JP6242271B2 - Polyester resin having a fluorene skeleton - Google Patents

Description

  The present invention relates to a novel polyester resin having a fluorene skeleton and a resin composition thereof.

  Compounds having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) are known to have excellent functions such as a high refractive index and high heat resistance. As a method for expressing the excellent function of such a fluorene skeleton in a resin and making it moldable, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene, etc. In general, a method in which (BCF), bisphenoxyethanol fluorene (BPEF), or the like is used as a constituent component of a resin and a fluorene skeleton is introduced into a part of the skeleton structure of the resin. Among the resins having such a fluorene skeleton, various polyester resins are being developed.

For example, JP-A-7-198901 (Patent Document 1) discloses an aromatic dicarboxylic acid or an ester-forming derivative thereof and 10 mol% or more of 9,9-bis (4-hydroxyC _2-4 alkoxyphenyl) fluorene. A polyester resin for plastic lenses, which is a substantially linear polyester polymer composed of a dihydroxy compound such as aliphatic glycol having 2 to 4 carbon atoms and a refractive index of 1.60 or more, is disclosed. Yes.

  However, in the polyester resin of this document, a polyester polymer having a relatively high birefringence can be obtained by using an aromatic dicarboxylic acid or an ester-forming derivative thereof, although a relatively high refractive index can be realized.

JP-A-2008-69224 (Patent Document 2) discloses a diol component (A1) having a fluorene skeleton [for example, 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (hydroxy (poly)). Diol component (A) composed at least of C _2-4 alkoxyphenyl) fluorene and the like, and dicarboxylic acid component (B1) having a fluorene skeleton [eg, 9,9-bis (carboxy-C _1-4 alkyl) fluorene , 2,7-dicarboxyfluorene, etc.], and a polyester resin having a dicarboxylic acid component (B) composed of at least a polymerization component. Note that this document does not specifically describe the relationship between the dicarboxylic acid component having a fluorene skeleton and birefringence, and that other dicarboxylic acid components and other diol components may be used in combination. However, there is no use example in the examples.

Japanese Patent Laid-Open No. 7-198901 (Claims) JP 2008-69224 A (claims, paragraphs [0042] and [0058])

  Accordingly, an object of the present invention is to provide a novel polyester resin having a fluorene skeleton and a molded body formed from the polyester resin.

  Another object of the present invention is to provide a polyester resin having a low birefringence or a negative birefringence and a molded body formed from the polyester resin.

  Still another object of the present invention is to provide a polyester resin capable of low birefringence or negative birefringence without impairing properties such as refractive index and heat resistance, and a molded body formed from the polyester resin. .

  Another object of the present invention is to provide a polyester resin having excellent affinity for the resin and a molded body formed from the polyester resin.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have succeeded in polymerization (condensation) even when a diol component is not a diol having a fluorene skeleton, which is essential in Patent Document 2, but a non-fluorene aromatic diol. ) Proceeds to obtain a polyester resin, and the resulting polyester resin is surprisingly surprising, despite the use of an aromatic diol, which is considered to easily increase birefringence, as a polymerization component, Having low birefringence and negative birefringence, and having a relatively high heat resistance and a high refractive index despite the fact that the diol component is not composed of a diol having a fluorene skeleton, It has been found that low birefringence and negative birefringence can be achieved while having excellent characteristics, and the present invention has been completed.

That is, the polyester resin of the present invention is a polymerization component comprising a dicarboxylic acid component (A) containing a fluorene-based dicarboxylic acid component (A1) and a non-fluorene-based diol component (B) containing a non-fluorene-based aromatic diol (B1). A polyester resin. In such a polyester resin, the fluorene-based dicarboxylic acid component (A1) includes 9,9-bis (carboxyalkyl) fluorenes [eg, 9,9-bis (carboxyC _2-5 alkyl) fluorenes] and esters thereof. It may be at least one selected from the forming derivatives. The dicarboxylic acid component (A) may contain 30 mol% or more of the fluorene-based dicarboxylic acid component (A1).

The aromatic diol (B1) may be composed of an araliphatic diol [for example, at least one araliphatic diol selected from di (hydroxyalkyl) arene and alkylene oxide adducts of bisphenols]. In particular, the aromatic diol (B1) is at least selected from di (hydroxyC _1-4 alkyl) C _6-10 arenes and C _2-4 alkylene oxide adducts of bis (hydroxyphenyl) C _1-8 alkanes. One kind may be sufficient.

  Typically, the dicarboxylic acid component (A) contains 50 mol% or more of the fluorene dicarboxylic acid component (A1), and the non-fluorene diol component (B) contains 50 mol% or more of the aromatic diol (B1). May be.

  The dicarboxylic acid component (A) further includes other dicarboxylic acids composed of at least one selected from non-fluorene-based arene dicarboxylic acids, cycloalkane dicarboxylic acids, bi- or tricycloalkane dicarboxylic acids, and ester-forming derivatives thereof. The acid component (A2) may be included. In such a case, the ratio of the fluorene-based dicarboxylic acid (A1) to the other dicarboxylic acid (A2) may be about the former / the latter (molar ratio) = 100/0 to 50/50.

  The diol component (B) may further contain another diol (B2) composed of an aliphatic diol (eg, alkane diol). In such a case, the ratio of the aromatic diol (B1) and the other diol (B2) may be, for example, the former / the latter (molar ratio) = 99/1 to 50/50.

In the polyester resin of the present invention, the intrinsic birefringence may be, for example, + 20 × 10 ⁻⁴ or less, and the refractive index at 20 ° C. and a wavelength of 589 nm may be, for example, 1.59 or more. Further, the glass transition temperature of the polyester resin of the present invention may be 70 ° C. or higher.

  The present invention includes a resin composition containing a resin (particularly a resin having positive intrinsic birefringence), the polyester resin, and another resin. In such a resin composition, the other resin may be a resin having an aromatic ring (for example, a resin having a 9,9-bisarylfluorene skeleton). Moreover, in such a resin composition, the ratio of the polyester resin may be, for example, about 1 to 500 parts by weight with respect to 100 parts by weight of other resins.

  Moreover, the molded object formed with the said polyester resin or the said resin composition is also contained in this invention. Such a molded body may in particular be an optical molded body (for example, an optical film).

  In the present invention, a novel polyester resin having a fluorene skeleton can be provided. Such a polyester resin is a polyester resin having a dicarboxylic acid component having a fluorene skeleton and a non-fluorene aromatic diol as polymerization components, and is usually a polyester resin having low birefringence or negative birefringence. Such a polyester resin can realize low birefringence or negative birefringence without impairing properties such as refractive index and heat resistance, even though a diol having a fluorene skeleton is not used. Moreover, the polyester resin of the present invention includes those having reverse wavelength dispersibility [characteristic that the phase difference (or birefringence) increases as the wavelength increases]. Therefore, the polyester resin of the present invention is also suitable as a resin for a retardation film.

  In addition, the polyester resin of the present invention has excellent characteristics as described above, and can be used as it is as a resin for constituting a resin molded body, or even when applied to other resins, the resin characteristics ( (Refractive index, heat resistance, mechanical properties, moisture resistance, etc.) are not impaired, so by adjusting the type of resin and the type and ratio of other dicarboxylic acid components and diol components combined in polyester, Such characteristics can also be improved or improved. In addition, as described above, the birefringence is low birefringence or negative birefringence, and a birefringence adjusting function (for example, a function of reducing birefringence in the negative direction) with respect to another resin can be exhibited. Moreover, reverse wavelength dispersion can also be provided (or expressed) to other resins.

  And the polyester resin of this invention is excellent in affinity (compatible etc.) with respect to other resin. Therefore, the function of adjusting the birefringence for the resin can be efficiently expressed. Therefore, it can be applied to a wide range of resins, and bleeding out and the like can be suppressed at a high level. And the polyester resin of the present invention does not impair the resin characteristics as described above even if added in a small amount or at a high ratio, but rather may improve the resin characteristics, depending on the application. It can be applied in a wide variety of modes and is extremely useful. Such a resin containing the polyester resin of the present invention (or a resin modified with the polyester resin of the present invention) has excellent characteristics as described above, and is an optical molded body such as an optical film or an optical lens. It can be suitably used for such as.

  The polyester resin of the present invention uses a specific dicarboxylic acid component and a specific diol component as polymerization components.

[Dicarboxylic acid component]
The dicarboxylic acid component (sometimes referred to as a dicarboxylic acid component (A) or the like) contains at least a fluorene-based dicarboxylic acid component.

(Fluorene dicarboxylic acid component)
Examples of the fluorene-based dicarboxylic acid component (or dicarboxylic acid component having a fluorene skeleton, fluorene-based dicarboxylic acid component (A1), dicarboxylic acid component (A1), etc.) include fluorene-based dicarboxylic acids (dicarboxylic acids having a fluorene skeleton). And ester-forming derivatives thereof. Examples of the ester-forming derivative include esters {for example, alkyl esters [for example, lower alkyl esters such as methyl esters and ethyl esters (for example, C _1-4 alkyl esters, particularly C _1-2 alkyl esters], etc.}}. , Acid halides (acid chlorides, etc.), acid anhydrides, etc. The ester-forming derivative may be a monoester (half ester) or a diester.The fluorene-based dicarboxylic acid component is used in the method for producing a polyester resin. The melt polymerization method often uses a dicarboxylic acid having a fluorene skeleton, a dicarboxylic acid ester having a fluorene skeleton, and the like (the same applies hereinafter).

  The fluorene-based dicarboxylic acid may be a compound in which two carboxyl group-containing groups are substituted on two benzene rings constituting fluorene [for example, fluorene carboxylic acid (for example, 2,7-dicarboxyfluorene, etc.)]. However, it may be a compound in which two carboxyl group-containing groups are usually substituted at the 9-position of fluorene. Examples of such a compound include 9-dicarboxyalkylfluorene [for example, 9- (1,2-dicarboxyethyl) fluorene and the like], di (9-carboxyalkylfluorenyl) alkane [for example, di (9 -Carboxyethyl-9-fluorenyl) methane, 1,2-di (9-carboxyethyl-9-fluorenyl) ethane and the like], in particular, compounds represented by the following formulas (1a) and (1b) Can be suitably used. Such a compound seems to have a high birefringence reduction effect in combination with a specific diol component described below.

(In formula, X _<1a >, X < _1b > is the same or different and is a bivalent hydrocarbon group, R < ¹ > is a substituent which is not a carboxyl group, n is an integer of 0-4, k shows the integer of 0-4. )
In the above formulas (1a) and (1b), the divalent hydrocarbon group represented by the groups X _1a and X _1b includes an aliphatic hydrocarbon group {for example, an alkylene group (or an alkylidene group such as a methylene group, ethylene Group, ethylidene group, trimethylene group, propylene group, propylidene group, tetramethylene group, 1,2-butanediyl group, ethylethylene group, butane-2-ylidene group, 1,2-dimethylethylene group, pentamethylene group, pentane- C _1-8 alkylene group such as 2,3-diyl group, preferably ethylene group, propylene group, C _2-4 alkylene group such as 1,2-butanediyl group), cycloalkylene group (for example, cyclopentylene group, cyclohexylene group, a cyclohexylene group methylcyclohexyl, C _5-10 cycloalkylene group such heptylene cyclohexane, preferably Is _{C 5-8} cycloalkylene group, more preferably a _{C 5-6} cycloalkyl _{C 2-4} alkylene group), an alkylene (or alkylidene) - cycloalkylene group [or cycloalkylene - alkylene group such as methylene - cyclohexylene group A C _1-6 alkylene-C _5-10 cycloalkylene group (preferably C _1-4 alkylene-C _5-8 cyclo) such as ethylene-cyclohexylene group, ethylene-methylcyclohexylene group, ethylidene-cyclohexylene group, etc. An alicyclic hydrocarbon group such as an alkylene group), a bridged cyclic hydrocarbon group such as a bi- or tricycloalkylene group such as a norbornane-diyl group], etc.}, an aromatic hydrocarbon group {eg, an arylene group (phenylene) Group, C _6-10 arylene group such as naphthalenediyl group), alkylene (or the like) Alkylidene) -arylene group [or arylene-alkylene group, for example, C _1-6 alkylene-C _6-20 arylene group such as methylene-phenylene group, ethylene-phenylene group, ethylene-methylphenylene group, ethylidenephenylene group (preferably C _1-4 alkylene-C _6-10 arylene group, preferably an araliphatic hydrocarbon group such as C _1-2 alkylene-phenylene group)], C _6-10 aryl C _2-4 alkylene such as phenylethylene group Group etc. can be illustrated. The alkylene-cycloalkylene group and the alkylene-arylene group are -R ^a -R ^b- (wherein R ^a is an alkylene group bonded to the 9th position of the carboxyl group or fluorene in the formulas (1a) and (1b)). And R ^b represents a cycloalkylene group or an arylene group). The two groups X _1a may be the same or different groups.

Among these, a divalent aliphatic hydrocarbon group, particularly an alkylene group which may have a substituent is preferable. The alkylene group represented by X _1a and X _1b is a linear or branched alkylene group such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a 2-ethylethylene group, 2-methylpropane-1, Examples thereof include a C _1-8 alkylene group such as a 3-diyl group. Preferred alkylene groups are linear or branched C _1-6 alkylene groups (eg, C _1-4 alkylene such as methylene group, ethylene group, trimethylene group, propylene group, 2-methylpropane-1,3-diyl group). Group).

  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).

X _1a is often a linear or branched C _2-4 alkylene group (eg, ethylene group, propylene group), and X _1b is a linear or branched C _1-3 alkylene group (eg, Methylene group, ethylene group) in many cases. The alkylene group X _1a having a substituent may be, for example, a 1-phenylethylene group, a 1-phenylpropane-1,2-diyl group, or the like.

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

In the above formulas (1a) and (1b), the group R ¹ may be any substituent that is not a carboxyl group, such as a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [for example , Alkyl groups, aryl groups (C _6-10 aryl groups such as phenyl groups)], acyl groups (eg, alkylcarbonyl groups such as methylcarbonyl, ethylcarbonyl, pentylcarbonyl), etc. In many cases. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, such as _{C 1-12} alkyl group _{(e.g., C 1-8} alkyl groups, especially methyl groups, such as t- butyl group _{C 1- 4} alkyl group) and the like. In addition, when k is plural (2 to 4), plural groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on different benzene rings may be the same or different. Further, the bonding position (substitution position) of the group R ¹ is not particularly limited, and examples thereof include the 2nd, 7th, 2nd and 7th positions of the fluorene ring. The preferred substitution number k is 0 to 1, in particular 0. The two substitution numbers k may be the same or different.

As a typical fluorene dicarboxylic acid component, in the formula (1a), a compound in which X _1a is a divalent aliphatic hydrocarbon group, for example, 9,9-bis (carboxyalkyl) fluorenes [for example, 9 , 9-bis (carboxymethyl) fluorene, 9,9-bis (2-carboxyethyl) fluorene, 9,9-bis (1-carboxyethyl) fluorene, 9,9-bis (1-carboxypropyl) fluorene, 9 , 9-bis (2-carboxypropyl) fluorene, 9,9-bis (2-carboxy-1-methylethyl) fluorene, 9,9-bis (2-carboxy-1-methylpropyl) fluorene, 9,9- Bis (2-carboxybutyl) fluorene, 9,9-bis (2-carboxy-1-methylbutyl) fluorene, 9,9-bis (5- 9,9-bis (carboxy C _1-6 alkyl) fluorene such as carboxypentyl) fluorene], 9,9-bis (carboxycycloalkyl) fluorenes [for example, 9,9-bis (carboxycyclohexyl) fluorene, etc. 9,9-bis (carboxy C _5-8 cycloalkyl) fluorene and the like] and the like.

Preferred compounds represented by the formula (1a) are compounds in which X _1a is a C _2-6 alkylene group, such as 9,9-bis (2-carboxyethyl) fluorene, 9,9-bis (2-carboxypropyl). ) 9,9-bis (carboxy C _2-6 alkyl) fluorene such as fluorene, and ester-forming derivatives thereof. A preferred compound represented by the formula (1b) is a compound in which n = 0 and X _1b is a C _1-6 alkylene group, such as 9- (1-carboxy-2-carboxyethyl) fluorene, n = 1 and X _1b is a C _1-6 alkylene group, for example, 9- (carboxy-carboxy C _2-6 alkyl) fluorene such as 9- (2-carboxy-3-carboxypropyl) fluorene, And ester-forming derivatives thereof. The fluorene dicarboxylic acid components may be used alone or in combination of two or more.

Among these, preferred fluorene-based dicarboxylic acid components include compounds represented by the formula (1a), for example, 9,9-bis (carboxyalkyl) fluorenes [for example, 9,9-bis (carboxyethyl) fluorene, 9,9-bis (carboxy C _2-4 alkyl) fluorene, such as 9,9-bis (2-carboxypropyl) fluorene, in particular 9,9-bis (carboxyethyl) fluorene] and its ester-forming derivatives And at least one (9,9-bis (carboxyalkyl) fluorene component).

  The ratio of the fluorene-based dicarboxylic acid component (A1) to the entire dicarboxylic acid component (A) is, for example, 10 mol% or more (for example, 20 mol% or more), preferably 30 mol% or more (for example, 40 mol% or more). ), More preferably 50 mol% or more (for example, 60 mol% or more), or 70 mol% or more (for example, 80 mol% or more).

(Other dicarboxylic acid components)
The dicarboxylic acid component (A) may be composed of only a fluorene-based dicarboxylic acid component, and other dicarboxylic acid components (non-fluorene-based dicarboxylic acid component, fluorene-based dicarboxylic acid) as long as the effects of the present invention are not impaired. A dicarboxylic acid component that is not a component, another dicarboxylic acid component (A2), or a dicarboxylic acid component (A2) may be included).

  Examples of the other dicarboxylic acid component (A2) include an aliphatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, and an aromatic dicarboxylic acid component. Among these, the aliphatic dicarboxylic acid component and the alicyclic dicarboxylic acid component can be preferably used from the viewpoint of the birefringence adjusting function. The alicyclic dicarboxylic acid component is also suitable from the viewpoint of heat resistance. Furthermore, the aromatic dicarboxylic acid component is suitable from the viewpoint of refractive index and heat resistance.

Examples of the aliphatic dicarboxylic acid component include alkane dicarboxylic acid components [for example, C _2-12 alkane dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid, and ester-forming derivatives thereof (such derivatives). Ingredients etc.]. The aliphatic dicarboxylic acid components may be used alone or in combination of two or more.

Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acid (for example, C _5-10 cycloalkane-dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, preferably C _5-8 cycloalkane-dicarboxylic acid, etc. ), Bi- or tricycloalkane dicarboxylic acids (e.g., bi- or tri-C _5-10 cycloalkane-dicarboxylic acids such as decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid), and their ester forming properties Derivatives (such as the above-described derivatives) and the like. The alicyclic dicarboxylic acid components may be used alone or in combination of two or more.

  As the aromatic dicarboxylic acid component (non-fluorene-based aromatic dicarboxylic acid component), arene dicarboxylic acid, for example, monocyclic aromatic dicarboxylic acid component, polycyclic aromatic dicarboxylic acid component (non-fluorene-based polycyclic aromatic component) Dicarboxylic acid component).

Examples of the monocyclic aromatic dicarboxylic acid component include C _6-10 arene-dicarboxylic acid such as terephthalic acid, isophthalic acid, and alkyl isophthalic acid (for example, C _1-4 alkyl terephthalic acid such as 4-methylisophthalic acid). And ester-forming derivatives thereof. The monocyclic aromatic dicarboxylic acid components may be used alone or in combination of two or more.

  Among these monocyclic aromatic dicarboxylic acid components, in particular, from the viewpoint of imparting a high refractive index and low birefringence (and high heat resistance) to the polyester resin in a balanced manner, a terephthalic acid component (terephthalic acid and / or Or an ester-forming derivative thereof). In the present invention, even if a terephthalic acid component (such as terephthalic acid or dimethyl terephthalate) that is generally considered to increase birefringence is used, the polyester resin can be more efficiently combined with the fluorene-based dicarboxylic acid component. Low birefringence can be achieved.

  In addition, asymmetric monocyclic aromatic dicarboxylic acid components [for example, isophthalic acid components (isophthalic acid and / or ester-forming derivatives thereof), alkylisophthalic acid components, phthalic acid components, etc., particularly isophthalic acid components] are preferably used. May be. Birefringence can be efficiently reduced by combining an asymmetric monocyclic aromatic dicarboxylic acid component and a fluorene-based dicarboxylic acid component.

Examples of the polycyclic aromatic dicarboxylic acid component include polycyclic aromatic dicarboxylic acids and ester-forming derivatives thereof (non-fluorene-based polycyclic aromatic dicarboxylic acid components). Examples of the polycyclic aromatic dicarboxylic acid include a dicarboxylic acid having no fluorene skeleton as the polycyclic aromatic skeleton, such as a condensed polycyclic aromatic dicarboxylic acid [for example, naphthalenedicarboxylic acid (for example, 1,5-naphthalenedicarboxylic acid). Acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid having two carboxyl groups in different rings such as 1,6-naphthalenedicarboxylic acid; 2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid and the like, naphthalenedicarboxylic acid having two carboxyl groups in the same ring), anthracene dicarboxylic acid, phenanthrene dicarboxylic acid and other condensed polycyclic C _10-24 arene-dicarboxylic acid, preferably fused polycyclic _{C 10-1} Arene - dicarboxylic acid, more preferably fused polycyclic _{C 10-14} arene - dicarboxylic acid, aryl array Nji carboxylic acid [e.g., biphenyl dicarboxylic acid (2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid C _6-10 aryl C _6-10 arene-dicarboxylic acid], diaryl alkane dicarboxylic acid [for example, diphenyl alkane dicarboxylic acid (for example, diphenyl C _1-4 alkane- such as 4,4′-diphenylmethane dicarboxylic acid) DiC _6-10 aryl C _1-6 alkane-dicarboxylic acid such as dicarboxylic acid], diaryl ketone dicarboxylic acid [for example, diC ₆ such as diphenyl ketone dicarboxylic acid (such as 4,4′-diphenyl ketone dicarboxylic acid) _-10 aryl ketone - dicarboxylic Acid] and the like. The polycyclic aromatic dicarboxylic acid components may be used alone or in combination of two or more.

  Among these polycyclic aromatic dicarboxylic acid components, in particular, from the viewpoint of imparting a high refractive index and low birefringence (and high heat resistance) to the polyester resin in a balanced manner, the condensed polycyclic aromatic dicarboxylic acid Components (particularly naphthalenedicarboxylic acid components) are preferred. In the present invention, the birefringence of the polyester resin is efficiently reduced even when a condensed polycyclic aromatic dicarboxylic acid component, which is generally considered to increase birefringence, is used as the other dicarboxylic acid component (A2). it can.

  A monocyclic aromatic dicarboxylic acid component and a polycyclic aromatic dicarboxylic acid component may be combined.

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

  Other dicarboxylic acid components (A2) may be used alone or in combination of two or more.

In particular, as other carboxylic acid component (A2), non-fluorene-based arene dicarboxylic acid (for example, C _6-10 arene-dicarboxylic acid such as terephthalic acid), alicyclic dicarboxylic acid (for example, C _5-10 cycloalkane) -Dicarboxylic acid, bi- or tri-C _5-10 cycloalkane-dicarboxylic acid etc.) and their ester-forming derivatives are preferred.

  When combining the fluorene-based dicarboxylic acid component (A1) and the other dicarboxylic acid component (A2), the ratio of the former / the latter (molar ratio) = 99.5 / 0.5 to 10/90 (for example, 99 / 1-15 / 85), preferably 98 / 2-20 / 80 (e.g. 97 / 3-25 / 75), more preferably 95 / 5-30 / 70 (e.g. 95 / 5-35 / 65). In particular, it may be about 93/7 to 40/60 (for example, 90/10 to 45/55), and usually 99/1 to 50/50 (for example, 95/5 to 60/40, preferably 90 / 10 to 70/30).

  In particular, when the other dicarboxylic acid component (A2) is composed of an aromatic dicarboxylic acid component, the ratio of the fluorene-based dicarboxylic acid component (A1) to the other dicarboxylic acid component (A2) is the former / the latter (molar ratio). = 99.5 / 0.5 to 30/70 (for example, 99/1 to 35/65), preferably 98/2 to 40/60 (for example, 97/3 to 45/55), more preferably 95 / It may be about 5-50 / 50 (for example, 95 / 5-55 / 45), and is usually 99 / 1-50 / 50 (for example, 95 / 5-60 / 40, preferably 90 / 10-70 / 30) or so.

[Diol component]
The diol component (sometimes referred to as diol component (B)) is a non-fluorene-based diol (that is, a diol component that does not include a diol having a fluorene skeleton), and an aromatic diol (non-fluorene-based aromatic diol, fluorene skeleton) At least an aromatic diol having no

(Aromatic diol)
Examples of aromatic diols (sometimes referred to as non-fluorene aromatic diols, aromatic diols (B1), diols (B1), etc.) include dihydroxyarenes (hydroquinone, resorcinol, etc.), bisphenols, araliphatic diols [ Examples thereof include di (hydroxyalkyl) arene and alkylene oxide adducts of bisphenols.

Examples of the di (hydroxyalkyl) arene include di (hydroxyC _1-4 alkyl) C _6-10 arenes such as benzenedimethanol (1,4-benzenedimethanol, 1,3-benzenedimethanol and the like). .

Examples of the bisphenol include dihydroxyarene [eg, di ( _{hydroxyC 6-10} arene) such as 4,4′-dihydroxybiphenyl], bis (hydroxyphenyl) alkane [eg, bis (4-hydroxyphenyl) methane, etc. 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis ( 4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2 Bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane Bis (hydroxy) such as 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) diphenylmethane Phenyl) C _1-10 alkanes, preferably bis (hydroxyphenyl) C _1-8 alkanes], bis (hydroxyphenylaryl) alkanes [eg 2,2-bis (4-hydroxy-3,3′- biphenyl) propane and bis (hydroxy _{biphenylyl) C 1-10} alkanes, preferably bis (arsenate B carboxymethyl _{biphenylyl) C 1-8} alkanes, bis (hydroxyphenyl) cycloalkane [e.g., 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis ( Bis (hydroxyphenyl) C _4-10 cycloalkanes such as 3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane , Preferably bis (hydroxyphenyl) C _5-8 cycloalkane], bis (hydroxyphenyl) ethers (for example, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyl) Diphenyl ether), bis (hydroxyphenyl) sulfones ( For example, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, 4,4′-dihydroxy-3,3′-diphenyldiphenylsulfone, etc.), bis (hydroxyphenyl) Sulfoxides (for example, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfoxide, etc.), bis ( Hydroxyphenyl) sulfides (eg, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, etc.) Bis (hydroxyphenyl-alkyl) array [For example, bis (hydroxyphenyl-C _1-4 alkyl) C _6-10 arenes such as 4,4 ′-(o, m or p-phenylenediisopropylidene) diphenol, preferably bis (hydroxyphenyl- C _1-4 alkyl) benzene] and the like.

In the alkylene oxide adduct of bisphenols, examples of the alkylene oxide include C _2-6 alkylene oxide (preferably C _2-6 alkylene oxide) such as ethylene oxide, propylene oxide, and butylene oxide. Moreover, in the adduct of alkylene oxide, the addition ratio of alkylene oxide is, for example, 1 mol or more (for example, 1 to 10 mol), preferably 1 to 6 mol (for example, 1 mol of hydroxyl group of bisphenol). For example, it may be about 1 to 5 mol), more preferably about 1 to 4 mol, particularly about 1 to 3 mol (for example, 1 to 2 mol).

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

Of these aromatic diols, araliphatic diols are preferred from the viewpoints of polymerizability and efficient low birefringence or negative birefringence. In particular, di (hydroxyalkyl) arene (eg, di (hydroxyC _1-4 alkyl) C _6-10 arene such as 1,4-benzenedimethanol), bisphenols (eg, 2,2-di [4- ( An alkylene oxide (for example, C _2-4 alkylene oxide) adduct of bis (hydroxyphenyl) C _1-8 alkanes such as 2-hydroxyethoxy) phenyl] propane is preferable. Therefore, the aromatic diol may be composed of an araliphatic diol.

  When the aromatic diol is composed of at least an araliphatic diol, the ratio of the araliphatic diol to the entire aromatic diol is, for example, 10 mol% or more (for example, 20 mol% or more), preferably 30 mol% or more. (For example, 40 mol% or more), more preferably 50 mol% or more (for example, 60 mol% or more), particularly 70 mol% or more (for example, 80 mol% or more) may be used.

  The ratio of the aromatic diol (B1) to the whole diol component (B) is, for example, 10 mol% or more (for example, 20 mol% or more), preferably 30 mol% or more (for example, 40 mol% or more), Preferably, it may be 50 mol% or more (for example, 60 mol% or more), or 70 mol% or more (for example, 80 mol% or more).

(Other diol components)
The diol component (B) may be composed only of an aromatic diol, and other diols (or other non-fluorene diols, other diols (B2), diols, as long as the effects of the present invention are not impaired. (Sometimes referred to as (B2)).

  The other diol (or other diol component) (B2) is not particularly limited, and examples thereof include aliphatic diol (or aliphatic diol component), alicyclic diol (or alicyclic diol component), and the like. . In particular, the aliphatic diol can be suitably used from the viewpoint of the birefringence adjusting function (function of reducing birefringence in the negative direction). The alicyclic diol is also suitable from the viewpoint of heat resistance.

Examples of the aliphatic diol (chain aliphatic diol) include alkane diols (for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol). , 1,3-butanediol, 1,4-pentanediol, 1,5-pentanediol, 1,3-pentanediol, C _2-10 alkanediol such as neopentyl glycol, preferably C _2-6 alkanediol, More preferably C _2-4 alkane diol), polyalkane diols (eg di- or tri-C _2-4 alkane diols such as diethylene glycol, dipropylene glycol, triethylene glycol, etc.) (especially ethylene glycol). 1,2-butanediol, etc.) Can be mentioned. Aliphatic diols may be used alone or in combination of two or more.

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), and bridged (bridged) cycloalkane. Diols (for example, bi or tricycloalkanediols such as norbornanediol, adamantanediol), di (hydroxyalkyl) cycloalkanes [for example, di (hydroxyC _1-4 alkyl) C ₄₋ such as 1,4-cyclohexanedimethanol. ₁₀ cycloalkane, preferably di (hydroxyC _1-3 alkyl) C _5-8 cycloalkane, more preferably di (hydroxyC _1-2 alkyl) C _5-6 cycloalkane, etc.], di (hydroxyalkyl) bridged ( Bridge ring type) cycloalkane [eg , Tricyclodecane dimethanol (tricyclo [5.2.1.0 (2,6)] decane dimethanol), adamantane dimethanol, di (hydroxyalkyl _{C 1-4} alkyl) such as norbornanedimethanol bi- or tri _{C 4 -10} cycloalkane, preferably di (hydroxy _{C 1-3} alkyl) bicycloaryl or tri _{C 5-10} cycloalkane, more preferably di (hydroxy _{C 1-2} alkyl) bicycloaryl or tri _{C 6-10} cycloalkane, bisphenol hydrogenated products of alkylene oxide adducts of the class (such as the compound) {e.g., di (hydroxycycloalkyl) alkanes [e.g., 2,2-bis (4-hydroxycyclohexyl) di propane (hydroxy _{C 4-10} cycloalkyl Alkyl) C _1-10 alkane, preferably di (hydroxy C _5-8) Chloroalkyl) C _1-4 alkane and the like], diol having a heterocycloalkane skeleton {eg oxamono or polycycloalkanediol (isosorbide etc.), diol having an oxaspiro skeleton [eg 3,9-bis (1 , 1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane and the like di (hydroxyalkyl) oxaspiroalkanes (eg di (hydroxyC _1-10 alkyl)) Tetraoxaspiroalkane, preferably di (hydroxyC _1-6 alkyl) tetraoxaspiroalkane) and the like. The alicyclic diols may be used alone or in combination of two or more.

Among the alicyclic diols, di (hydroxyalkyl) cycloalkane [eg, di (hydroxyC _1-3 alkyl) C _5-8 cycloalkane], di (hydroxyalkyl) -bridged cycloalkane [eg, di (hydroxyC _{1 -3} alkyl) bi or tri-C _5-10 cycloalkane], etc., in combination with the fluorene-based dicarboxylic acid component, seems to have a high effect of reducing birefringence in the negative direction. Birefringence (intrinsic birefringence) can also be used. Therefore, when the polyester resin of the present invention is used as a birefringence adjusting agent (birefringence adjusting agent for reducing birefringence in the negative direction) for other resins, these alicyclic diols are suitable. You may use for.

The other diol (B2) may be composed of at least an aliphatic diol (for example, C _2-6 alkane diol) from the viewpoint of polymerizability.

  When the aromatic diol (B1) is combined with another diol (B2), these ratios are the former / the latter (molar ratio) = 99.5 / 0.5 to 10/90 (for example, 99/1 to 15). / 85), preferably 98/2 to 20/80 (eg 97/3 to 25/75), more preferably 95/5 to 30/70 (eg 95/5 to 35/65), in particular 93 / It may be about 7 to 40/60 (for example, 90/10 to 45/55), and usually 99/1 to 50/50 (for example, 95/5 to 60/40, preferably 90/10 to 70 / 30) or so.

[Polyester resin]
The polyester resin is a polyester resin having a dicarboxylic acid component (A) and a diol component (B) as polymerization components. Such a polyester resin usually has a feature that it has low birefringence (the absolute value of birefringence is small) or negative birefringence. Therefore, such a polyester resin can be used alone as a low birefringence resin or a resin having negative birefringence, and the birefringence of a resin having positive birefringence in the negative direction as described later. It can also be used as a birefringence adjusting agent (birefringence reducing agent) for reduction.

The intrinsic birefringence value of the polyester resin can be selected from the range of about + 50 × 10 ⁻⁴ (for example, −150 × 10 ⁻⁴ to + 50 × 10 ⁻⁴ ), for example, + 40 × 10 ⁻⁴ or less (for example, − 120 × 10 ⁻⁴ to + 35 × 10 ⁻⁴ ), preferably + 30 × 10 ⁻⁴ or less (for example, −120 × 10 ⁻⁴ to + 25 × 10 ⁻⁴ ), more preferably + 20 × 10 ⁻⁴ or less (for example, It may be about −100 × 10 ⁻⁴ to + 15 × 10 ⁻⁴ ).

In particular, the polyester resin of the present invention has a negative birefringence [for example, −5 × 10 ⁻⁴ or less (for example, −100 × 10 ⁻⁴ to ⁻¹⁰ × 10 ⁻⁴ )], more preferably − 10 × ^{10 -4} or less ^{(e.g., -90 × 10 -4 ~-15} × 10 -4) may be about, to -20 × ^{10 -4} or less (e.g., -30 × ^{10 -4} or less) You can also.

The polyester resin of the present invention has an intrinsic birefringence of 30 × 10 ⁻⁴ or less (for example, 0 to 25 × 10 ⁻⁴ ), preferably 20 × 10 ⁻⁴ or less (for example, 0 to 15 ×) in absolute value. 10 ⁻⁴ ), more preferably 10 × 10 ⁻⁴ or less (for example, 0 to 8 × 10 ⁻⁴ ), and particularly 5 × 10 ⁻⁴ or less (for example, 0 to 4 × 10 ⁻⁴ ).

  Further, the polyester resin of the present invention often has a relatively high refractive index. Therefore, it can be used alone as an optical resin, etc., and even when used as a composition with other resins, the refractive index of other resins can be maintained at a relatively high level, and depending on the type of other resins The refractive index can also be improved. For example, the refractive index of the polyester resin can be selected from a range of 1.53 or more (for example, 1.54 or more) at 20 ° C. and a wavelength of 589 nm, 1.55 or more (for example, 1.55 to 1.75), Preferably, it may be about 1.56 or more (for example, 1.56 to 1.72), 1.57 or more [for example, 1.58 to 1.75, preferably 1.59 or more (for example, 1. 595 to 1.72), more preferably 1.6 or more (for example, 1.60 to 1.7)].

  Furthermore, the polyester resin of the present invention has relatively high heat resistance even when a diol component having a fluorene skeleton is not used as a polymerization component. For example, the glass transition temperature (Tg) is 50 ° C. or higher (for example, 60 ° C.). For example, the temperature may be 70 ° C. or higher (for example, about 70 to 200 ° C.), preferably 75 ° C. or higher (for example, 75 to 150 ° C.).

  The weight average molecular weight of the polyester resin can be selected from the range of about 1,000 to 500,000 (for example, 3000 to 300,000), for example, 5,000 to 200,000, preferably 10,000 to 150,000, and more preferably about 15,000 to 100,000. Usually, about 20000-100,000 (for example, 30000-70000) may be sufficient.

  The polyester resin can be produced by a conventional method. For example, the polyester resin can be produced by reacting (polymerizing or condensing) the dicarboxylic acid component (A) and the diol component (B). The polymerization method (manufacturing method) can be appropriately selected according to the type of dicarboxylic acid component to be used and the like, and is a conventional method such as a melt polymerization method (a method in which a dicarboxylic acid component and a diol component are polymerized under melt mixing). Examples thereof include a solution polymerization method and an interfacial polymerization method. A preferred method is a melt polymerization method.

  In addition, in the reaction, the amount used (ratio of use) of the dicarboxylic acid component (A), the diol component (B), etc. can be selected from the same range as described above. You may let them. For example, in the diol component, the aliphatic diol may be used in excess of a desired ratio of the skeleton derived from the aliphatic diol in the polyester resin. In addition, the reaction may be performed in the presence or absence of a solvent as appropriate depending on the polymerization method.

The reaction may be performed in the presence of a catalyst. As the catalyst, various catalysts used for producing a polyester resin, for example, a metal catalyst can be used. 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 metal (germanium, etc.), periodic table group 15 metal (antimony, etc.) and the like are 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, for example, about 0.01 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol, preferably about 0.1 × 10 ⁻⁴ to 40 × 10 ⁻⁴ mol, relative to 1 mol of the dicarboxylic acid component. There may be.

  Moreover, you may perform reaction in presence of additives, such as stabilizers (an antioxidant, a heat stabilizer, etc.) as needed.

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. For example, the reaction temperature in the melt polymerization method may be 150 to 300 ° C, preferably 180 to 290 ° C, and more preferably about 200 to 280 ° C.

[Resin composition and molded body]
The polyester resin of this invention can comprise a molded object independently as a resin component. In addition, such a polyester resin of this invention can also comprise a resin composition (or resin molding) with an additive (after-mentioned component etc.).

  Moreover, the polyester resin of this invention has the outstanding characteristic as mentioned above, and can also comprise a resin composition and a molded object in combination with other resin. In particular, as described above, the polyester resin of the present invention has low birefringence or negative birefringence, and a birefringence adjusting agent for other resins (additive for adjusting the birefringence of other resins). ) Can also be used. When used for such a birefringence modifier, the birefringence modifier (the polyester resin of the present invention) may be a component that reduces the birefringence of other resins in the positive direction. It may be an additive that reduces the birefringence (inherent birefringence) of other resins in the negative direction.

When used for birefringent dispensing applications, the intrinsic birefringence of other resins is positive intrinsic birefringence, for example, + 10 × 10 ⁻⁴ or more (for example, + 20 × 10 ⁻⁴ to + 300 × 10 ⁻⁴ ), preferably Is + 30 × 10 ⁻⁴ or more (for example, + 40 × 10 ⁻⁴ to + 250 × 10 ⁻⁴ ), more preferably + 50 × 10 ⁻⁴ or more (for example, + 60 × 10 ⁻⁴ to + 200 × 10 ⁻⁴ ), particularly +70. × 10 ⁻⁴ or more (for example, + 80 × 10 ⁻⁴ to + 150 × 10 ⁻⁴ ) may be used.

As other resins, a wide range of resins can be used, and any of thermoplastic resins and curable resins (thermal or photocurable resins) may be used. Examples of the thermoplastic resin include olefin resins, halogen-containing vinyl resins (polyvinyl chloride, etc.), polycarbonate resins (for example, bisphenol A type polycarbonate), polythiocarbonate resins, polyester resins [for example, polyalkylenes. Terephthalate (poly _C2-4 alkylene terephthalate such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, etc.), polyalkylene arylate resin such as polyethylene naphthalate, polyarylate resin (for example, aromatic dicarboxylic acid) Acids (such as terephthalic acid) and aromatic diols (biphenol, bisphenol A, xylylene glycol, adducts of these alkylene oxides) Etc.), polyacetal resins, polyamide resins, polyphenylene ether resins, polysulfone resins, polyphenylene sulfide resins, polyimide resins, polyether ketone resins, heat, etc. Examples thereof include plastic elastomers. The thermoplastic resins may be used alone or in combination of two or more.

  Examples of the curable resin include phenol resin, amino resin (urea resin, melamine resin, etc.), furan resin, unsaturated polyester resin, epoxy resin, thermosetting urethane resin, silicone resin, thermosetting polyimide. Resin, diallyl phthalate resin, vinyl ester resin and the like. The curable resins may be used alone or in combination of two or more. The curable resin may contain a curing agent, a curing accelerator, or the like depending on the type.

  The resin is a resin containing an aromatic ring (such as a benzene ring), for example, an aromatic polycarbonate resin (such as bisphenol A type polycarbonate), an aromatic polyester resin (such as the polyalkylene arylate resin), or a polysulfone resin. Polyphenylene ether resins, polyphenylene sulfide resins, phenol resins, and the like may be used.

  In particular, the resin may be a resin having a 9,9-bisarylfluorene skeleton among the resins having an aromatic ring. The polyester resin of the present invention is excellent in affinity to a wide range of resins, but is also excellent in affinity to a resin having a 9,9-bisarylfluorene skeleton, and has a high-functionality 9,9-bisarylfluorene skeleton. The birefringence of the resin it has can be easily reduced.

  Examples of the resin having a 9,9-bisarylfluorene skeleton include the thermoplastic resins and curable resins exemplified above, and examples thereof include thermoplastic resins [for example, polyester resins, polycarbonate resins, polyurethane resins, etc.] Examples thereof include curable resins (for example, phenol resins and epoxy resins).

For example, as a polyester resin having a 9,9-bisarylfluorene skeleton, 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes {for example, 9,9-bis [4- (2-hydroxyethoxy) phenyl ] and 9,9-bis (hydroxy (poly) C _2-4 alkoxyphenyl) a diol component comprising the like exemplified compounds} like fluorene and fluorene, non fluorene-based dicarboxylic acid component (i.e., the fluorene-based dicarboxylic acid component And a polyester resin having a polymerization component as a dicarboxylic acid component that is not (A1).

  The diol component may contain a diol other than 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes. Examples of such diol components include the diol components exemplified above (for example, aliphatic diols).

The ratio of 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes to other diols [for example, aliphatic diols such as alkanediol ( _C2-4 alkanediol etc.)] is, for example, the former / The latter (molar ratio) = 50/50 to 99/1, preferably 55/45 to 98/2, more preferably 60/40 to 95/5 (for example, 65/35 to 93/7) Usually, it may be about 70/30 to 95/5 (for example, 75/25 to 92/8).

  Although it does not specifically limit as a non-fluorene type dicarboxylic acid component, For example, an aromatic dicarboxylic acid component (such as the compound illustrated above), an alicyclic dicarboxylic acid component (such as the compound illustrated above), etc. are included. It is.

  The use ratio of the polyester resin (birefringence adjusting agent when used for birefringence adjustment, the same shall apply hereinafter) is, for example, 0.1 parts by weight or more (for example, 0.00% with respect to 100 parts by weight of other resins). 5 to 1500 parts by weight), 0.5 parts by weight or more (eg 0.7 to 1000 parts by weight), preferably 1 part by weight or more (eg 2 to 800 parts by weight), more preferably It may be about 3 parts by weight or more (for example, 4 to 600 parts by weight), particularly about 5 parts by weight or more (for example, 7 to 500 parts by weight), and usually 1 to 500 parts by weight (for example, 3 to 300 parts by weight). It may be a degree.

  Since the polyester resin of the present invention can efficiently obtain a birefringence adjusting effect and the like even with a small amount, for example, the use ratio of the birefringence adjusting agent is 70 parts by weight or less (for example, 1 To 60 parts by weight), preferably 50 parts by weight or less (for example, 2 to 40 parts by weight), more preferably 30 parts by weight or less (for example, 3 to 25 parts by weight).

  Moreover, since the polyester resin of this invention has the outstanding characteristic, the usage-amount is 70 weight part or more (for example, 80-1000 weight part) with respect to 100 weight part of resin, Preferably it is 100 weight part. It can be more than (for example, 100 to 800 parts by weight), more preferably 120 parts by weight or more (for example, 130 to 600 parts by weight), particularly 150 parts by weight or more (for example, 200 to 500 parts by weight).

  The resin composition (a resin composition containing only the polyester resin as a resin component, and a resin composition containing the polyester resin and other resin as a resin component) may contain various additives [for example, fillers] Or reinforcing agents, colorants (dyeing pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, A flow control agent, a leveling agent, an antifoaming agent, a surface modifier, a stress reducing agent, a carbon material, etc.]. These additives may be used alone or in combination of two or more.

  Moreover, the molded object formed with the said polyester resin or the said resin composition is also contained in this invention. The shape of such a molded body is not particularly limited, and can be appropriately selected depending on the application. For example, a two-dimensional structure (film shape, sheet shape, plate shape, etc.), a three-dimensional structure (tubular, rod shape, tube) Shape, hollow shape, etc.).

  In particular, since the polyester resin or resin composition of the present invention is excellent in optical properties, an optical material or an optical molded body (particularly, an optical film, an optical lens, etc.) may be suitably formed.

  The molded body can be manufactured using, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a casting molding method, and the like.

  In particular, since the resin composition of the present invention is excellent in various optical properties, it is useful for forming a film (particularly an optical film). Therefore, the present invention includes a film (optical film) formed from the polyester resin or the resin composition.

  The thickness of such a film can be selected according to the use from the range of about 1 to 1000 μm, and may be, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably about 10 to 120 μm.

  Such a film (optical film) is formed (or molded) from the polyester resin or resin composition by using a conventional film forming method, casting method (solvent casting method), melt extrusion method, calendar method, or the like. Can be manufactured.

  The film may be a stretched film. Even if the film of the present invention is a stretched film, low birefringence can be maintained at a high level. Such a stretched film may be either a uniaxially stretched film or a biaxially stretched film.

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

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

  Such a stretched film can be obtained by subjecting a film after film formation (or an unstretched film) to a stretching treatment. The stretching method is not particularly limited. In the case of uniaxial stretching, either a wet stretching method or a dry stretching method may be used. In the case of biaxial stretching, a tenter method (also referred to as a flat method) may be used. However, a tenter method that is excellent in uniformity of stretch thickness is preferable.

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

  In addition, the measurement and evaluation of the characteristic of resin 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 (DSC 6220, manufactured by Seiko Instruments Inc.), a sample was put in an aluminum pan, and Tg was measured in the range of 30 ° C to 200 ° C.

(Refractive index, Abbe number)
Using a multi-wavelength Abbe refractometer “DR-M2 / 1550” (manufactured by Atago Co., Ltd.), the measurement was performed at a measurement temperature of 20 ° C. Refractive index is that of the refractive index _{n d} at a wavelength of 589 nm. The Abbe number (ν _d ) here indicates the wavelength dependence of the refractive index, that is, the degree of dispersion, and can be obtained by the following equation.

ν _d = (n _d −1) / (n _F −n _C )
Each symbol in the above formula is ν _d : Abbe number, n _d : refractive index at d line (wavelength 589 nm), n _F : refractive index at F line (wavelength 486 nm), n _C : at C line (wavelength 656 nm) It means the refractive index, respectively.

(Birefringence)
Birefringence was measured with monochromatic light at 600 nm using a retardation measuring device RETS-100 manufactured by Otsuka Electronics. The test piece used for the measurement was press-molded at 160 to 240 ° C. to obtain a film having a thickness of 100 to 400 μm. The obtained film was obtained by cutting it into a 15 × 50 mm strip. The test specimen for measurement was stretched 2 times, 3 times or 4 times at 25 mm / min at a glass transition temperature (Tg) + 10 ° C. to obtain a stretched film. The birefringence of these films was measured using the above apparatus, the degree of orientation was calculated from the draw ratio, and the intrinsic birefringence was determined from the degree of orientation and birefringence. Specifically, birefringence was measured when the film was stretched 2 times, 3 times and 4 times. Among these, those stretched 3 times were designated as "3 times birefringence". The degree of orientation (F) corresponding to each draw ratio (λ) was determined from the following conversion formula, and the birefringence value for each degree of orientation was plotted.
F = (3 <cos ² θ> −1) / 2
<Cos ² θ> = (1 + r ² ) (r-tan ⁻¹ r) / r ³
r = (λ ³ −1) ^0.5
λ: Stretch ratio, F: Orientation degree An approximate straight line was obtained using the least square method, and the birefringence when the orientation degree (F) = 1.0 (that is, infinite stretch ratio) was obtained by extrapolation. Here, it is assumed that the molecules in the film are ideally oriented to the limit, and in the present invention, the value of birefringence at this time is defined as “intrinsic birefringence”.

Example 1
9,9-di (2-methoxycarbonylethyl) fluorene (9,9-di (2-carboxyethyl) fluorene or dimethyl ester of fluorene-9,9-dipropionic acid, hereinafter referred to as FDPM. No. 1 in this publication was synthesized in the same manner except that t-butyl acrylate was changed to methyl acrylate (37.9 g (0.44 mol)). 1.00 mol, 1,4-benzene dimethanol (1,4-dihydroxy-methylbenzene) (hereinafter, BDM referred) 0.80 mol of ethylene glycol (hereinafter, EG hereinafter) 2.20 mol, manganese acetate as an ester exchange catalyst hydrates 2 × 10 ^{- 4} mol and gradually heated and melted with stirring addition of calcium monohydrate 8 × 10 ^-4 mol acetic, after heating to 230 ° C., DOO Methyl phosphate 14 × ^{10 -4} mol, germanium oxide 20 × 10 ^-4 mol was added, 270 ° C., to remove the ethylene glycol gradually increased, while reducing the pressure until it reaches below 0.13 kPa. After reaching a predetermined stirring torque, the contents were taken out of the reactor to obtain polyester resin pellets.

  The obtained pellet was analyzed by NMR. As a result, 100 mol% of the dicarboxylic acid component introduced into the polyester resin was derived from FDPM, and 80 mol% of the diol component introduced into the polyester resin was derived from BDM, 20 mol%. Was derived from EG.

  The obtained polyester resin had a weight average molecular weight Mw of 47600, a glass transition temperature Tg of 78.6 ° C., a refractive index of 1.6094 and an Abbe number of 26.0.

Further, the intrinsic birefringence of the obtained polyester resin was -39.8 × 10 ⁻⁴ , and the triple birefringence was −19.4 × 10 ⁻⁴ , which was negative birefringence.

(Example 2)
In Example 1, instead of 0.80 mol of BDM, 2,2-di [4- (2-hydroxyethoxy) phenyl] propane (an adduct obtained by adding 2 mol of ethylene oxide to 1 mol of bisphenol A, hereinafter referred to as BisA) A polyester resin pellet was obtained in the same manner as in Example 1 except that 0.8 mol of -EO was used.

  When the obtained pellet was analyzed by NMR, 100 mol% of the dicarboxylic acid component introduced into the polyester resin was derived from FDPM, and 80 mol% of the diol component introduced into the polyester resin was derived from BisA-EO, 20 Mole% was derived from EG.

  The obtained polyester resin had a weight average molecular weight Mw of 54400, a glass transition temperature Tg of 76.0 ° C., a refractive index of 1.620 and an Abbe number of 27.9.

Further, the obtained polyester resin had a birefringence as low as 7.8 × 10 ⁻⁴ .

(Example 3)
In Example 1, polyester resin pellets were obtained in the same manner as in Example 1, except that 0.60 mol of BisA-EO was used instead of 0.80 mol of BDM.

  When the obtained pellet was analyzed by NMR, 100 mol% of the dicarboxylic acid component introduced into the polyester resin was derived from FDPM, and 60 mol% of the diol component introduced into the polyester resin was derived from BisA-EO, 40 Mole% was derived from EG.

  The obtained polyester resin had a weight average molecular weight Mw of 56,200, a glass transition temperature Tg of 75.2 ° C., a refractive index of 1.6018 and an Abbe number of 27.2.

Further, the obtained polyester resin had a low birefringence of 3.2 × 10 ⁻⁴ and a triple birefringence of 2.3 × 10 ⁻⁴ .

Example 4
In Example 1, a polyester resin was used in the same manner as in Example 1 except that 0.80 mol of FDPM and 0.20 mol of dimethyl terephthalate (hereinafter referred to as DMT) were used instead of 1.00 mol of FDPM. Pellets were obtained.

  The obtained pellet was analyzed by NMR. As a result, 80 mol% of the dicarboxylic acid component introduced into the polyester resin was derived from FDPM, 20 mol% was derived from DMT, and 80 mol% of the diol component introduced into the polyester resin. Was derived from BDM and 20 mol% was derived from EG.

  The obtained polyester resin had a weight average molecular weight Mw of 47900, a glass transition temperature Tg of 78.4 ° C., a refractive index of 1.6091, and an Abbe number of 26.2.

Moreover, the intrinsic birefringence of the obtained polyester resin was 21.2 × 10 ⁻⁴ and the triple birefringence was a low birefringence of 13.6 × 10 ⁻⁴ .

(Example 5)
In Example 1, polyester resin pellets were obtained in the same manner as in Example 1 except that 2.20 mol of 1,2-butanediol was used instead of 2.20 mol of EG.

  The obtained pellet was analyzed by NMR. As a result, 100 mol% of the dicarboxylic acid component introduced into the polyester resin was derived from FDPM, and 80 mol% of the diol component introduced into the polyester resin was derived from BDM, 20 mol%. Was derived from 1,2-butanediol.

  The obtained polyester resin had a weight average molecular weight Mw of 58,800, a glass transition temperature Tg of 79.1 ° C., a refractive index of 1.6057, and an Abbe number of 26.5.

Moreover, the intrinsic birefringence of the obtained polyester resin was a low birefringence of −10.5 × 10 ⁻⁴ and the triple birefringence of −7.1 × 10 ⁻⁴ .

(Reference Example 1)
In Example 1, polyester resin pellets were obtained in the same manner as in Example 1 except that 3.0 mol of EG was used instead of 0.80 mol of BDM and 2.20 mol of EG.

  When the obtained pellet was analyzed by NMR, 100 mol% of the dicarboxylic acid component introduced into the polyester resin was derived from FDPM, and 100 mol% of the diol component introduced into the polyester resin was derived from EG.

  The obtained polyester resin had a weight average molecular weight Mw of 60425, a glass transition temperature Tg of 71.7 ° C., a refractive index of 1.6005, and an Abbe number of 26.2.

Moreover, the intrinsic birefringence of the obtained polyester resin is −30.2 × 10 ⁻⁴ , and the triple birefringence is −16.3 × 10 ⁻⁴ , confirming that it has negative birefringence. did.

  From this result, in Examples 1-5, it turns out that the polyester resin which has a high glass transition temperature and a high refractive index was obtained.

  The polyester resin of the present invention has low birefringence or negative birefringence. Moreover, it has excellent heat resistance and has characteristics such as high refractive index, high heat resistance, and high transparency. Thus, since the polyester resin of the present invention has such excellent characteristics, it is possible to form molded articles and resin compositions for various uses as a single resin without being combined with other resins. In particular, since it has unique birefringence characteristics, it can be used as an additive for adjusting (reducing) the birefringence of other resins. Moreover, such additives can be expected not only to adjust birefringence, but also to have effects other than birefringence adjustment, such as maintaining or improving high refractive index and high heat resistance, and improving moisture resistance. Highly useful.

  Therefore, the polyester resin or resin composition of the present invention [for example, a resin modified with a birefringence adjusting agent (or a polyester resin of the present invention) (or a resin composition containing another resin and a birefringence adjusting agent) For example, it can be suitably used for optical lenses, optical films, optical sheets, pickup lenses, holograms, liquid crystal films, organic EL films, and the like. Polyester resins or resin compositions can be used for paints, antistatic agents, inks, adhesives, pressure-sensitive adhesives, resin fillers, charging trays, conductive sheets, protective films (such as protective films for electronic devices and liquid crystal members), Electronic materials (carrier transport agents, light emitters, organic photoreceptors, thermal recording materials, hologram recording materials), electrical / electronic components or equipment (optical discs, inkjet printers, digital paper, organic semiconductor lasers, dye-sensitized solar cells, It can be suitably used as a resin for EMI shield films, photochromic materials, organic EL elements, color filters, etc.), a resin for mechanical parts or equipment (automobiles, aerospace materials, sensors, sliding members, etc.), and the like.

  In particular, since the polyester resin or resin composition of the present invention is excellent in optical properties, it is useful for constituting (or forming) a molded product for optical use (optical molded product). Examples of such an optical molded body include an optical film and an optical lens.

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

Claims (11)

A polyester resin comprising a dicarboxylic acid component (A) containing a fluorene-based dicarboxylic acid component (A1) and a non-fluorene-based diol component (B) containing a non-fluorene-based aromatic diol (B1) as polymerization components , A polyester resin in which the fluorene-based dicarboxylic acid component (A1) is at least one selected from a compound represented by the following formula (1a) or (1b) and an ester-forming derivative thereof .

(In the formula, X _1a and X _1b are the same or different, and an alkylene group which may have an aryl group, R ¹ is a cyano group, a halogen atom, an alkyl group, an aryl group or an acyl group, and n is 0. An integer of -4, k represents an integer of 0-4.)   The polyester resin according to claim 1, wherein the aromatic diol (B1) is composed of an araliphatic diol.   The fluorene-based dicarboxylic acid component (A1) is at least one selected from 9,9-bis (carboxyalkyl) fluorenes and ester-forming derivatives thereof, and the aromatic diol (B1) is di (hydroxyalkyl) arene And at least one araliphatic diol selected from alkylene oxide adducts of bisphenols and the polyester resin according to claim 1 or 2. The fluorene dicarboxylic acid component (A1) is at least one selected from 9,9-bis (carboxy C _2-5 alkyl) fluorenes and ester-forming derivatives thereof, and the aromatic diol (B1) is di ( 4. The compound according to claim 1, which is at least one selected from a hydroxy C _1-4 alkyl) C _6-10 arene and a C _2-4 alkylene oxide adduct of bis (hydroxyphenyl) C _1-8 alkanes. The polyester resin as described in.   The polyester resin in any one of Claims 1-4 in which a dicarboxylic acid component (A) contains 30 mol% or more of fluorene type dicarboxylic acid components (A1).   The dicarboxylic acid component (A) contains 50 mol% or more of the fluorene dicarboxylic acid component (A1), and the non-fluorene diol component (B) contains 50 mol% or more of the aromatic diol (B1). The polyester resin in any one.   The dicarboxylic acid component (A) is further composed of at least one selected from non-fluorene arene dicarboxylic acid, cycloalkane dicarboxylic acid, bi- or tricycloalkane dicarboxylic acid and ester-forming derivatives thereof. The polyester resin according to any one of claims 1 to 6, comprising an acid component (A2), and the diol component (B) further comprises another diol (B2) composed of an alkanediol.   The ratio of the fluorene-based dicarboxylic acid component (A1) to the other dicarboxylic acid component (A2) is the former / the latter (molar ratio) = 100/0 to 50/50, and the aromatic diol (B1) and the other diol The polyester resin according to claim 7, wherein the ratio of (B2) is the former / the latter (molar ratio) = 99/1 to 50/50. The polyester resin according to claim 1, wherein the intrinsic birefringence is + 20 × 10 ⁻⁴ or less, the refractive index at 20 ° C. and the wavelength of 589 nm is 1.59 or more.   The optical molded object formed with the polyester resin in any one of Claims 1-9.   The molded article for optics according to claim 10, which is an optical film.