JP5600248B2 - Polycarbonate resin composition and molded article - Google Patents

Description

  The present invention relates to a polycarbonate resin composition comprising a polycarbonate resin and a polyester oligomer having a fluorene skeleton (for example, a 9,9-bis (aryl) fluorene skeleton).

  Polycarbonate (particularly aromatic polycarbonate) is widely used as an optical member because it is excellent in heat resistance and hygroscopicity, has high transparency, and exhibits a high refractive index. However, since polycarbonate has a high birefringence, it is not necessarily suitable for the use of high-precision optical members (for example, optical lenses and optical films).

  Therefore, it has been proposed to use a fluorene compound such as 9,9-bis (4-hydroxyphenyl) fluorene having high refractive index and low birefringence characteristics. Specifically, a method in which a fluorene compound or a resin containing this compound as a polymerization component (such as a fluorene skeleton-containing polyester) is added to polycarbonate has been studied.

  For example, JP-A-8-41303 (Patent Document 1) discloses a substantially linear polyester polymer comprising an aromatic dicarboxylic acid or a derivative thereof, a dihydroxy compound having a fluorene skeleton and an aliphatic glycol, and an aromatic A resin composition comprising a homogeneous blend mixture with a group polycarbonate is disclosed. It is described that the polymerization degree of the dihydroxy compound having a fluorene skeleton is 0.3 to 0.8 in terms of intrinsic viscosity, and the ratio (weight ratio) between the polyester polymer and the aromatic polycarbonate is the former / the latter = 5. / 95 to 95/5. Furthermore, in the examples of this document, a polyester having an intrinsic viscosity of about 0.5 obtained by reacting dimethyl terephthalate, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and ethylene glycol. It is described that a resin composition was obtained by blending a copolymer and a bisphenol A-type polycarbonate resin at a ratio of 20:80 (weight ratio).

JP 2004-315676 A (Patent Document 2) includes a diol component composed of a diol having a 9,9-bisphenolfluorene skeleton and a dicarboxylic acid component composed of at least an alicyclic dicarboxylic acid. A resin composition containing an aromatic polyester resin and a polycarbonate resin is disclosed. In this document, the weight average molecular weight of the aromatic polyester resin is 0.5 × 10 ^{4 to} 100 × 10 ⁴ , and the amount of the polycarbonate resin used is 10 to 300 weights with respect to 100 parts by weight of the aromatic polyester resin. Part. Also, in the examples of this document, 1,4-cyclohexanedicarboxylic acid, ethylene glycol, and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene are melt-polymerized, and the weight average molecular weight is 51000. It is described that a copolyester was obtained. Furthermore, it is also described that 50 parts by weight of this copolyester and 50 parts by weight of polycarbonate are melt-mixed to obtain a resin composition.

  However, when such a fluorene-based polyester resin is added to the polycarbonate resin, handling and workability become difficult. In particular, when a small amount is added, the miscibility with the polycarbonate resin becomes low and birefringence cannot be sufficiently reduced. In addition, when added in a large amount, toughness such as elongation strength is lowered.

  JP-A-2005-162785 (Patent Document 3) includes a compound having a fluorene skeleton such as (meth) acrylate of 9,9-bis (hydroxyphenyl) fluorene and a thermoplastic resin such as a polycarbonate resin. A resin composition that is configured and has high optical properties such as low birefringence is disclosed. Moreover, in the Example of this literature, it describes that the cast film was obtained using 40 weight part of bisphenoxyethanol full orange acrylate and 100 weight part of polycarbonate-type resin.

  However, when these low molecular compounds having a fluorene skeleton are added to the resin, the compound having the fluorene skeleton is likely to bleed out, and the mechanical strength may be extremely reduced.

JP-A-8-41303 (Claim 1, paragraphs [0010] [0013], Example) JP 2004-315676 A (claims 1 and 7, paragraphs [0036] and [0057], examples) JP-A-2005-162785 (Claims 1 and 4, Examples)

  Accordingly, an object of the present invention is to provide a polycarbonate resin composition having reduced birefringence and excellent optical properties, and a molded body formed from this resin composition.

  Another object of the present invention is to provide a resin composition that can reduce birefringence and is excellent in toughness without impairing the properties (for example, mechanical properties) of the polycarbonate-based resin, and a molded body formed from this resin composition. It is to provide.

  Still another object of the present invention is to provide a resin composition in which bleed-out is suppressed and a molded body formed from this resin composition.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that birefringence is greatly reduced when a fluorene polyester oligomer is added to a polycarbonate resin, thereby completing the present invention.

  That is, the polycarbonate resin composition of the present invention is composed of a polycarbonate resin and a fluorene polyester oligomer having a 9,9-bis (aryl) fluorene skeleton.

  The weight average molecular weight of the fluorene polyester oligomer may be about 2000 to 15000 (for example, 8000 to 12000). The fluorene polyester oligomer is represented by the following formula (1).

(In the formula, ring Z represents an aromatic hydrocarbon ring, and R ¹ and R ³ are the same or different, and are hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio. Group, arylthio group, aralkylthio group, halogen atom, nitro group, cyano group, N, N-disubstituted amino group, R ² represents an alkylene group, k is an integer of 0 to 4, n and p are respectively (It is an integer of 0 or more.)
The diol component containing the fluorene compound represented by this, and the condensate of a dicarboxylic acid component may be sufficient.

  The ratio of the fluorene polyester oligomer may be about 1 to 50 parts by weight (for example, 10 to 25 parts by weight) with respect to 100 parts by weight of the polycarbonate resin.

  This invention contains the molded object (for example, optical member) formed with the said resin composition.

  In the present specification, the fluorene polyester oligomer is an oligomer (ester oligomer, polyester) obtained by condensation of a diol component containing a compound having at least a 9,9-bis (hydroxyaryl) fluorene skeleton and a dicarboxylic acid component. Oligomer).

  In the present invention, since the fluorene polyester oligomer is added to the polycarbonate resin, high optical properties (high refractive index, low birefringence) of fluorene can be imparted. In addition, compared to the addition of high molecular weight fluorene polyester, the birefringence of the polycarbonate resin composition can be greatly reduced even if the addition amount is small, and by adjusting the molecular weight and addition amount of the fluorene polyester oligomer, Both properties and mechanical properties can be achieved. Moreover, since the fluorene polyester in the oligomer region is added, the compatibility with the polycarbonate resin is high, and the function of the fluorene skeleton can be efficiently imparted. Furthermore, unlike the addition of low molecular weight compounds, bleed out can be suppressed and high optical properties can be maintained for a long period of time.

[Polycarbonate resin composition]
The resin composition of the present invention is a resin composition composed of a polycarbonate resin and a fluorene polyester oligomer.

(Polycarbonate resin)
As the polycarbonate-based resin, an aromatic polycarbonate-based resin (a polycarbonate-based resin having an aromatic dihydroxy compound as a polymerization component), particularly a bisphenol-type polycarbonate-based resin (a polycarbonate-based resin having a bisphenol as a polymerization component) is preferable.

Examples of bisphenols include bis (hydroxyphenyl) alkanes [for example, bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane (bisphenol AD), 2,2 -Bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis ( Bis (hydroxyaryl) C _1-6 alkanes such as 4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxytolyl) propane, 2,2-bis (4-hydroxyxylyl) propane, etc.] Bis (hydroxyaryl) cycloalkanes [for example, 1,1-bis (4-hydroxy Phenyl) cyclopentane, bis (hydroxyaryl) C _4-10 cycloalkane such as 1,1-bis (4-hydroxyphenyl) cyclohexane, etc.], bis (hydroxyaryl) fluorenes [for example, 9,9-bis (4 -Hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc.], bis (hydroxyaryl) ethers [for example, bis (4-hydroxyphenyl) ether, etc.], bis (hydroxyaryl) ) Ketones [for example, 4,4′-di (hydroxyphenyl) ketone, etc.], bis (hydroxyphenyl) sulfones [for example, bis (4-hydroxyphenyl) sulfone (bisphenol S), etc.], bis (hydroxyphenyl) Sulfoxides [for example, bis (4- Examples thereof include droxyphenyl) sulfoxide and the like] and bis (hydroxyphenyl) sulfides [for example, bis (4-hydroxyphenyl) sulfide and the like]. These bisphenols can be used alone or in combination of two or more.

Of these bisphenols, bis ( _{hydroxyC 6-10} aryl) C _1-6 alkanes such as bisphenol A are preferred.

  The number average molecular weight of the polycarbonate-based resin may be, for example, about 10,000 to 100,000, preferably about 15,000 to 80,000, and more preferably about 20,000 to 50,000.

  The polycarbonate resin can be obtained by a conventional method (for example, phosgene method, transesterification method, etc.).

(Fluorene polyester oligomer)
Compared with high molecular weight fluorene polyester, the fluorene polyester in the oligomer region is more compatible with a polycarbonate resin even if the addition amount is small, and is advantageous in reducing birefringence with a small addition amount. Moreover, even if a fluorene polyester oligomer is added to a polycarbonate-based resin, bleeding out is suppressed, and high optical properties can be imparted over a long period of time.

  The fluorene polyester oligomer may be linear or may have a branched structure. The fluorene polyester oligomer may be a condensate obtained by condensing a diol component containing at least a fluorene compound and a dicarboxylic acid component.

(Diol component containing fluorene compound)
The fluorene compound is not particularly limited as long as it has a 9,9-bis (hydroxyaryl) fluorene skeleton.

(In the formula, ring Z represents an aromatic hydrocarbon ring, and R ¹ and R ³ are the same or different, and are hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio. Group, arylthio group, aralkylthio group, halogen atom, nitro group, cyano group, N, N-disubstituted amino group, R ² represents an alkylene group, k is an integer of 0 to 4, n and p are respectively (It is an integer of 0 or more.)
The compound represented by these may be sufficient.

In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z include a condensed polycyclic aromatic hydrocarbon ring having at least a benzene ring skeleton in addition to a benzene ring [for example, a condensed bicyclic hydrocarbon Ring (C _8-20 condensed bicyclic hydrocarbon ring such as indene ring, naphthalene ring, etc., preferably C _10-16 condensed bicyclic hydrocarbon ring etc.), condensed tricyclic hydrocarbon ring (anthracene ring, phenanthrene ring) Etc.) and the like.

  The two rings Z substituted at the 9-position of fluorene may be the same or different from each other, and are usually the same ring in many cases.

  Of the rings Z, a benzene ring, a naphthalene ring (particularly a benzene ring) and the like are preferable. In addition, the substitution position of the ring Z substituted by 9-position of fluorene is not specifically limited. For example, when the ring Z is a naphthalene ring, the group corresponding to the ring Z substituted at the 9-position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, or the like.

Examples of the hydrocarbon group represented by the group R ¹ and the group R ³ include an alkyl group (for example, a C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, preferably _{C 1-4} alkyl group, more preferably a _{C 1-3} alkyl group, especially methyl or ethyl group), a cycloalkyl group (cyclopentyl, _{C 5-8} cycloalkyl groups such as cyclohexyl group, preferably C _5-6 cycloalkyl group, etc.), aryl groups [eg, phenyl group, alkylphenyl group (mono or dimethylphenyl group (tolyl group, 2-methylphenyl group, xylyl group etc.)), naphthyl group, etc. _6-10 aryl group, preferably phenyl group, etc.], aralkyl group (C _6-10 aryl-C _1-4 such as benzyl group, phenethyl group, etc.) An alkyl group etc.) can be illustrated.

Examples of the alkoxy group represented by the groups R ¹ and R ³ include C _1-6 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, and a t-butoxy group (preferably a C _1-4 alkoxy group). Group, more preferably C _1-3 alkoxy group, etc.), and examples of the cycloalkoxy group include C _5-8 cycloalkyloxy groups such as cyclohexyloxy groups (C _5-6 cycloalkyloxy groups, etc.). it can. Furthermore, examples of the aryloxy group include C _6-10 aryloxy groups such as a phenoxy group, and examples of the aralkyloxy group include C _6-10 aryl-C _1-4 alkyloxy groups such as a benzyloxy group. Etc. can be exemplified.

Examples of the alkylthio group, cycloalkylthio group, arylthio group, and aralkylthio group represented by the group R ¹ and the group R ³ include groups corresponding to the above alkoxy group, cycloalkoxy group, aryloxy group, and aralkyloxy group, respectively. it can.

Examples of the halogen atom represented by the group R ¹ and the group R ³ include a fluorine atom, a chlorine atom and a bromine atom.

As the N, N-disubstituted amino group represented by the group R ¹ and the group R ³ , an N, N-dialkylamino group (a diC _1-6 alkylamino group such as an N, N-dimethylamino group, preferably A di-C _1-4 alkylamino group, etc.).

Examples of the alkylene group represented by the group R ² include C _2-6 alkylene such as ethylene group, propylene group (or 1,2-propanediyl group), trimethylene group, 1,2-butanediyl group, and tetramethylene group. Group, preferably a _C2-4 alkylene group, more preferably a _C2-3 alkylene group. Of these alkylene groups, an ethylene group is particularly preferable. In addition, when n is an integer greater than or equal to 2, the alkylene group in each oxyalkylene unit may be the same or different, and is usually the same in many cases. In the two rings Z, the groups R ² may be the same or different from each other and are usually the same in many cases.

N indicating the oxyalkylene group repeating number of (OR ²⁾ (number of moles added) is 0-15 (e.g., 0-10) can be selected from the range of about, for example, 0-6 (e.g., 1-5), preferably May be 0 to 4 (for example, 1 to 3), more preferably about 0 to 2 (particularly 0 or 1). The oxyalkylene groups bonded to the two rings Z may be the same or different from each other and are usually the same in many cases. P representing the number of substitutions of the group R ³ substituted on the ring Z may be, for example, 0 to 6, preferably 0 to 3, and more preferably about 0 to 2.

  Typical examples of the compound represented by the formula (1) include 9,9-bis (hydroxyaryl) fluorenes and 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes.

As 9,9-bis (hydroxyaryl) fluorenes, for example, 9,9-bis (hydroxyphenyl) fluorenes {for example, 9,9-bis (hydroxyphenyl) fluorene [for example, 9,9-bis (4 -Hydroxyphenyl) fluorene and the like], 9,9-bis (hydroxy-alkylphenyl) fluorene [for example, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy- 3-ethylphenyl) fluorene, 9,9-bis (3-hydroxy-2-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4 - hydroxy-2,6-dimethylphenyl) fluorene such as 9,9-bis (hydroxy - mono- or _{di-C 1-4} a Alkenyl) fluorene], 9,9-bis (hydroxy-arylphenyl) fluorene [e.g., 9,9-bis (hydroxy-mono or 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, etc. DiC _6-10 arylphenyl) fluorene etc.] ;; 9,9-bis (hydroxynaphthyl) fluorenes {compounds corresponding to {9,9-bis (hydroxyphenyl) fluorenes, wherein the phenyl group is substituted with a naphthyl group , For example, 9,9-bis (hydroxynaphthyl) fluorene [for example, 9,9-bis (6-hydroxy-2-naphthyl) fluorene and the like].

As 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes, compounds corresponding to the 9,9-bis (hydroxyaryl) fluorenes such as 9,9-bis (hydroxyalkoxyphenyl) fluorene {for example, 9,9-bis [hydroxy (C ₂ ) such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- or 3-hydroxypropoxy) phenyl] fluorene _-4 alkoxy-phenyl) fluorene, etc., 9,9-bis (hydroxyalkoxy-alkylphenyl) fluorene {e.g., 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9, 9-bis [2- (2-hydroxyethoxy) -5-methylphenyl] fluorene, 9, 9,9-bis such as 9-bis [4- (3-hydroxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene (Such as hydroxy C _2-4 alkoxy-mono or di C _1-6 alkylphenyl) fluorene}, 9,9-bis (hydroxyalkoxy-arylphenyl) fluorene {eg, 9,9-bis [4- (2-hydroxy 9,9-bis (hydroxyalkoxyphenyl) fluorene such as 9,9-bis (hydroxy C _2-4 alkoxy-mono or di-C _6-10 arylphenyl) fluorene} such as ethoxy) -3-phenylphenyl] fluorene 9,9-bis (hydroxyalkoxynaphthyl) fluorene {e.g., 9,9-bis [2- (6- (2-hydroxyethoxy) naphthyl)] fluorene such as 9,9-bis 9,9-bis (hydroxyalkoxy naphthyl) fluorene such as (hydroxy _{C 2-4} alkoxy naphthyl) fluorene}; these compounds In which a hydroxyalkoxy group is substituted with a hydroxypolyalkoxy group, for example, 9,9-bis (hydroxypolyalkoxyaryl) -fluorenes {for example, 9,9-bis {4- [2- (2 9,9-bis [(hydroxy C _2-4 alkoxy) C _2-4 alkoxyphenyl] -fluorene, etc.] such as -hydroxyethoxy) ethoxy] phenyl} -fluorene.

  These fluorene compounds can be used alone or in combination of two or more. Among these fluorene compounds, 9,9-bis (hydroxyalkoxyphenyl) fluorenes such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene are widely used.

  A commercially available product may be used as the fluorene compound. In addition, fluorene compounds are described in the literature [J. Appl. Polym. Sci. 27 (9), 3289, 1982], JP-A-6-145087, JP-A-8-217713, JP-A-2000-26349, JP-A-2002-47227, JP-A-2003-221352. It may be produced by the method described in 1.

The diol component containing a fluorene compound may contain a diol component other than the fluorene compound in order to adjust fluidity and flexibility within a range not impairing the properties of the fluorene. Examples of diol components other than fluorene compounds include alkylene glycols (eg, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, decanediol, etc. Chain or branched C _2-12 alkylene glycol), (poly) oxyalkylene glycol (for example, di to tetra C _2-4 alkylene glycol such as diethylene glycol, triethylene glycol, dipropylene glycol, etc.) and the like. . Diol components other than these fluorene compounds can be used alone or in combination of two or more. Of these diol components other than the fluorene compound, linear or branched C _2-4 alkylene glycol such as ethylene glycol is preferable.

  The ratio (molar ratio) between the fluorene compound and the diol component other than the fluorene compound is the former / the latter = 60/40 to 99.9 / 0.1, preferably 70/30 to 99/1, and more preferably 80/20. About 90/10 may be sufficient.

(Dicarboxylic acid component)
The dicarboxylic acid component may be a dicarboxylic acid or a reactive derivative thereof (eg, acid anhydride, acid halide (eg, acid chloride), etc.). The dicarboxylic acid may be an aliphatic dicarboxylic acid, but from the viewpoint of maintaining the balance of mechanical strength, high refractive index and low birefringence, an alicyclic dicarboxylic acid, an aromatic dicarboxylic acid (particularly an alicyclic dicarboxylic acid). Dicarboxylic acid) is preferred.

Examples of the alicyclic dicarboxylic acid include saturated alicyclic dicarboxylic acid [monocyclic alkane dicarboxylic acid (for example, C _3-10 cycloalkane-dicarboxylic acid such as cyclopentane dicarboxylic acid, cyclohexane dicarboxylic acid, cycloheptane dicarboxylic acid, etc. Etc.), polycyclic alkane dicarboxylic acids (eg di or tricyclo C _7-10 alkane dicarboxylic acids such as bornane dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, etc.)], unsaturated alicyclic dicarboxylic acids [mono Cyclic alkene dicarboxylic acids (eg, C _3-10 cycloalkene-dicarboxylic acids such as cyclohexene dicarboxylic acid), polycyclic alkene dicarboxylic acids (eg, di- or tricyclo C _7- such as bornene dicarboxylic acid, norbornene dicarboxylic acid, etc.) ₁₀ alkenes -Dicarboxylic acid etc.)] and the like. As aromatic dicarboxylic acids, C _6-12 arene-dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid; 4,4′-biphenyldicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, 4 , 4′-diphenylmethane dicarboxylic acid, C _12-16 bisphenol-dicarboxylic acid such as 4,4′-diphenyl ketone dicarboxylic acid, etc.]. These dicarboxylic acids can be used alone or in combination of two or more.

  The ratio (molar ratio) between the alicyclic dicarboxylic acid and the other dicarboxylic acid is the former / the latter = 50/50 to 100/0, preferably 60/40 to 100/0, and more preferably 70/30 to 100 /. It may be about 0 (for example, 80/20 to 90/10).

  The fluorene polyester oligomer is 0.5 to 1.5 mol, preferably 0.6 to 1.4 mol, more preferably 0.8 to 1. mol of the dicarboxylic acid component with respect to 1 mol of the diol component containing the fluorene compound. It may be a condensate which is used at a ratio of about 2 mol and condensed (esterified).

(Multifunctional component)
The fluorene polyester oligomer may be a condensate obtained by condensing a polyfunctional component in addition to the diol component and the dicarboxylic acid component. This condensate often has a branched structure.

  The polyfunctional component may have a function of forming a branched structure. As the polyfunctional component, at least one functional group selected from a hydroxyl group and a carboxyl group or a reactive derivative group thereof (acyl halide group, acid anhydride group, etc.) per molecule is 3 or more (for example, 3 or 4 and particularly 3). Specifically, (i) trifunctional or higher functional polyols listed below, (ii) trifunctional or higher functional polycarboxylic acids, (iii) hydroxycarboxylic acids having a total of three or more hydroxyl groups and carboxyl groups, etc. Can be mentioned.

(I) As trifunctional or higher functional polyols, aliphatic C _3-10 alkanetriols such as glycerin, trimethylolethane and trimethylolpropane; tetravalent or higher such as diglycerin, polyglycerin, pentaerythritol and dipentaerythritol Examples of these alcohols. (ii) Trifunctional or higher functional polycarboxylic acids include carboxylic acids such as trimellitic acid, methylcyclohexeric carboxylic acid, pyromellitic acid or derivatives thereof [for example, acid anhydride, acid halide (for example, acid chloride), etc. ] Can be illustrated. (iii) Examples of hydroxycarboxylic acids having 3 or more hydroxyl groups and carboxyl groups in total include compounds having 2 hydroxyl groups and 1 carboxyl group (for example, dihydroxy C _3-6 alkanes such as glyceric acid and tartaric acid) Acid; dihydroxy aromatic carboxylic acid such as protocatechuic acid, etc.) compound having one hydroxyl group and two carboxyl groups (for example, hydroxy C _3-6 alkanedioic acid such as tartronic acid, malic acid, etc.), 3 Compound having one hydroxyl group and one carboxyl group (for example, trihydroxy aromatic carboxylic acid such as gallic acid) Compound having one hydroxyl group and three carboxyl groups (for example, citric acid) Etc. can be exemplified. These polyfunctional components can be used alone or in combination of two or more.

  The fluorene polyester oligomer is a polyfunctional component in an amount of 0 to 0.1 mol, preferably 0.001 to 0.05 mol, more preferably 0.002 to 1 mol of a diol component containing a fluorene compound and 1 mol of a dicarboxylic acid component. There may be a condensed product which is used at a ratio of about 0.01 mol and condensed. When the condensation ratio of the polyfunctional component is within the above range, gel generation can be suppressed.

  These fluorene polyester oligomers can be used alone or in combination of two or more.

  Such a fluorene polyester oligomer can be prepared using (A) a method of polymerizing (condensing) each component, (B) a method of depolymerizing a fluorene skeleton-containing polyester resin with a depolymerizer, and the like. These methods can be selected according to the application.

  The method (A) may be a method of polymerizing a diol component containing a fluorene compound, a dicarboxylic acid component, and, if necessary, a polyfunctional component. Examples of the polymerization method include conventional methods such as a melt polymerization method, a solution polymerization method, and an interfacial polymerization method, and the melt polymerization method is widely used.

  The proportion of the dicarboxylic acid component used is 0.5 to 1.5 mol, preferably 0.6 to 1.4 mol, more preferably 0.8 to 1.2, per 1 mol of the diol component containing the fluorene compound. It is preferable that one component is used in excess of the other component, particularly from the viewpoint of efficiently producing an oligomer. Moreover, when using a polyfunctional component, the usage-ratio is 0-0.1 mol with respect to 1 mol of diol components and dicarboxylic acid components containing a fluorene compound, Preferably it is 0.001-0.05 mol, More preferably May be about 0.002 to 0.01 mol.

  The reaction may be appropriately performed in the presence or absence of a solvent depending on the polymerization method.

The reaction may be carried out in the presence of a catalyst in order to obtain oligomers under mild conditions. As the catalyst, for example, a metal catalyst can be used. As the metal catalyst, for example, a metal compound containing an alkali metal (such as sodium), an alkaline earth metal (such as magnesium or barium), a transition metal (such as zinc, cadmium, lead, or cobalt) is used. Examples of the metal compound include alkoxide, organic acid salt (acetate, propionate, etc.), inorganic acid salt (borate, carbonate, etc.), metal oxide and the like. These catalysts can be used alone or in combination of two or more. The amount of the catalyst used is 0.01 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol, preferably 0.1 × 10 ⁻⁴ to 10 × 10, with respect to 1 mol of the diol component or dicarboxylic acid component containing the fluorene compound. ^{About -4} mol may be sufficient.

The reaction can usually be performed in an inert gas (nitrogen, helium, etc.) atmosphere, and may 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. For example, the reaction temperature in the melt polymerization method may be about 150 to 300 ° C, preferably about 180 to 290 ° C, and more preferably about 200 to 280 ° C.

  The method (B) may be a method in which a fluorene polyester is melt-kneaded with a depolymerizing agent using a solvent capable of dissolving the fluorene polyester as necessary, and the fluorene polyester is depolymerized.

  Examples of the fluorene polyester used for depolymerization include a condensate obtained by condensing the diol component containing the fluorene compound and the dicarboxylic acid component. The weight average molecular weight of the fluorene polyester is not limited to the high molecular weight, and can be selected from the oligomer region. When measured using gel permeation chromatography (solvent: tetrahydrofuran, reference resin: polystyrene), for example, 10,000 to 100,000, preferably May be about 15000 to 80000, more preferably about 20000 to 50000.

The depolymerizer is preferably composed of at least one component selected from a diol component other than the fluorene compound, the dicarboxylic acid component, and the polyfunctional component. The depolymerizing agent may be the same as or different from the polymerization component of the fluorene polyester. The depolymerizer may be, for example, the polyfunctional component, particularly an aliphatic C _3-10 alkanetriol such as trimethylolpropane. In addition, a hydroxyl value can be improved when diol or a polyol is used as a depolymerizing agent. On the other hand, when dicarboxylic acid or polycarboxylic acid is used as the depolymerizing agent, the acid value can be improved.

  The proportion of the depolymerizer is 1 to 30 parts by weight, preferably 1.2 to 28 parts by weight, more preferably 1.5 to 25 parts by weight, particularly 1.8 to 20 parts by weight, based on 100 parts by weight of the fluorene polyester. It may be about (for example, 2 to 20 parts by weight).

  The depolymerization reaction may be performed in the air, but is usually performed in an inert gas (nitrogen, helium, argon, etc.) atmosphere or a degassed atmosphere in many cases. The depolymerization reaction may be performed under normal pressure, reduced pressure, or increased pressure. Furthermore, the depolymerization reaction temperature may be, for example, about 200 to 300 ° C, preferably about 220 to 290 ° C, and more preferably about 230 to 280 ° C.

  The reaction time can be appropriately selected according to the desired degree of polymerization of the fluorene polyester oligomer, reaction conditions, and the like. For example, the reaction time can be selected from about 1 to 90 minutes, 1 to 80 minutes, preferably 3 to 75 minutes, more preferably 5 It may be about 70 minutes.

  The hydroxyl value or acid value of the fluorene polyester oligomer can be selected from the range of about 1 to 300 mgKOH / g, and is 20 mgKOH / g or less [eg 0.1 to 10 mgKOH / g (eg 1 to 5 mgKOH / g ) Degree], 20 mgKOH / g or more [for example, about 20 to 200 mgKOH / g (for example, about 50 to 150 mgKOH / g)].

  The weight average molecular weight of the fluorene polyester oligomer can be selected from the range of 2000 to 15000 when measured using gel permeation chromatography (solvent: tetrahydrofuran, reference resin: polystyrene), and is compatible with optical properties and mechanical properties. From 3,000 to 15000 (for example, 8000 to 12000), preferably 4000 to 12000 (for example, 5000 to 10000), more preferably about 6000 to 10000 (for example, 8000 to 10,000). For example, it may be about 2000 to 8000, preferably about 3000 to 7000, and more preferably about 4000 to 6000. When the fluorene polyester oligomer in the oligomer region is added, the compatibility with the polycarbonate resin is excellent, and the function of the fluorene skeleton can be efficiently imparted. Moreover, in the molded object formed with this resin composition, the bleeding out of a fluorene polyester oligomer can be suppressed and the characteristic which fluorene has can be hold | maintained over a long period of time.

  The ratio of the fluorene polyester oligomer can be selected from the 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 polycarbonate-based resin, for example, 5 to 80 parts by weight, preferably 10 to 10 parts by weight. It may be about 60 parts by weight, more preferably about 15 to 50 parts by weight, and the proportion of the fluorene polyester oligomer is a polycarbonate resin from the viewpoint that both optical properties (particularly low birefringence) and mechanical properties can be achieved. For example, 3 to 40 parts by weight, preferably 5 to 30 parts by weight, and more preferably 10 to 25 parts by weight (particularly 15 to 20 parts by weight) may be used per 100 parts by weight.

(Optional component)
The resin composition of the present invention includes a lubricant, a stabilizer (an antioxidant, an ultraviolet absorber, a heat stabilizer), a mold release agent, an antistatic agent, a colorant, and a filler within the range not impairing the effects of the present invention. Fillers), flame retardants, plasticizers, dispersants, flow modifiers, leveling agents, antifoaming agents, surface modifiers, low stress agents, liquid rubber, heat resistance improvers, water repellency improvers, etc. Also good.

  The ratio of the optional component is 10 parts by weight or less, for example, 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the polycarbonate resin. It may be about a part.

The resin composition of the present invention has excellent transparency, high refractive index, low birefringence, mechanical strength, and excellent heat resistance. In particular, the resin composition of the present invention can significantly reduce birefringence even when the amount of fluorene polyester oligomer added is small. The birefringence of a sheet obtained by stretching a sheet having a thickness of 0.5 mm by 1.7 times under the condition of Tg + 30 ° C. is 1 × 10 ⁻³ or less, preferably 8 × 10 ⁻⁴ or less, more preferably 5 × at a wavelength of 600 nm. It may be 10 ⁻⁴ or less (particularly 4.5 × 10 ⁻⁴ or less (eg, about 0.5 × 10 ^{−4 to} 4.5 × 10 ⁻⁴ )). Since it is a refraction, it is particularly advantageous when the molded body is further molded or when the stretching ratio is increased in the stretching process.

[Polycarbonate resin composition and method for producing molded article]
The resin composition of the present invention may be prepared by mixing a polycarbonate resin and a fluorene polyester oligomer. The mixing method is not particularly limited, and for example, a method by melt kneading using a mixer such as a ribbon blender, a tumble mixer, a Henschel mixer, or a mixing means using a kneader such as an open roller, a kneader, a Banbury mixer, or an extruder. Is available. These mixing methods may be used alone or in combination of two or more.

  Further, the resin composition may be in the form of a coating agent mixed with a solvent. The solvent constituting the coating agent is not particularly limited as long as it is a solvent in which the polycarbonate resin can be dissolved. For example, hydrocarbons (benzene, toluene, etc.), halogen solvents (dichloromethane, etc.), ethers (diethyl) Examples include ethers, tetrahydrofuran, etc., esters (ethyl acetate, etc.), ketones (acetone, ethyl methyl ketone, diisopropyl ketone, cyclohexanone, etc.). These solvents may be used alone or in combination of two or more.

  The ratio of the solvent may be in a range that does not impair the coatability. The solvent content is 1 to 100 parts by weight, preferably 2 to 50 parts by weight, more preferably 3 to 30 parts by weight based on 1 part by weight of the resin composition. It may be about parts by weight.

  The molded product of the present invention can be produced by a known molding method [for example, an injection molding method, an injection compression molding method, an extrusion molding method (for example, T Die method, inflation method, etc.), calendering method, thermoforming method (especially heat press method), transfer molding method, blow molding method, casting molding method, etc.] to obtain the resin composition. be able to.

  The molded product of the present invention may be in the form of a sheet (or film) or may be a stretched (or stretched) sheet (or film). Stretching may be uniaxial stretching (for example, longitudinal stretching or lateral stretching) or biaxial stretching (for example, equal stretching or partial stretching). The stretching ratio may be, for example, about 1.1 to 10 times in each direction (or unidirectional) in uniaxial stretching and biaxial stretching, preferably 1.2 to 5 times, more preferably 1.3. About 3 times (especially 1.5 to 2 times) may be sufficient. The molded article of the present invention can suppress an increase in birefringence even when stretched at a high magnification.

  The elongation at break of the molded article of the present invention may be about 10 to 200%, preferably 15 to 180%, more preferably about 20 to 160% in accordance with JIS K7113. Further, the breaking strength may be about 50 to 100 MPa, preferably 55 to 95 MPa, more preferably about 60 to 90 MPa (for example, 60 to 70 MPa) in accordance with JIS K7113.

  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, each evaluation method in an Example and a comparative example is as follows.

(Birefringence)
The sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were stretched 1.7 times under the condition of Tg + 30 ° C., and the retardation was measured using a retardation measuring apparatus (Otsuka Electronics Co., Ltd., RETS-100). Birefringence was calculated by measuring the retardation at 600 nm and dividing by the thickness of the sheet.

(Elongation at break)
The elongation at break was measured according to JIS K7113 using the sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 2.

(Breaking strength)
The breaking strength was measured according to JIS K7113 using the sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 2.

Example 1
20 parts by weight of a fluorene polyester oligomer (manufactured by Osaka Gas Chemical Co., Ltd., weight average molecular weight 5700) and 80 parts by weight of a polycarbonate resin (manufactured by Teijin Chemicals Ltd., Panrai K-1300Y) were set at a temperature of 230 ° C A resin composition was obtained by performing melt kneading for 10 minutes using a Banbury mixer. This resin composition was press-molded under the conditions of 240 ° C. and 20 MPa to produce a sheet having a thickness of 0.5 mm. The results of measuring the birefringence, breaking elongation, and breaking strength of this sheet are shown in Table 1.

Example 2
Except that 15 parts by weight of a fluorene polyester oligomer (Osaka Gas Chemical Co., Ltd., weight average molecular weight 9700) and 85 parts by weight of a polycarbonate resin (Teijin Kasei Co., Ltd., Panrai K-1300Y) were melt-kneaded, The same operation as in Example 1 was performed. The results are shown in Table 1.

Example 3
Except that 30 parts by weight of a fluorene polyester oligomer (Osaka Gas Chemical Co., Ltd., weight average molecular weight 9700) and 70 parts by weight of a polycarbonate resin (Teijin Kasei Co., Ltd., Panrai K-1300Y) were melt-kneaded, The same operation as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 1
A sheet having a thickness of 0.5 mm was produced by molding a polycarbonate resin (Teijin Kasei Co., Ltd., Panrai K-1300Y). The results of measuring the birefringence, breaking elongation, and breaking strength of this sheet are shown in Table 1.

Comparative Example 2
Banbury which set 20 parts by weight of fluorene polyester (Osaka Gas Chemical Co., Ltd., weight average molecular weight 35000) and 80 parts by weight of polycarbonate resin (Teijin Chemicals Co., Ltd., Panrai K-1300Y) at a temperature of 260 ° C. A resin composition was obtained by performing melt kneading for 10 minutes using a mixer. This resin composition was press-molded under the conditions of 240 ° C. and 20 MPa to produce a sheet having a thickness of 0.5 mm. The results of measuring the birefringence, breaking elongation, and breaking strength of this sheet are shown in Table 1.

  As is clear from Table 1, the birefringence of the polycarbonate resin to which the fluorene polyester oligomers of Examples 1 to 3 were added was significantly lower than that of the polycarbonate resin of Comparative Example 1, and the fluorene of Comparative Example 2 The birefringence was lower than that of the polycarbonate resin to which polyester was added. Further, the polycarbonate resin to which the fluorene polyester oligomer of Example 2 was added exhibited the same breaking elongation and breaking strength as the polycarbonate resin of Comparative Example 1. In contrast, the polycarbonate-based resin of Example 3 had a lower birefringence than the polycarbonate-based resin of Example 2, but had a reduced elongation at break. That is, when fluorene polyester oligomer having a weight average molecular weight of 9700 is used in a proportion of 15 parts by weight with respect to 85 parts by weight of the polycarbonate-based resin, both optical properties such as low birefringence and toughness such as elongation strength can be achieved.

  Polycarbonate resins exhibit good properties in terms of transparency, mechanical strength, and refractive index, but are not necessarily suitable for high-precision optical members (for example, optical lenses and optical films) because of their high birefringence. . However, by adding a small amount of fluorene polyester oligomer, the birefringence can be significantly reduced while maintaining the properties of the polycarbonate resin, so that it is possible to provide a highly accurate optical member based on the polycarbonate resin in particular. it can. The resin composition of the present invention and the molded product thereof are, for example, CD (compact disc) [for example, CD-ROM (compact disc-read only memory)], CD-ROM pickup lens, Fresnel lens, and fθ lens for laser printer. Optical lenses such as camera lenses and rear projection television projection lenses; polarizing films and polarizing elements and polarizing plate protective films, retardation films, alignment films, viewing angle widening films, diffuser films, prism sheets, lead films Optical 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 (ACF) film Electromagnetic wave shielding (EMI) film, For electrode substrate film, a color filter substrate film, barrier film, a color filter layer, etc. suitably used for an optical film such as a black matrix layer.

Claims (5)

A polycarbonate-based resin, a polycarbonate-based resin composition which is composed of a full orange polyester oligomer,
The fluorene polyester oligomer is represented by the following formula (1):

(In the formula, ring Z represents an aromatic hydrocarbon ring, and R ¹ and R ³ are the same or different, and are hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio. Group, arylthio group, aralkylthio group, halogen atom, nitro group, cyano group, N, N-disubstituted amino group, R ² represents an alkylene group, k is an integer of 0 to 4, and n is 0 to 15 And p is an integer of 0 or more.)
Is a condensate of a diol component containing a fluorene compound represented by
The fluorene polyester oligomer has a weight average molecular weight of 2000 to 10,000,
The polycarbonate-type resin composition whose ratio of the said fluorene polyester oligomer is 1-50 weight part with respect to 100 weight part of polycarbonate-type resin. Ratio of fluorene polyester oligomer, relative to 100 parts by weight of a polycarbonate resin, according to claim 1 Symbol placement of the resin composition is 3 to 40 parts by weight. The resin composition according to claim 1 or 2 , wherein the weight average molecular weight of the fluorene polyester oligomer is 2000 to 8000, and the ratio of the fluorene polyester oligomer is 10 to 25 parts by weight with respect to 100 parts by weight of the polycarbonate resin. The molded object formed with the resin composition in any one of Claims 1-3 . The molded article according to claim 4, which is an optical member.