JP2015218265A - Method for improving fluidity of resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of improving melt fluidity of a thermoplastic resin.SOLUTION: A structural unit represented by formula (1a) and/or (1b) is introduced into a thermoplastic resin to improve melt fluidity of the thermoplastic resin. (In the formula, Rand Rare the same or different and each represent an optionally substituted alkylene group; Rrepresents an inert substituent; m represents an integer of 0-4; and k represents 0 or an integer of 1-4.)

Description

  The present invention relates to a method for improving fluidity (melt fluidity) of a thermoplastic resin or a thermoplastic resin composition using a predetermined compound having a fluorene skeleton.

  A compound having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) is useful for producing a resin having excellent functions such as a high refractive index and high heat resistance. As the compound having a hydroxyl group, for example, bis (hydroxyethoxyphenyl) fluorene (BPEF) is known. Further, as the compound having a carboxyl group, 9,9-bis (2-carboxyethyl) fluorene, 2,7-dicarboxy-9,9-dimethylfluorene and the like are known.

  JP-A-2002-179611 (Patent Document 1) discloses a carboxylic acid having a fluorene skeleton [9,9-bis by reaction of fluorene with an α, β-unsaturated carboxylic acid or an ester thereof (such as acrylic acid). (Carboxyethyl) fluorene etc.] is described, and it is described that such carboxylic acids are useful as raw materials for polyesters, polyamides, and epoxy resins.

  US Patent Publication US 2012/0171118 A1 (Patent Document 2) includes 9,9-bis (ethoxycarbonylethyl) fluorene and ethylene glycol, butylene glycol, or fluorenedipropanol (9,9-bis (3-hydroxypropyl). ) Fluorene) is reacted to prepare a polyester.

  JP-A-2008-69224 (Patent Document 3) discloses a diol component containing a diol component having a fluorene skeleton [9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, etc.] and a fluorene skeleton. It is described that a polyester resin is prepared using a dicarboxylic acid component (B) containing a dicarboxylic acid component [9,9-bis (2-carboxyethyl) fluorene and the like] having such a polyester resin. , It describes that it has excellent optical properties (refractive index) and solvent solubility.

  However, the polyester resins described in these documents may not show high melt fluidity. Therefore, the molding processability and productivity of a molded body such as an optical molded body cannot be improved.

JP 2002-179611 (Claims, paragraph [0002]) US 2012/0171118 A1 (paragraph [0044], Examples 1a-1d, Examples 6, 7, 9) JP 2008-69224 A (Claims, Examples, [Effects of the Invention])

  Accordingly, an object of the present invention is to provide a method for improving the melt fluidity of a thermoplastic resin.

  Another object of the present invention is to provide a method capable of improving the melt fluidity of a thermoplastic resin without impairing mechanical properties, thermal properties, and optical properties.

  Still another object of the present invention is to provide a fluidity improver that can improve the melt fluidity of a thermoplastic resin.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have prepared a thermoplastic resin by introducing a predetermined structural unit having a fluorene skeleton as the structural unit of the thermoplastic resin, or have the fluorene skeleton. It was found that when a predetermined compound is added to a thermoplastic resin to prepare a thermoplastic resin composition, the melt fluidity of the thermoplastic resin and the thermoplastic resin composition is greatly improved, and the present invention has been completed.

  That is, in the method of the present invention, a structural unit represented by the following formula (1a) and / or (1b) is introduced as the structural unit of the thermoplastic resin to improve the melt fluidity of the thermoplastic resin.

(Wherein, R _1a and R _1b are the same or different and each represents an alkylene group which may have a substituent, R ₂ represents an inert substituent, m represents an integer of 0 to 4, and k represents 0 or an integer of 1 to 4 is shown)
In order to further improve the melt fluidity, a copolymer unit represented by the following formula (2-2) may be further introduced as a structural unit of the thermoplastic resin.

(In the formula, ring Z represents a hydrocarbon ring, R ₄ represents an inert substituent, and n represents 0 or an integer of 1 to 4)
The introduction ratio of the structural unit represented by the formula (1a) and / or (1b) may be 10 mol% or more with respect to the entire structural unit of the thermoplastic resin. The ratio (molar ratio) between the unit represented by the formula (1a) and / or (1b) and the unit represented by the formula (2-2) was about the former / the latter = 100/0 to 30/70. May be.

  Examples of the thermoplastic resin into which the structural unit is introduced include a polyester resin and a polyamide resin.

  Furthermore, the present invention provides a method for improving the melt fluidity of the thermoplastic resin by adding a fluorene compound represented by the following formula (1a-1) and / or (1b-1) to the thermoplastic resin; An additive for improving melt fluidity by adding to a plastic resin, comprising a fluorene compound represented by the following formula (1a-1) and / or (1b-1) Is also included.

(Wherein, R _3a and R _3b are the same or different and represent a hydrogen atom or a hydrocarbon group, and R _1a , R _1b , R ₂ , m and k are the same as above)
In the present specification, the dicarboxylic acid and its reactive derivative may be collectively referred to as “dicarboxylic acid component”, and the first and second dicarboxylic acid components may be simply referred to as “dicarboxylic acid component”. In addition, the structural unit and the compound represented by the predetermined formula (A) may be referred to as “unit (A)” and “compound (A)”, respectively. Furthermore, the unit represented by the formula (1a) and the unit represented by the formula (1b) may be simply referred to as a unit (1) in some cases.

  In the present invention, a predetermined structural unit having a fluorene skeleton is introduced into a thermoplastic resin, or a predetermined compound having a fluorene skeleton is added to the thermoplastic resin. Therefore, the melt fluidity of the thermoplastic resin and the thermoplastic resin composition Can be greatly improved. In addition, the melt fluidity can be improved without impairing mechanical properties, thermal properties (heat resistance, etc.), and optical properties (high refractive index, low birefringence, negative birefringence, etc.). Therefore, it is possible to improve the molding processability and productivity of various molded bodies, for example, optical members [for example, optical films and optical molded bodies (lenses, etc.)].

  The present invention provides an embodiment in which a unit having a fluorene skeleton represented by the formula (1a) and / or (1b) is introduced as a structural unit of the thermoplastic resin, the formula (1a-1) and / or (1b- And an embodiment in which a predetermined compound having a fluorene skeleton represented by 1) is added to a thermoplastic resin.

[Structural unit (1a) (1b) (or first dicarboxylic acid component)]
In the formula (1a) and / or (1b), the alkylene group represented by R _1a and R _1b is a linear or branched alkylene group such as a methylene group, an ethylene group, a trimethylene group, or a propylene group. And C _1-8 alkylene groups such as 2-ethylethylene group and 2-methylpropane-1,3-diyl group. Preferred alkylene groups are linear or branched C _1-6 alkylene groups (for example, C _1-4 alkylene groups such as methylene group, ethylene group, propylene group).

R _1a is often a linear or branched C _2-4 alkylene group (eg, ethylene group, propylene group), and R _1b is a linear or branched C _1-3 alkylene group (eg, Methylene group, ethylene group) in many cases.

Examples of the substituent of the alkylene group include an aryl group (such as a phenyl group) and a cycloalkyl group (such as a cyclohexyl group). The alkylene group R _1a having a substituent may be, for example, a 1-phenylethylene group or a 1-phenylpropane-1,2-diyl group.

  The coefficient m can be selected from an integer of 0 to 4, and may be usually 0 to 2, preferably 0 or 1.

Examples of the inert substituent represented by R ₂ include a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [eg, alkyl group, aryl group (C ₆ such as phenyl group). _-10 aryl group) and the like], acyl groups (for example, C _1-6 alkylcarbonyl groups such as acetyl, ethylcarbonyl, butylcarbonyl, etc.). The inert substituent represented by R ₂ is often a cyano group or an alkyl group. Examples of the alkyl group include a linear or branched C _1-6 alkyl group (preferably a C _1-4 alkyl group) such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group. Can be illustrated.

  The coefficient k represents 0 or an integer of 1 to 4, and is usually a positive integer of 0 to 2, particularly 0 or 1. The two substitution numbers k may be the same or different in different benzene rings.

In addition, when the coefficient k is plural (2 to 4), plural groups R ₂ substituted on the same or different benzene rings may be the same or different from each other. Examples of the bonding position (substitution position) of the group R ₂ include the 2-position, 7-position, 2- and 7-position of the fluorene ring.

  The thermoplastic resin only needs to include at least one of the structural units (1a) and (1b), and includes both the structural units (1a) and (1b). May be. In many cases, the thermoplastic resin contains the structural unit (1a). The ratio (molar ratio) between the structural unit (1a) and the structural unit (1b) can be selected, for example, from the range of unit (1a) / unit (1b) = 100/0 to 0/100. It may be 0 to 25/75 (for example, 95/5 to 35/65), preferably about 100/0 to 50/50 (for example, 90/10 to 55/45).

  The structural unit (1a) is derived from or corresponds to a compound represented by the following formula (1a-2) (for example, 9,9-bis (carboxyalkyl) fluorene or a reactive derivative thereof), and the structural unit (1b) is derived from or corresponds to a compound represented by the following formula (1b-2) (for example, 9,9-bis (hydroxyalkyl) fluorene or a reactive derivative thereof).

(Wherein, L ₁ represents a leaving group, and R _1a , R _1b , R ₂ , m and k are the same as above)
Examples of the leaving group represented by L ₁ include a hydroxyl group, a lower alkoxy group, and a halogen atom. Examples of the lower alkyl group include C _1-4 alkyl groups such as a methyl group, an ethyl group, a pullyl group, a butyl group, and a t-butyl group, and usually a methyl group or an ethyl group. Examples of the halogen atom include a chlorine atom and a bromine atom.

A typical dicarboxylic acid component represented by the formula (1a-2) is a compound corresponding to the formula (1a), in which R _1a is a C _2-6 alkylene group, for example, 9,9-bis (2 -Carboxyethyl) fluorene, 9,9-bis (carboxy C _2-6 alkyl) fluorene such as 9,9-bis (2-carboxypropyl) fluorene, and reactive derivatives thereof (ester-forming derivatives) .

A typical dicarboxylic acid component represented by the formula (1b-2) is a compound corresponding to the formula (1b), wherein m = 0 and R _1b is a C _1-6 alkylene group, for example, 9- (1-carboxy-2-carboxyethyl) fluorene, a compound wherein m = 1 and R _1b is a C _1-6 alkylene group, such as 9- (2-carboxy-3-carboxypropyl) fluorene 9- (carboxy-carboxy C _2-6 alkyl) fluorene, and reactive derivatives thereof (ester-forming derivatives).

Examples of reactive derivatives (ester-forming derivatives) of these compounds (1a-2) and (1b-2) include alkoxycarbonyl compounds [for example, C _1-4 alkoxy-carbonyl-C _1-6 alkyl) fluorene, etc. Roh 9,9-bis _{(C 1-4} alkoxy - carbonyl - alkyl) fluorene], acid halides thereof [e.g., 9,9-bis (chlorocarbonyl _{-C 1-6} alkyl) fluorene such as 9,9-bis ( Halocarbonyl-alkyl) fluorene] and the like.

[Copolymerized unit (or second dicarboxylic acid component)]
The thermoplastic resin may contain the structural unit (1a) and / or the structural unit (1b) corresponding to the first dicarboxylic acid component, and together with the structural unit (1a) and / or the structural unit (1b). These may be represented by the following formula (2-1) and / or formula (2-2) and may have a copolymer unit (structural unit) corresponding to the second dicarboxylic acid component. Thermoplastic resins containing copolymerized units exhibit high melt fluidity. In particular, the copolymer unit (structural unit) having a hydrocarbon ring is rigid and has high heat resistance, and is expected to decrease the melt fluidity, but can greatly improve the melt fluidity contrary to expectations.

(Wherein R ₃ represents an alkylene group, ring Z represents a hydrocarbon ring, R ₄ represents an inert substituent, and n represents 0 or an integer of 1 to 4)
The copolymer unit (structural unit) represented by formula (2-1) is simply referred to as copolymer unit (2-1), and the copolymer unit (structural unit) represented by formula (2-2) is simply It may be called a copolymerization unit (2-2).

  The copolymer unit (structural unit) represented by formula (2-1) is derived from or corresponds to an aliphatic dicarboxylic acid (alkane dicarboxylic acid) or a reactive derivative thereof, and is represented by formula (2-2) The unit (structural unit) is derived from or corresponds to an alicyclic dicarboxylic acid (cycloalkanedicarboxylic acid), an aromatic dicarboxylic acid (arene dicarboxylic acid) or a reactive derivative thereof.

Examples of the alkylene group represented by R ₃ include a linear or branched alkylene group (for example, a C _1-12 alkylene group, preferably a C _2-10 alkylene group, and more preferably a C _4-12 alkylene group). Can be illustrated. Examples of the aliphatic dicarboxylic acid (alkanedicarboxylic acid) corresponding to the copolymer unit (structural unit) represented by the formula (2-1) include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and undecane. Examples thereof include C _2-12 alkanedicarboxylic acids such as dicarboxylic acid and dodecanedicarboxylic acid. Aliphatic dicarboxylic acids may be used alone or in combination of two or more.

Examples of the ring Z include a cycloalkane ring and an arene ring. Examples of the cycloalkane ring include C _5-10 cycloalkane rings such as cyclopentane ring, cyclohexane ring, methylcyclohexane ring, and cyclooctane ring; bi- or tricycloalkane rings (such as norbornane-diyl group) Examples thereof include a bridged cyclic hydrocarbon group. A preferred cycloalkane ring is a C _5-8 cycloalkane ring.

The arene ring represented by ring Z is a monocyclic arene ring (such as a benzene ring) or a condensed polycyclic arene ring (such as a condensed polycyclic C _6-16 arene ring such as a naphthalene ring, an anthracene ring, or a fluorene ring) A ring assembly arene ring (a ring assembly C _12-18 arene ring such as a biphenyl ring or a terphenyl ring). The arene ring includes a bisaryl ring in which two aryl rings are connected via a connecting group such as an alkylene group, an ether group, a carbonyl group, a sulfide group, and a sulfone group, such as a diarylalkane ring, a diaryl ether ring, a diaryl ketone ring, A diaryl sulfone ring and the like are also included. Preferred arene rings are benzene ring, naphthalene ring, biphenyl ring and the like.

As the substituent R ₄ , a substituent inert to the reaction, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, t -Linear or branched _C1-4 alkyl group such as butyl group), cycloalkyl group (such as _C5-10 cycloalkyl group such as cyclohexyl group), aryl group (phenyl group, naphthyl group, etc.) C _6-10 aryl group), hydroxyl group, alkoxy group (linear or branched C _1-4 alkoxy group such as methoxy group, ethoxy group, butoxy group, t-butoxy group), acyl group (for example, acetyl group) Alkylcarbonyl group such as a group), nitro group, cyano group and the like. The inert substituent represented by R ₄ is often an alkyl group such as a methyl group.

Examples of the alicyclic dicarboxylic acid corresponding to the copolymer unit (structural unit) represented by the formula (2-2) include cycloalkane dicarboxylic acid [for example, C _5-10 such as 1,4-cyclohexanedicarboxylic acid. Cycloalkane-dicarboxylic acid]; bridged cyclic cycloalkane dicarboxylic acid [for example, bi- or tricycloalkane dicarboxylic acid (for example, decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecanedicarboxylic acid, etc.)] Can be mentioned. The alicyclic dicarboxylic acids may be used alone or in combination of two or more.

Among the aromatic dicarboxylic acids corresponding to the copolymer units (structural units) represented by the formula (2-2), examples of the monocyclic aromatic dicarboxylic acid include terephthalic acid which is a dicarboxylic acid having a symmetric structure; Examples thereof include dicarboxylic acids having a structure, such as isophthalic acid, alkylisophthalic acid (for example, C _1-4 alkyl terephthalic acid such as 4-methylisophthalic acid, C _6-10 arene dicarboxylic acid such as phthalic acid), and the like. Monocyclic aromatic dicarboxylic acids can be used alone or in combination of two or more.

Examples of the polycyclic aromatic dicarboxylic acid include condensed polycyclic aromatic dicarboxylic acids [for example, naphthalenedicarboxylic acid (for example, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid). , 2,7-naphthalenedicarboxylic acid), anthracene dicarboxylic acid, fluorene dicarboxylic acid (2,7-dicarboxyfluorene, 9,9-dimethyl-2,7-dicarboxyfluorene, etc.) _10-18 arene-dicarboxylic acid (preferably condensed polycyclic C _10-16 arene-dicarboxylic acid, more preferably condensed polycyclic C _10-14 arene-dicarboxylic acid)], ring-assembled arene dicarboxylic acid [for example, biphenyl Dicarboxylic acids (such as 4,4'-biphenyldicarboxylic acid), terphenyl dica Bi- or tel-C _6-10 aryl-dicarboxylic acids such as rubonic acid (such as 4,4 "-terphenyl dicarboxylic acid)], diarylalkanedicarboxylic acids [eg di-C _6- such as 4,4'-diphenylmethane dicarboxylic acid, etc. ₁₀ aryl C _1-6 alkane-dicarboxylic acid], diaryl ether dicarboxylic acid [eg, diC _6-10 aryl ether-dicarboxylic acid such as 4,4′-diphenyl ether dicarboxylic acid], diaryl ketone dicarboxylic acid [eg, 4, DiC _6-10 aryl ketone-dicarboxylic acid such as 4′-diphenyl ketone dicarboxylic acid], diaryl sulfone dicarboxylic acid [for example, di C _6-10 aryl sulfone-dicarboxylic acid such as 4,4′-diphenyl sulfone dicarboxylic acid] Polycyclic aromatic dicarboxylic acid The acids may be used alone or in combination of two or more.

Examples of the reactive derivative of the second dicarboxylic acid component include reactive derivatives (ester-forming derivatives) having the same leaving group L ₁ as the compounds represented by formulas (1a-2) and (1b-2). it can.

  When an alicyclic dicarboxylic acid component, a monocyclic aromatic dicarboxylic acid component (such as terephthalic acid and / or isophthalic acid), or a condensed polycyclic aromatic dicarboxylic acid component (such as naphthalenedicarboxylic acid) is used as a copolymer component, It is expected that the rigidity and heat resistance of the plastic resin will increase and the melt fluidity will decrease. However, when the copolymer unit (2-2) is introduced as a copolymer unit in combination with the structural units (1a) and (1b), the thermoplastic resin does not decrease the heat resistance and high refractive index of the thermoplastic resin. The melt fluidity of can be improved. Therefore, the alicyclic dicarboxylic acid component, the monocyclic aromatic dicarboxylic acid component, the condensed polycyclic aromatic dicarboxylic acid component may be used alone or in combination of two or more, If necessary, an aliphatic dicarboxylic acid component may be used in combination. In addition to the structural units (1a) and (1b), the copolymer unit contained in the thermoplastic resin is often a copolymer unit represented by the formula (2-2).

  In the thermoplastic resin, the ratio (molar ratio) between the structural units represented by the formulas (1a) and (1b) and the copolymer units (structural units) represented by the formulas (2-1) and (2-2) Can be selected from the range of the former / the latter = 100/0 to 5/95 (for example, 100/0 to 15/85, preferably 100/0 to 30/70), and includes copolymer units (structural units). In the thermoplastic resin, the former / the latter = 99/1 to 20/80 (for example, 99/5 to 25/75), preferably about 90/10 to 30/70 (for example, 80/20 to 40/60). There may be. The said ratio respond | corresponds to the introduction | transduction ratio of the structural unit represented by Formula (1a) and (1b) with respect to the whole structural unit formed with the 1st and 2nd dicarboxylic acid component. The above ratio also corresponds to the ratio of the first dicarboxylic acid component to the entire first and second dicarboxylic acid components.

  The introduction ratio of the structural units represented by the formulas (1a) and (1b) is 10 mol% or more (for example, 10 to 50 mol%, preferably 20) with respect to the entire structural units (or repeating units) of the thermoplastic resin. To 50 mol%), and may be generally about 25 to 50 mol% (for example, 25 to 45 mol%), preferably about 30 to 50 mol% (for example, 35 to 45 mol%). .

[Thermoplastic resin]
As the thermoplastic resin into which the structural units (1a) and (1b) are introduced, a thermoplastic resin having the first dicarboxylic acid component (and optionally the second dicarboxylic acid component) as a reaction component, for example, a polyester resin, A polyamide resin etc. can be illustrated.

Polyester Resin A polyester resin can be prepared by reacting the dicarboxylic acid component with a diol component, and the diol component may be an aliphatic diol, an alicyclic diol, or an aromatic diol. These diol components can be used alone or in combination of two or more, and different diols may be used in combination.

Aliphatic diols include alkanediols [eg, C ₂₋ such as ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, etc. ₁₀ alkane diols, preferably C _2-6 alkane diols, more preferably C _2-4 alkane diols], polyalkane diols (eg di- or tri-C _2-4 alkane diols such as diethylene glycol, dipropylene glycol, triethylene glycol, etc.) Etc.) and the like.

Examples of the alicyclic diol include cycloalkane diol (for example, C _4-10 cycloalkane diol such as 1,4-cyclohexane diol, preferably C _5-8 cycloalkane diol), bridged cycloalkane diol ( for example, norbornane diol, bi- or tri-Sik alkanediol such as adamantane diol), di (hydroxyalkyl) cycloalkanes [e.g., such as 1,4-cyclohexane dimethanol di (hydroxyalkyl _{C 1-4 alkyl) C 4-10} cycloalkyl Alkanes, etc.], bridged cyclic (hydroxyalkyl) cycloalkanes [for example, tricyclodecane dimethanol (tricyclo [5.2.1.0 (2,6)] decane dimethanol), adamantane dimethanol, norbornane dimethanol Di (Hide etc. Roxy C _1-4 alkyl) bi or tri C _6-12 cycloalkane etc.], di (hydroxy C) such as alkylene oxide adduct [2,2-bis (4-hydroxycyclohexyl) propane, etc.] of hydrogenated products of the following bisphenols _5-10 cycloalkyl) alkylene oxide adducts such as C _1-10 alkanes], diols having an oxacycloalkane ring {eg, condensed oxaC _4-6 cycloalkane diols (eg, isosorbide), spirocyclic diols [eg , 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane and the like di (hydroxyC _1-10 alkyl) tetraoxaspiro Oxaspirocyclic diols such as alkanes] and the like.

  An alicyclic diol such as di (hydroxyalkyl) cycloalkane is useful for improving the heat resistance and optical properties (refractive index and birefringence) of the polyester resin.

Examples of the aromatic diol include dihydroxyarene (hydroquinone, resorcinol, etc.), bisphenols, araliphatic diol {eg, di (hydroxyalkyl) arene [eg, benzenedimethanol (1,4-benzenedimethanol, 1, Di (hydroxy C _1-4 alkyl) C _6-10 arene etc.] such as 3-benzenedimethanol), alkylene oxide adducts of bisphenols and the like.

  Bisphenols contain the compound represented by following formula (3).

(In the formula, ring Z ₁ is an arene ring, R ₅ is an alkylene group, p is an integer of 0 or more and an integer of 10 to 10, X is a linking group, q is 0 or 1, and R ₄ and n are as defined above. the same)
Examples of the arene ring represented by the ring Z ₁ include the same arene rings as the ring Z (monocyclic arene ring, condensed bicyclic arene ring, condensed tricyclic arene ring, ring assembly arene ring, etc.). . Preferred arene rings are benzene ring, naphthalene ring, biphenyl ring and the like.

Examples of the alkylene group represented by R ₅ include a linear or branched C _1-10 alkylene group such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a butane-1,2-diyl group, and a tetramethylene group. And a C _2-6 alkylene group such as a hexylene group. Preferred alkylene groups are C _2-4 alkylene groups, especially C _2-3 alkylene groups (ethylene group, trimethylene group, propylene group, etc.).

  The integer p is an integer of 0 or more, and can usually be selected from a range of about 0 to 15 (for example, 0 to 10), for example, 0 to 8 (for example, 1 to 8), preferably 0 to 6 (for example, 1 to 6), more preferably about 0 to 4 (for example, 1 to 4). The integer p may be 1 to 3, preferably 1 or 2.

As the linking group X, for example, an alkylene group (or alkylidene group) (for example, linear or branched C _1-10 such as methylene group, ethylene group, ethylidene group, propylene group, 2-propylidene group, butylene group) C _4-10 such as an alkylene group, preferably a C _1-6 alkylene group, more preferably a C _1-4 alkylene group, a cycloalkylene group or a cycloalkylidene group (1,4-cyclohexylene group, cyclohexylidene group). A cycloalkylene group or a C _4-10 cycloalkylidene group, preferably a C _5-8 cycloalkylene group or a C _5-8 cycloalkylidene group), an arylene group (eg, a C _6-10 arylene group such as a phenylene group), an arylarene Diyl groups (eg C _6-10 aryls such as biphenyl-4,4′-diyl groups) Ru-C _6-10 arenediyl group), oxygen atom or ether group (—O—), carbonyl group (—CO—), sulfur atom or thio group (—S—), sulfinyl group (—SO—), sulfonyl group _(-SO 2 -), and the like 9,9-diyl group represented by the following formula (4-1) to (4-3).

(In the formula, X ₁ represents an oxygen atom, a carbonyl group, a sulfur atom, a sulfinyl group or a sulfonyl group, R ₆ represents an alkylene group or an arylene group, R ₇ represents an alkylene group or a diarylalkylene group, and R ₂ and k are Same as above)
Examples of the alkylene group represented by R ₆ include linear or branched C _1-10 alkylene groups such as an ethylene group, a propylidene group, a tetramethylene group, and an octamethylene group. The arylene group includes a phenylene group. Examples thereof include C _6-10 arylene groups. Examples of the alkylene group represented by R ₇ include linear or branched C _1-6 alkylene groups such as a methylene group, an ethylene group and a 2-propylidene group. Examples of the diarylalkylene group include a diphenylmethylene group, Examples thereof include a diC _6-10 aryl-C _1-6 alkylene group such as a diphenylethylene group.

A typical linking group X includes an alkylene group or an alkylidene group, a cycloalkylene group or a cycloalkylidene group, an arylene group, an oxygen atom or an ether group (—O—), a carbonyl group (—CO—), a sulfur atom, or a thio group ( -S-), sulfinyl group (-SO-), a sulfonyl group _(-SO 2 -), and the like 9,9-diyl group represented by the formula (4-3).

The linking group X having a hydrocarbon group may have the same substituent as R ₄ , for example, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a halogen atom and the like. For example, the alkylene group as the linking group X includes C _5-10 cycloalkyl C _1-6 alkylene group such as cyclohexylmethylene group, phenylmethylene group, 2,4-dichlorophenylmethylene group, 4-fluorophenylmethylene group, naphthylmethylene group. _{C 6-10} aryl _{C 1-6} alkylene group such group, diphenylmethylene group, even an alkylene group having a substituent such as a _{di-C 6-10} aryl _{C 1-6} alkylene group such as ditrifluoromethyl methylene group Good.

Examples of bisphenols include compounds of q = 0 in the formula (3) (biphenol and the like); compounds of the formula (3) in which X is an alkylene group and q = 1 (bis (hydroxyphenyl) alkanes, for example, Bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (3 Bis (hydroxyphenyl) C _1-10 alkane such as 5-dimethyl-4-hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl) butane; in the formula (3), X is a cycloalkylene group or A compound having a cycloalkylidene group and q = 1 (bis (hydroxyphenyl) cycloalkane), such as 1,1 - bis (4-hydroxyphenyl) bis (hydroxyphenyl) such as cyclohexane C _4-10 cycloalkane such as; the formula (3), X is an oxygen atom, a carbonyl group, a sulfur atom or a thio group, a sulfinyl group or a sulfonyl group And q = 1 compounds (for example, bis (hydroxyphenyl) ethers such as 4,4′-dihydroxydiphenyl ether, such as 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3 Bis (hydroxyphenyl) sulfones such as 3,3′-dimethyldiphenylsulfone, for example, bis (hydroxyphenyl) sulfoxides such as 4,4′-dihydroxydiphenylsulfoxide, for example, bis such as 4,4′-dihydroxydiphenylsulfide (Hydroxyphenyl) sulfides In the formula (3), X is a group represented by the formula (4-1), and a compound having q = 1 (for example, 4,4 ′-(o, m or p-phenylenediisopropylidene) Bis (hydroxyphenyl-C _1-4 alkyl) C _6-10 arene etc.) such as diphenol).

  Furthermore, in the formula (3), X is a group represented by the formula (4-3), and the compound of q = 1 is 9,9-bis (hydroxyaryl) fluorene, for example, 9,9- Bis (hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc.], 9,9-bis (hydroxynaphthyl) Fluorene [eg, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9-bis (5-hydroxy1-naphthyl) fluorene, etc.], 9-bis (hydroxybiphenyl) fluorene [eg, 9, 9-bis ((3-hydroxy-4-phenyl) phenyl) fluorene etc.] and the like.

In the alkylene oxide adduct of bisphenols, examples of the alkylene oxide include C _2-4 alkylene oxide (preferably C _2-3 alkylene oxide) such as ethylene oxide, propylene oxide, and butylene oxide. The number of moles of alkylene oxide added is, for example, 1 mole or more (for example, 1 to 10 moles), preferably 1 to 5 moles, more preferably 1 to 3 moles per mole of hydroxyl groups of bisphenols (for example). For example, it may be about 1-2 mol).

  The alkylene oxide adduct includes part or all of a hydroxyalkoxy compound obtained by a reaction of a bisphenol with an alkylene carbonate (ethylene carbonate, propylene carbonate, etc.) or a haloalkanol.

Examples of the alkylene oxide adduct include 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane and 2,2-bis (4- (2- (2-hydroxyethoxy) ethoxy) phenyl) propane. In addition to the alkylene oxide adduct of bisphenol A, in the above formula (3), X is a group represented by the formula (4-3), and an alkylene oxide adduct of a compound of q = 1 is also included. As such a fluorene compound, 9,9-bis (hydroxyalkoxyaryl) fluorene, for example, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2 9,9-bis (hydroxyC _1-6 alkoxyphenyl) fluorene such as -hydroxypropoxy) phenyl] fluorene, 9,9-bis [4- (4-hydroxybutoxy) phenyl] fluorene; 9,9-bis [4 -(2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (4-hydroxybutoxy) ) -3-methylphenyl] fluorene such as 9,9-bis (alkyl - hydroxy _{C 1-6} Arukokishife E) fluorene; 9,9-bis [4-phenyl-3- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4-phenyl-3- (2-hydroxypropoxy) phenyl] fluorene, 9,9-bis (phenyl-hydroxyC _1-6 alkoxyphenyl) fluorene such as 9-bis [4-phenyl-3- (4-hydroxybutoxy) phenyl] fluorene; 9,9-bis [6- (2- Hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, 9,9-bis [6- (3-hydroxypropoxy) -2-naphthyl] Fluorene, 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] fluorene, 9,9-bis [6- (4-hydroxyl) Carboxymethyl) -2-naphthyl] 9,9-bis fluorene [(hydroxy _{C 1-6} alkoxy) naphthyl] fluorene; p = 2 to 10 In these compounds (e.g., 2-5, preferably 2 or 3) The compound of the grade etc. can be illustrated.

In the reaction of bisphenols with alkylene carbonate or haloalkanol (such as bromo C _1-10 alkanol), a hydroxyalkoxy compound having a longer carbon number than an adduct of alkylene oxide (eg, hydroxy C _1-10 alkoxy compound) You can also get

  Of the aromatic diols, araliphatic diols [for example, di (hydroxyalkyl) arene and the like], alkylene oxide adducts of bisphenols, and the like are preferable. When at least one selected from an alicyclic diol and an aromatic diol (particularly at least an aromatic diol) and an aliphatic diol (an alkane diol such as ethylene glycol) are used in combination, the alkane diol can be used as a reaction solvent, The esterification reaction can proceed smoothly.

  The ratio of at least one selected from alicyclic diols and aromatic diols (particularly at least aromatic diols) and aliphatic diols is the former / the latter (molar ratio) = 100/0 to 5/95 (for example, 98 / 2 to 10/90), for example, 95/5 to 30/70 (for example, 90/10 to 50/50), more preferably 85/15 to 55/45 (for example, 80 / 20-60 / 40).

  The polyester resin can be prepared by using a conventional method such as a melt polymerization method, a solution polymerization method, an interfacial polymerization method. An industrially preferred method is a melt polymerization method.

  In the reaction, one of the dicarboxylic acid component and the diol component may be used in excess of the other component. For example, reaction components that volatilize in the reaction system (such as alkanediols such as ethylene glycol) may be used in excess.

The reaction may be performed in the presence of a metal catalyst. Examples of the metal catalyst include alkali metals (sodium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (manganese, zinc, cadmium, Lead, cobalt, etc.), periodic table group 13 metals (aluminum, etc.), periodic table group 14 metals (germanium, etc.), periodic table group 15 metals (antimony, etc.) are used. Examples of the metal compound include alkoxides, organic acid salts (such as acetates), inorganic acid salts (such as borates and carbonates), and metal oxides. These catalysts can be used alone or in combination of two or more. The amount of the catalyst used may be, for example, about 0.01 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol with respect to 1 mol of the dicarboxylic acid component.

The reaction may be performed in the presence of an additive such as a stabilizer (antioxidant, heat stabilizer, etc.) as necessary. The reaction can usually be performed in an inert gas (nitrogen, helium, etc.) atmosphere. The reaction can also be performed under reduced pressure (for example, about 1 × 10 ² to 1 × 10 ⁴ Pa). The reaction temperature can be selected according to the polymerization method, and the reaction temperature in the melt polymerization method may be, for example, about 200 to 300 ° C, preferably about 230 to 290 ° C.

The weight average molecular weight of the polyester resin can be selected from the range of about 0.1 × 10 ⁴ to 50 × 10 ⁴ , for example, 1 × 10 ⁴ to 15 × 10 ⁴ , preferably 2 × 10 ⁴ to 10 × 10 ⁴ , More preferably, it may be about 3 × 10 ⁴ to 8 × 10 ⁴ .

  The polyester resin of the present invention often has a relatively high refractive index. Therefore, it can be used alone or in combination with other resins as an optical resin. The refractive index of the polyester resin is 1.53 or more (for example, 1.54 or more), preferably 1.55 or more (for example, 1.55 to 1.75), more preferably 1.50 at 20 ° C. and a wavelength of 589 nm. It may be about 56 or more (for example, 1.56 to 1.72).

The polyester resin may have low birefringence (the absolute value of birefringence is small) or negative birefringence. The intrinsic birefringence value of the polyester resin is, for example, −150 × 10 ⁻⁴ to + 40 × 10 ⁻⁴ (for example, −120 × 10 ⁻⁴ to + 35 × 10 ⁻⁴ ), preferably −120 × 10 ⁻⁴ to It may be about + 25 × 10 ⁻⁴ . In particular, the polyester resin of the present invention has an intrinsic birefringence, negative, for ^{example, -100 × 10 -4 ~-10} × 10 -4, preferably ^{-90 × 10 -4 ~-15 ×} 10 about ^-4 It may be.

  Furthermore, the polyester resin of the present invention has a relatively high heat resistance. For example, the glass transition temperature (Tg) can be selected from the range of 50 to 200 ° C. (for example, 60 to 180 ° C.), for example, 70 to 200. C., preferably 75 to 180.degree. C. (for example, 100 to 180.degree. C.), more preferably about 80 to 170.degree. C. (for example, 120 to 170.degree. C.).

Polyamide resin Polyamide resin can be prepared by the reaction of a dicarboxylic acid component and a diamine component. The reaction component is an aminocarboxylic acid component [aminocarboxylic acid (for example, 6-aminocaproic acid, 12-aminododecanoic acid, etc.), lactam (ε -Caprolactam etc.) etc.] may be included.

  The diamine component includes an aliphatic diamine, an alicyclic diamine, and an aromatic diamine. These diamines may be used alone or in combination of two or more.

Aliphatic diamines include alkane diamines such as ethylene diamine, propylene diamine, 1,3-trimethylene diamine, 1,4-tetramethylene diamine, 1,6-hexamethylene diamine, 1,8-octamethylene diamine, 1, C _2-20 alkane diamines (preferably C _2-12 alkane diamines) such as 9-nonamethylene diamine, 1,10-decamethylene diamine, 1,11-undecamethylene diamine, 1,12-dodecamethylene diamine, etc. It can be illustrated.

Examples of the alicyclic diamine include cycloalkane diamine (for example, C _5-8 cycloalkane diamine such as diaminocyclohexane and methylcyclohexane diamine), isophorone diamine, bridged bi- or tricycloalkane diamine (for example, norbornane diamine). Etc.).

Aromatic diamines include, for example, arene diamines (for example, C _6-10 arene diamines such as m-phenylene diamine and p-phenylene diamine), di (aminoalkyl) arenes [for example, m-xylylenediamine, p-xylylene. Di (amino C _1-4 alkyl) C _6-10 arene] such as range amine] and the like.

Furthermore, the alicyclic diamine and the aromatic diamine are compounds represented by the following formula (5) (in the formula (3), the ring Z ₁ is a cycloalkane ring or an arene ring, and —O— (R ₅ O And a compound having an amino group instead of _p- H).

(In the formula, ring Z ₂ represents a cycloalkane ring or an arene ring, and X, q, R ₄ and n are the same as above)
Examples of the cycloalkane ring and arene ring represented by the ring Z ₂ include the same cycloalkane ring as the ring Z, and the same arene ring as the ring Z or Z ₁ .

Examples of the alicyclic diamine represented by the formula (5) (a compound in which the ring Z ₂ is a cycloalkane ring) include di (aminocycloalkyl) alkanes [for example, 4,4′-diaminodicyclohexylmethane, 4 , 4'-like diaminodicyclohexylmethane propane (amino _{C 5-8 cycloalkyl) C 1-4} alkanes; 4,4'-diamino-3,3'-such as dimethyl dicyclohexylmethane (amino _{-C 1-4} Alkyl C _5-10 cycloalkyl) C _{1-4 and the} like] and the like.

Examples of the aromatic diamine represented by the formula (5) (a compound in which the ring Z ₂ is an arene ring) include di (aminoaryl) alkanes [for example, di (amino C ₆₋ ) such as 4,4′-diaminodiphenylmethane. _{8 aryl) C 1-4} alkane such as]; di (amino aryloxyaryl) alkanes [e.g., 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- ( Di (amino C _6-10 aryloxy C _6-10 aryl) C _1-10 alkane such as 4-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane Etc.]; di (alkyl-aminoaryloxyaryl) alkanes [eg, 2,2-bis [3-methyl-4- (4-aminophenoxy) fe Nyl] propane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] propane and the like (C _1-10 alkyl-amino C _6-10 aryloxy C _6-10 aryl) C _1-10 alkanes and the like]; di (halo-aminoaryloxyaryl) alkanes [eg di (halo-amino) such as 2,2-bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] propane. Amino C _6-10 aryloxy C _6-10 aryl) C _1-10 alkane and the like]; di (aminoaryloxyaryl) cycloalkanes [eg, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclopentane, 1,1-bis [4- (4-aminophenoxy) phenyl] di cyclohexane (amino _{C 6-10} Ariruoki C _{6-10 aryl) C 5-8} cycloalkane, etc.]; di (aminoaryl oxy) bis-aryl compound [for example, 4,4'-bis (4-aminophenoxy) biphenyl, etc.) di (amino _{C 6-10,} such as Aryloxy) bis C _6-10 aryl and the like]; di (aminoaryl) ethers [eg, di (amino C _6-10 aryl) ether such as 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, etc. Di (aminoaryloxyaryl) ethers [e.g., di (amino C _6-10 aryloxy C _6-10 aryl) ethers such as di [4- (4-aminophenoxy) phenyl] ether, etc.]; Aminoaryl) sulfones [eg, 4,4′-diaminodiphenylsulfone, 3,3′-diamino Di diphenyl sulfone (amino _{C 6-10} aryl) sulfone]; di (amino aryloxyaryl) sulfones [e.g., di [4- (4-aminophenoxy) phenyl] di and sulfonic (amino _{C 6- 10} aryloxy C _6-10 aryl) sulfone and the like].

  In addition, as a preparation method of a polyamide resin, a conventional method, for example, a melt polymerization method (or melt polycondensation method), a solution polymerization method, an interfacial polymerization method etc. can be illustrated. The usage-amount of a dicarboxylic acid component and a diamine component can be selected according to a polymerization method.

  Specifically, in the melt polycondensation method, a salt prepared from a dicarboxylic acid component and a diamine component, or a dicarboxylic acid component and a diamine component are heated and melted, and elimination components such as water and alcohol are removed from the reaction system. The reaction can be performed. In the reaction, an excessive amount of a component that easily volatilizes may be used (for example, at a ratio of 0.01 to 3 mol% or more higher than the theoretical amount). Moreover, in order to prevent volatilization of volatile components (such as a diamine component), the reaction may be performed under pressure at the initial stage of the reaction. The polymerization reaction may be performed under normal pressure or reduced pressure, but in the latter stage of polymerization, the elimination component may be removed from the reaction system under reduced pressure (under reduced pressure of about 150 Pa). In the solution polycondensation method, the reaction is carried out while removing the elimination component in the solvent by azeotropic distillation, an acid acceptor such as a tertiary amine, or a condensing agent such as a triphenyl phosphite / pyridine mixed system. Can do. Further, in the interfacial polycondensation method, an acid halide of a dicarboxylic acid can be dissolved in a nonpolar solvent (organic phase) and reacted with a diamine component at the interface with an alkaline aqueous solution such as sodium hydroxide.

  The polyamide resin has excellent characteristics such as high heat resistance and a high refractive index. The glass transition temperature (Tg) of the polyamide resin can be selected from the range of 120 to 400 ° C. (for example, 140 to 350 ° C., preferably 150 to 330 ° C.), 200 to 350 ° C., preferably 210 to 300 ° C., more preferably. 215-280 degreeC may be sufficient.

  The refractive index of the polyamide resin can be selected from a range of 1.53 or more (for example, 1.54 or more) at 25 ° C. and a wavelength of 589 nm, and 1.55 to 1.75 (for example, 1.56 to 1.72). , Preferably 1.57 to 1.75 (for example, 1.58 to 1.72), more preferably about 1.59 to 1.7 (for example, 1.60 to 1.68).

  In addition, the thermoplastic resin into which the structural units (1a) and (1b) are introduced may contain various additives [for example, stabilizers (such as antioxidants, ultraviolet absorbers, thermal stabilizers, etc.), lubricants, Release agent, antistatic agent, colorant (dye / pigment), filler or reinforcing agent, conductive agent, flame retardant, plasticizer, dispersant, leveling agent, etc.]. These additives may be used alone or in combination of two or more.

[Addition of fluidity improver]
Even when a fluorene compound represented by the following formula (1a-1) and / or (1b-1) is added to the thermoplastic resin, the melt fluidity of the thermoplastic resin composition can be improved.

(Wherein, R _3a and R _3b are the same or different and represent a hydrogen atom or a hydrocarbon group, and R _1a , R _1b , R ₂ , m and k are the same as above)
As the hydrocarbon group represented by R _3a and R _3b , an alkyl group (for example, a linear or branched chain such as a methyl group, an ethyl group, a purpyr group, a butyl group, a t-butyl group, a hexyl group, and an octyl group) C _1-10 alkyl group, etc.), cycloalkyl group (C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group, methylcyclohexyl group, cyclooctyl group etc.), aryl group (C such as phenyl group) _6-10 aryl group), aralkyl groups (C _6-10 aryl-C _1-4 alkyl group such as benzyl group) and the like. R _3a and R _3b are often a hydrogen atom or an alkyl group (C _1-4 alkyl group such as a methyl group). In addition, the fluorene compound represented by the formulas (1a-1) and (1b-1) includes a part of the compound represented by the formula (1a-2) and the compound represented by the formula (1b-2). A compound in which —OR _3a and —OR _3b (wherein L ₁ and L ₂ are each a halogen atom) may be used, but such a compound has high reactivity and is difficult to handle. .

Examples of the thermoplastic resin to which the fluorene compounds (1a-1) and (1b-1) are added include olefin resins, halogen-containing vinyl resins (polyvinyl chloride, etc.), (meth) acrylic resins, and styrene resins. resins, polyester resins [e.g., polyalkylene terephthalate (polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, etc. of poly C _2-4 alkylene terephthalate, poly cyclohexane dimethylene terephthalate, etc.), polyalkylene arylate-series resin such as polyethylene naphthalate, Polysynthesis of polyarylate resins (for example, aromatic dicarboxylic acids (terephthalic acid, etc.) and aromatic diols (biphenol, bisphenol A, xylylene glycol, alkylene oxide adducts thereof, etc.) Polyarylate resin used as the like], polycarbonate resin (for example, bisphenol A type polycarbonate), polythiocarbonate resin, polyacetal resin, polyamide resin, polyphenylene ether resin, polyether ketone resin, polysulfone Resin, polyphenylene sulfide resin, polyimide resin, thermoplastic elastomer and the like. The thermoplastic resins may be used alone or in combination of two or more.

The thermoplastic resin is a resin containing an aromatic ring (such as a benzene ring), for example, an aromatic polycarbonate resin (such as a bisphenol A polycarbonate), an aromatic polyester resin (such as the polyalkylene arylate resin), or a polysulfone resin. Polyphenylene ether resins, polyphenylene sulfide resins and the like may be used. The thermoplastic resin is a resin having a 9,9-bisarylfluorene skeleton, for example, 9,9-bis (hydroxyaryl) fluorenes (9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-phenyl-3-hydroxyphenyl) fluorene, 9,9-bis (6-hydroxynaphthyl) fluorene, etc.); 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes (eg, 9,9-bis (hydroxy (poly) C _2-4 such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene) Polyester resin, polycarbonate resin, polyurethane resin using alkoxyphenyl) fluorene) Anyway.

  The amount of the fluorene compound (1a-1) (1b-1) used can be selected from a range of about 1 to 100 parts by weight (for example, 1 to 50 parts by weight) with respect to 100 parts by weight of the thermoplastic resin, It may be about 2.5 to 50 parts by weight, preferably 5 to 30 parts by weight, and more preferably about 10 to 25 parts by weight. If the amount of the fluorene compound (1a-1) (1b-1) used is too small, the melt fluidity of the resin composition will not be improved so much. If it is too large, the mechanical properties of the resin composition may be reduced. There is.

  The resin composition to which the fluorene compounds (1a-1) and (1b-1) are added may contain various additives [for example, thermoplastics into which the structural units (1a) and (1b) are introduced. The additives exemplified in the section of resin] may be contained alone or in combination of two or more.

  The thermoplastic resin is improved in melt flowability by introducing the structural units (1a) and (1b), and the resin composition is improved by adding the fluorene compounds (1a-1) and (1b-1). . Therefore, the thermoplastic resin and the resin composition are suitable for molding various molded articles by melt formation. The shape of the molded body may be, for example, a two-dimensional structure (film, sheet, plate, etc.) or a three-dimensional structure (tubular, rod-shaped, tube-shaped, hollow, block-shaped, etc.) There may be. 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.

  Since the thermoplastic resin and resin composition of the present invention are excellent in optical properties, they are suitable for forming optical materials or optical molded articles (in particular, optical films, optical lenses, etc.).

  The thickness of the film can be selected from the range of about 1 to 1000 μm depending on the application, and may be, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably about 10 to 120 μm. The film (optical film) can be formed (or molded) using a conventional film forming method, melt extrusion method, calendar method, or the like.

  The film may be a stretched film (uniaxial or biaxially stretched film). The stretching ratio may be about 1.1 to 10 times (for example, 1.2 to 5 times, preferably 1.5 to 3 times) in each direction of uniaxial or biaxial stretching. 0.1 to 2.5 times (for example, 1.2 to 2.3 times), preferably about 1.5 to 2.2 times.

  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 or a film were performed with the following method.

(Molecular weight)
Using gel permeation chromatography (manufactured by Tosoh Corporation, HLC-8120GPC), the sample was dissolved in chloroform, and the molecular weight was measured in terms of polystyrene.

(Glass transition temperature (Tg))
Using a differential scanning calorimeter (Seiko Instruments Co., Ltd., DSC 6220), the sample was placed in an aluminum pan and Tg was measured.

(Refractive index)
Using Kalnew precision refractometer (Ltd. Shimadzu Device Corporation "KPR-2000"), at a measurement temperature of 20 ° C., it was measured refractive index _{n d} at a wavelength of 589 nm.

(Melt flow rate (MFR)
The melt flow rate (MFR) was measured according to JIS K7210 at a temperature (glass transition temperature Tg of a thermoplastic resin Tg + 120 ° C.) under a load of 2.16 kg.

Example 1
In Example 1 of Japanese Patent Application Laid-Open No. 2005-89422, 9,9-di (2- (2)) was similarly used except that methyl acrylate (37.9 g (0.44 mol)) was used instead of t-butyl acrylate. Methoxycarbonylethyl) fluorene (hereinafter referred to as FDPM) was synthesized.

FDPM 0.5 mol, terephthalic acid dimethyl ester (hereinafter referred to as DMT) 0.5 mol, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (hereinafter referred to as BPEF) 0.85 mol and ethylene Glycol (hereinafter referred to as EG) 0.15 mol, manganese acetate tetrahydrate 2 × 10 ⁻⁴ mol and calcium acetate monohydrate 8 × 10 ⁻⁴ mol as transesterification catalysts were added and gradually stirred. After heating and melting and raising the temperature to 230 ° C., trimethyl phosphate 14 × 10 ⁻⁴ mol and germanium oxide 20 × 10 ⁻⁴ mol were added, and the temperature was gradually raised and reduced until reaching 270 ° C. and 0.13 kPa or less. The ethylene glycol was removed. After reaching a predetermined stirring torque, the contents were taken out of the reactor to obtain polyester resin pellets.

Comparative Example 1
A polyester resin was obtained in the same manner as in Example 1 except that 1.0 mol of DMT, 0.85 mol of BPEF and 0.15 mol of EG were used.

Example 2
A polyester resin was obtained in the same manner as in Example 1, except that 0.5 mol of FDPM, 0.5 mol of dimethyl isophthalate (hereinafter referred to as DMI), 0.85 mol of BPEF and 0.15 mol of EG were used.

Comparative Example 2
A polyester resin was obtained in the same manner as in Example 1 except that 1.0 mol of DMI, 0.85 mol of BPEF and 0.15 mol of EG were used.

Example 3
Other than using 0.5 mol of FDPM, 0.5 mol of 2,6-dimethoxycarbonylnaphthalene (2,6-naphthalenedicarboxylic acid methyl ester) (hereinafter simply referred to as DMN), 0.85 mol of BPEF and 0.15 mol of EG In the same manner as in Example 1, a polyester resin was obtained.

Example 4
A polyester resin was obtained in the same manner as in Example 1 except that 1.0 mol of FDPM, 0.85 mol of BPEF and 0.15 mol of EG were used.

Comparative Example 3
A polyester resin was obtained in the same manner as in Example 1 except that 1.0 mol of DMN, 0.85 mol of BPEF and 0.15 mol of EG were used.

Example 5
Other than using 0.5 mol of FDPM, 0.5 mol of DMT, 0.80 mol of ethylene oxide adduct of bisphenol A (addition mol number 4 mol, simply referred to as “Bis-A 2EO”), and 0.2 mol of EG, A polyester resin was obtained in the same manner as in Example 1.

Comparative Example 4
A polyester resin was obtained in the same manner as in Example 1 except that 1 mol of DMT, 0.80 mol of “Bis-A 2EO”, and 0.2 mol of EG were used.

Example 6
Except for using 0.5 mol of FDPM, 0.5 mol of methyl 1,4-cyclohexanedicarboxylate (CHDM), 0.80 mol of “Bis-A 2EO”, and 0.2 mol of EG, the same as in Example 1. A polyester resin was obtained.

Example 7
A polyester resin was obtained in the same manner as in Example 1 except that 1 mol of FDPM, 0.80 mol of “Bis-A 2EO”, and 0.2 mol of EG were used.

Comparative Example 5
A polyester resin was obtained in the same manner as in Example 1 except that 1 mol of CHDM, 0.80 mol of “Bis-A 2EO”, and 0.2 mol of EG were used.

  The results are shown in Table 1.

  As is apparent from the above table, the melt flowability of the thermoplastic resins obtained in the examples is greatly improved while maintaining a high refractive index and heat resistance.

  In the present invention, melt fluidity can be improved while maintaining high heat resistance. Therefore, a thermoplastic resin into which a predetermined structural unit is introduced and a thermoplastic resin composition to which a predetermined fluorene compound is added are suitable for molding various molded articles using high melt fluidity. Since the thermoplastic resin and the resin composition have a high refractive index and excellent optical characteristics, they are useful for constructing (or forming) a molded article (optical molded article) for optical use. . Such an optical molded body can be used for molding optical lenses, optical films or sheets, pickup lenses, holograms, liquid crystal films, organic EL films, and the like. 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, color filter layer, black matrix layer, barrier film, adhesive layer or release layer between optical films. Furthermore, the film is useful as an optical film for use in equipment displays. Examples of the display include personal computer monitors, televisions, mobile phones, car navigation systems, FPD devices such as touch panels (for example, LCDs, PDPs, etc.).

  Further, the thermoplastic resin and the thermoplastic resin composition include paints, antistatic agents, inks, adhesives, pressure-sensitive adhesives, resin fillers, charging trays, conductive sheets, protective films (protective films such as electronic devices and liquid crystal members). Etc.), electrical / electronic materials (carrier transport agents, light emitters, organic photoreceptors, thermal recording materials, hologram recording materials), electrical / electronic components or equipment (optical disks, inkjet printers, digital paper, organic semiconductor lasers, dye sensitization) Resin for type solar cell, EMI shield film, photochromic material, organic EL element, color filter, etc.), resin for machine parts or equipment (automobile, aviation / space material, sensor, sliding member, etc.), etc. .

Claims (7)

A method for improving the fluidity of a thermoplastic resin, wherein the structural unit of the resin is represented by the following formula (1a) and / or (1b):

(Wherein, R _1a and R _1b are the same or different and each represents an alkylene group which may have a substituent, R ₂ represents an inert substituent, m represents an integer of 0 to 4, and k represents 0 or an integer of 1 to 4 is shown)
A method for improving the melt fluidity of a thermoplastic resin by introducing a structural unit represented by As a structural unit of thermoplastic resin, the following formula (2-2)

(In the formula, ring Z represents a hydrocarbon ring, R ₄ represents an inert substituent, and n represents 0 or an integer of 1 to 4)
The method of Claim 1 which introduce | transduces the unit represented by these.   The method of Claim 1 or 2 which introduce | transduces the structural unit represented by Formula (1a) and / or (1b) in the ratio of 10 mol% or more with respect to the whole structural unit of a thermoplastic resin.   The ratio (molar ratio) between the unit represented by the formula (1a) and / or (1b) and the unit represented by the formula (2-2) is the former / the latter = 100/0 to 30/70 Item 3. The method according to Item 2.   The method according to any one of claims 1 to 4, wherein the thermoplastic resin is at least one selected from a polyester resin and a polyamide resin. In the thermoplastic resin, the following formula (1a-1) and / or (1b-1)

(Wherein R _3a and R _3b are the same or different and represent a hydrogen atom or a hydrocarbon group, and R _1a , R _1b , R ₂ , m and k are the same as in claim 1).
A method for improving the melt fluidity of the thermoplastic resin by adding a fluorene compound represented by the formula: An additive for improving melt flowability by adding to a thermoplastic resin, the following formula (1a-1) and / or (1b-1)

(Wherein R _3a and R _3b are the same or different and represent a hydrogen atom or a hydrocarbon group, and R _1a , R _1b , R ₂ , m and k are the same as in claim 1).
A flow improver composed of a fluorene compound represented by: