium, s-butyllithium and t-butyllithium; and aryllithiums such as phenyllithium. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of reactivity, a base is preferable, an alkali metal hydroxide is more preferable, and potassium hydroxide is more preferable.

  From the viewpoint of reactivity, the amount of the strong acid or strong base used is usually preferably 0.1 to 100 mol, and more preferably 1 to 20 mol, per 1 mol of the fluorene compound (5).

  The reaction can usually be carried out in the presence of a solvent. As a solvent which can be used, the organic solvent besides water which hydrolyzes a fluorene compound (5) can also be used. Organic solvents include aromatic hydrocarbon solvents such as toluene, xylene and benzene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane and diisopropyl ether; methyl chloride, chloroform, dichloromethane, dichloroethane, dibromoethane and the like Halogenated hydrocarbon solvents; ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as dimethylformamide and dimethylacetamide; nitrile solvents such as acetonitrile; methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2-ethoxyethanol Alcohol solvents such as; dimethyl sulfoxide and the like. These may be used alone or in combination of two or more. Among them, from the viewpoint of reactivity, alcohol solvents are preferable, and 2-methoxyethanol is more preferable.

  The reaction is preferably performed under an inert gas (nitrogen gas, argon gas), and may be performed under reduced pressure. The reaction temperature may be usually 50 to 200 ° C, preferably 80 to 180 ° C. The reaction time can be such that the reaction proceeds sufficiently.

  The reaction mixture after completion of the reaction may contain, in addition to the fluorene compound (1), a solvent, a strong acid or a strong base, an unreacted component, and the like. Therefore, the fluorene compound (1) may be separated and purified from the reaction mixture after the reaction by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, or a combination of these. Good. In addition, since the reaction of the present invention easily proceeds ideally (quantitatively), the purity is sufficiently high even in separation by filtration or the like, but in order to further increase the purity, purification such as distillation or recrystallization may be performed .

3. Method for Producing Polyester The polyester of the present invention is a polyester comprising the diol component and the dicarboxylic acid component as the polymerization component (or the diol component and the dicarboxylic acid component are polymerized), and the diol component and the dicarboxylic acid component Can be produced by reacting (polymerizing or condensing). The method of the polymerization reaction or condensation reaction (production method) can be appropriately selected according to the type of the dicarboxylic acid component to be used, etc., and may be a conventional method, for example, a method of dehydration by heating, acetyl group of hydroxy group of diol component A method of heating to release acetic acid after activation with an etc., a method of converting a carboxy group into a phenyl ester, a methyl ester, etc. and then heating to remove phenol or demethanolation, a carboxy group with thionyl chloride, oxalyl chloride or the like A method of dehydrochlorination with a base after conversion to an acid chloride and the like can be mentioned. Among them, in the present invention, the cost can be reduced according to the method of dephenolating or demethanolation by heating after converting the carboxy group into phenyl ester, methyl ester or the like, while the reactivity is higher using acid chloride. From the viewpoint of being able to lower the polymerization temperature, a method in which the carboxyl group is converted to a phenyl ester, methyl ester etc. and then heated to dephenolate or demethanolized, or after converted to an acid chloride with thionyl chloride, oxalyl chloride etc. Preferably, the method of dehydrochlorination or the like is selected according to requirements.

  Hereinafter, a method of dehydrochlorination with a base after conversion to an acid chloride with thionyl chloride, oxalyl chloride or the like can be carried out according to a conventional method, but will be described in detail below. Other methods can also be performed according to a conventional method.

  The amount of thionyl chloride, oxalyl chloride and the like to be used is not particularly limited, and is preferably in excess with respect to the fluorene compound (1). For example, 1-10 mol is preferable with respect to 1 mol of fluorene compounds (1), and 2-5 mol is more preferable.

  The step of converting the carboxy group of the fluorene compound (1) into an acid chloride with thionyl chloride, oxalyl chloride or the like can usually be carried out in the presence of a solvent. As a solvent which can be used, for example, aromatic hydrocarbon solvents such as toluene, xylene and benzene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane and diisopropyl ether; methyl chloride, chloroform, dichloromethane, dichloroethane, dibromo Halogenated hydrocarbon solvents such as ethane; ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as dimethylformamide and dimethylacetamide; nitrile solvents such as acetonitrile; methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2 Alcohol solvents such as ethoxyethanol; dimethyl sulfoxide and the like. These may be used alone or in combination of two or more. Among them, from the viewpoint of reactivity, ether solvents and amide solvents are preferable, and tetrahydrofuran, dimethylformamide and the like are more preferable.

  The step of converting the carboxy group of the fluorene compound (1) into an acid chloride with thionyl chloride, oxalyl chloride or the like is preferably performed under an inert gas (nitrogen gas, argon gas), and may be performed under reduced pressure. The reaction temperature may be usually 0 to 150 ° C, preferably 50 to 100 ° C. The reaction time can be such that the reaction proceeds sufficiently.

  The reaction mixture after completion of the reaction may contain, in addition to the acid chloride of the fluorene compound (1), a solvent, unreacted components, and the like. Therefore, the acid chloride of the fluorene compound (1) is separated and purified from the reaction mixture after the reaction by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization and the like, or a combination of these. You may In addition, since the reaction of the present invention easily proceeds ideally (quantitatively), the purity is sufficiently high even in separation by filtration or the like, but in order to further increase the purity, purification such as distillation or recrystallization may be performed . In addition, in order to carry out the synthesis of polyester following this reaction, it is not necessary to carry out the above separation and purification.

  Next, in the step of dehydrochlorination with a base, the amount of the diol component to be used is preferably 0.2 to 5 moles with respect to 1 mole of the fluorene compound (1) from the viewpoint of reactivity. -2 mol is more preferable.

  Next, as a base which can be used in the step of dehydrochlorination with a base, any of an inorganic base and an organic base can be adopted, and an organic base is preferable. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as sodium carbonate and sodium hydrogencarbonate; alkaline earths such as calcium carbonate Trimetals such as triethylamine; aromatic tertiary amines such as benzyldimethylamine; heterocyclic tertiary amines such as pyridine; and the like. These may be used alone or in combination of two or more. Among them, from the viewpoint of reactivity, heterocyclic tertiary amines are preferable, and pyridine is more preferable.

  The amount of the base used is not particularly limited, and is preferably in excess with respect to the fluorene compound (1). For example, 1-10 mol is preferable with respect to 1 mol of fluorene compounds (1), and 1.5-5 mol is more preferable.

  The step of dehydrochlorinating with a base can usually be carried out in the presence of a solvent. In addition, when using a liquid as a base, a solvent can also be used. As a solvent which can be used, for example, aromatic hydrocarbon solvents such as toluene, xylene and benzene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane and diisopropyl ether; methyl chloride, chloroform, dichloromethane, dichloroethane, dibromo Halogenated hydrocarbon solvents such as ethane; ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as dimethylformamide and dimethylacetamide; nitrile solvents such as acetonitrile; methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2 Alcohol solvents such as ethoxyethanol; dimethyl sulfoxide and the like. These may be used alone or in combination of two or more. Among them, from the viewpoint of reactivity, ether solvents are preferable, and tetrahydrofuran is more preferable.

  The step of dehydrochlorination with a base is preferably performed under an inert gas (nitrogen gas, argon gas), and may be performed under reduced pressure. The reaction temperature may be usually 0 to 150 ° C, preferably 50 to 100 ° C. The reaction time can be such that the reaction proceeds sufficiently.

  The reaction mixture after completion of the reaction may contain, in addition to the polyester of the present invention, a solvent, a base, unreacted components and the like. Therefore, the polyester of the present invention may be separated and purified from the reaction mixture after the reaction by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization and the like, or a combination of these. . In addition, since the reaction of the present invention easily proceeds ideally (quantitatively), the purity is sufficiently high even in separation by filtration or the like, but in order to further increase the purity, purification such as distillation or recrystallization may be performed .

4. Additive for resin and resin composition The polyester of the present invention described above can be added to a resin (used as an additive for resin) to raise the glass transition temperature of the resin. Therefore, the polyester of the present invention can function as a resin heat resistance improver. Generally, the addition of a lower molecular weight compound to the resin reduces the glass transition temperature, whereas the addition of the polyester of the present invention to the resin increases the glass transition temperature. it can.

  The polyester of the present invention described above can be added to a resin (used as an additive for a resin) to improve the flowability of the resin. Thus, the polyester of the present invention can function as a resin flowability improver.

  The resin composition of the present invention contains a resin and the additive for resin (the polyester of the present invention).

  It does not specifically limit as resin used for the resin composition of this invention, All well-known resin can be used. For example, resins such as polycarbonate resins, polyester resins and polycycloolefin resins can be used. These resins may be used alone or in combination of two or more. Among them, polycarbonate resins, polyester resins and the like are preferable from the viewpoint of compatibility with the polyester of the present invention.

  As polycarbonate resin, bisphenol-based polycarbonate resin etc. are mentioned, for example. As polyester resin, fluorene type polyester resin etc. are mentioned, for example. As a polycyclo olefin resin, norbornene-type cyclo olefin resin etc. are mentioned, for example. For these, commercially available products may be used. For example, OKP 4 (polyester resin for optics; manufactured by Osaka Gas Chemical Co., Ltd.), Eupilon H-4000 (polycarbonate resin; manufactured by Mitsubishi Engineering Plastics Co., Ltd.), Arton F 4520 (polycyclo resin) Olefin resin; JSR Co., Ltd. product etc. are mentioned.

  The content of the additive for resin (the polyester of the present invention) in the resin composition of the present invention is not particularly limited as long as a desired effect (heat resistance improvement of resin, flowability improvement, etc.) can be obtained. For example, 1 to 20 parts by weight is preferable, and 2 to 15 parts by weight is more preferable with respect to 100 parts by weight of the resin.

  Further, the resin composition of the present invention may contain known additives other than the additive for resin (the polyester of the present invention) as long as the effects of the present invention are not impaired. Other additives include, for example, fillers or reinforcing agents, colorants (dyes and pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, UV absorbers, heat stabilizers, etc.), Release agents, antistatic agents, dispersants, flow control agents, leveling agents, antifoaming agents, surface modifiers, stress reducing agents (silicone oil, silicone rubber, various plastic powders, various engineering plastic powders, etc.), heat resistance And modifiers (such as sulfur compounds and polysilanes) and carbon materials. These additives may be used alone or in combination of two or more.

  The resin composition of the present invention has excellent heat resistance as well as excellent fluidity. For this reason, the resin composition of the present invention is suitable for optical applications. Although various molded articles composed of the polyester or resin composition of the present invention can be employed, for example, the polyester or resin composition of the present invention can be used as an optical material or an optical molded article (optical film, optical lens, etc.) It can be used. Molded articles are, for example, injection molding method, press molding, injection compression molding method, extrusion molding method, transfer molding method, blow molding method, pressure molding method, casting molding method (in particular, melt press method of pressing after melt casting) And so on). When obtaining an optical film, the obtained optical molded body may be stretched.

  The present invention will be described in more detail based on examples given below, but the present invention is not limited by these examples.

  The glass transition temperature (Tg), refractive index, birefringence, and fluidity were measured by the following methods.

Glass transition temperature (Tg)
Using a differential scanning calorimeter (DSC 6220, manufactured by Seiko Instruments Inc.), the sample was placed in an aluminum pan, and the glass transition temperature (Tg) was measured in the range of 30 ° C. to 220 ° C.

The refractive index was measured at a light source wavelength of 589 nm and a measurement temperature of 20 ° C. using a refractive index multi-wavelength Abbe refractometer (DR-M2 / 1550, manufactured by Atago Co., Ltd.).

Using a birefringence “RETS-100” (manufactured by Otsuka Electronics Co., Ltd.), the measurement method measures retardation at a wavelength of 600 nm by the parallel Nicol rotation method, and this retardation value is divided by the thickness of the measurement site. did. The test piece used for measurement was produced in the following procedures. The resin was press-molded at 160 to 240 ° C. to obtain a film having a thickness of 100 to 400 μm. The obtained film was cut into strips of 15 × 50 mm and uniaxially stretched at a temperature of glass transition temperature (Tg) + 10 ° C. to a draw ratio of 3 × 25 mm / min to prepare test pieces for measurement. The obtained test piece was measured by the above-mentioned method, and threefold birefringence was determined.

The temperature-viscosity relationship was measured by flowability flow tester measurement, and the temperature at which the viscosity reached 5000 Pa · s was read and evaluated (T5000). The temperature range was 120 to 300 ° C., and the measurement was performed under the condition of 5 ° C./min. The lower the value, the better the fluidity.

Reference Example 1: Synthesis of 9,9-bis (cyanodibenzo [1,4] dioxin-2-yl) fluorene

  20.67 g (37.1 mmol) of 9,9-biscatechol fluorene (BCAF) and 12.95 g (75.3 mmol) of 3,4-dichlorobenzonitrile (DCBN) dissolved in 100 mL of N, N-dimethylformamide (DMF) Then, 20.39 g (147 mmol) of potassium carbonate was added, and the mixture was heated and stirred at an oil bath temperature of 140 ° C. for 17 hours. The reaction solution was concentrated as much as possible with a rotary evaporator. Water was added to the residue and the precipitate was collected by filtration. The resulting precipitate was dried with warm air at 60 ° C. for 17 hours, and further dried under reduced pressure at 60 ° C. for 6 hours. The resulting solid was dissolved by heating in toluene, and the insolubles were filtered. The filtrate is concentrated under reduced pressure, and the obtained residue is purified by silica gel column chromatography with eluent toluene to obtain 9,9-bis (cyanodibenzo [1,4] dioxin-2-yl) fluorene (BCNDF) 17 as a pale yellow solid. .0 g (yield 79%) were obtained. Moreover, it is a compound (molecular weight is 580.59) observed by m / z = 580 by the field desorption mass spectrometry (FD-MS) measurement of the obtained solid, and it is a compound represented by said Formula It was confirmed.

Reference Example 2: Synthesis of 9,9-bis (carboxydibenzo [1,4] dioxin-2-yl) fluorene

  21.98 g (37.86 mmol) of BCNDF obtained in Reference Example 1 was added to 100 mL of 2-ethoxyethanol (EET), and heated and dissolved at an oil bath temperature of 120 ° C. A solution of 10.0 g (250.02 mmol) of sodium hydroxide in 12 mL of water was added to the BCNDF / EET solution. The temperature of the oil bath was raised to 140 ° C., and the EET was distilled and heated and stirred for 5 hours while repeating the addition of water. It was confirmed that the reaction solution vapor was neutral on pH test paper. The reaction solution had a slight precipitate, but when it was allowed to cool to room temperature, a precipitate formed. The temperature was raised again to an oil bath temperature of 100 ° C. to dissolve, and hydrochloric acid was added to the solution to make it acidic and to precipitate. After cooling, the precipitate was collected by filtration and washed with water. After air drying at 60 ° C., it was dried under reduced pressure at 60 ° C. to obtain 24.2 g (quantitative) of an off-white solid 9,9-bis (carboxydibenzo [1,4] dioxin-2-yl) fluorene (BCDF). The HPLC purity was 98%. In addition, the molecular weight of the obtained solid determined by liquid chromatography mass spectrometry (LCMS) measurement is 618 (ESI, anion, m / z = 617, corresponding to MH), and the compound represented by the above formula It confirmed that it was.

Example 1: Synthesis of BCDF-EG polyester

  Dissolve 5.00 g (8.08 mmol) of 9,9-bis (7-carboxydibenzo [1,4] dioxin-2-yl) fluorene (BCDF) obtained in Reference Example 2 in 50 mL of tetrahydrofuran (THF) to obtain chloride 3.28 g (27.57 mmol) of thionyl were added. Two to three drops of N, N-dimethylformamide (DMF) were added, and the mixture was heated and stirred under an argon atmosphere at an oil bath temperature of 70 ° C. for 3 days. The reaction mixture was concentrated under reduced pressure, toluene was added to the obtained residue, and concentrated under reduced pressure. This operation was repeated twice more. The resulting residue was dissolved in 50 mL of THF, and 1.47 g (18.62 mmol) of pyridine was added. 0.50 g (8.08 mmol) of ethylene glycol (EG) was added, and the mixture was heated and stirred in an argon atmosphere at an oil bath temperature of 70 ° C. for 17 hours. The reaction solution was added dropwise to 200 mL of methanol, and the resulting precipitate was collected by filtration. The obtained solid was air dried at 60 ° C. for 2 hours and then dried under reduced pressure at 60 ° C. for 17 hours. Yield: 4.30 g, the yield calculated from BCDF-EG unit molecular weight was 83%.

Example 2: Preparation of resin composition Using a kneader mill (manufactured by Toshin), kneading of the resin and the polyester of Example 1 was carried out under the conditions of a resin temperature of 240 to 250 ° C and a rotation number of 300 rpm for 5 minutes. . The type of resin used is shown in Table 1, and the preparation ratio of resin to BCDF oligomer is shown in Table 2.

  Usually, when a low molecular weight compound is added to the resin, the glass transition temperature rises when the polyester of the present invention is added to the resin as described above, although the glass transition temperature is lowered. The heat resistance was improved. Moreover, the improvement of fluidity was also seen by adding the polyester of the present invention to the resin.

  The polyester of the present invention can achieve excellent properties such as high heat resistance and high flowability. Therefore, the polyester (or the resin composition thereof) of the present invention can be suitably used for an optical lens, an optical film, an optical sheet, a pickup lens, a hologram, a film for liquid crystal, a film for organic EL and the like. Further, the polyester (or the resin composition thereof) of the present invention is a paint, an antistatic agent, an ink, an adhesive, an adhesive, an adhesive, a resin filler, a charging tray, a conductive sheet, a protective film (electronic equipment, liquid crystal member etc. Films, etc.), electric / electronic materials (carrier transport agent, light emitter, organic photoreceptor, thermosensitive recording material, hologram recording material), electric / electronic parts or devices (optical disc, ink jet printer, digital paper, organic semiconductor laser, dye sensitization) Suitable for solar cells, resins for EMI shielding films, photochromic materials, organic EL elements, color filters, etc., resins for mechanical parts or devices (automobiles, aviation materials, space materials, sensors, sliding members, etc.), etc. it can.

  In particular, the polyester of the present invention is useful for constructing (or forming) molded articles for optical use (optical molded articles). As an optical molded article formed (constructed) by such polyester, an optical film, an optical lens, etc. are mentioned, for example.

  As an optical film, a polarizing film (and its polarizing element and polarizing plate protective film), a retardation film, an alignment film (alignment film), a viewing angle widening (compensation) film, a diffusion plate (film), a prism sheet, Light guide plate, brightness enhancement film, near infrared absorption film, reflective film, antireflection (AR) film, reflection reduction (LR) film, antiglare (AG) film, transparent conductive (ITO) film, anisotropic conductive film (ACF) And EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filters, black matrix layers, adhesive layers or release layers between optical films, and the like. Specifically, in an optical film used for a display member (or display) of an apparatus, a monitor of a personal computer, a television, a mobile phone, a car navigation system, an FPD device such as a touch panel (for example, LCD, PDP etc.), etc. Can be mentioned.

Claims (7)

The diol component and the general formula (1 A ):

[In the formula , one of R ^3a and R ^3b is a hydrogen atom and the other is a carboxy group. One of R ^3c and R ^3d is a hydrogen atom and the other is a carboxy group . ]
The resin flowability improving agent which consists of polyester which uses as a polymerization component the dicarboxylic acid component containing the fluorene compound represented by these. The resin flowability improver according to claim 1, wherein the diol component comprises ethylene glycol. General formulas (2A) to (2C):

[ Wherein, R ³ represents a divalent group. ]
At least it consists of Lupolen Riesuteru that having a single repeat unit, the resin flowability improving agent represented in. The resin flowability improver according to claim 3 , wherein R ³ is an ethylene group. The resin composition containing resin and the resin flowability improvement agent in any one of Claims 1-4 . The resin composition according to claim 5 , wherein a content of the resin flowability improving agent is 1 to 20 parts by weight with respect to 100 parts by weight of the resin. A molded article comprising the resin flowability improver according to any one of claims 1 to 4 or the resin composition according to claim 5 or 6 .