JP6242270B2 - Birefringence modifier - Google Patents

Description

  The present invention relates to a novel birefringence adjusting agent (or retardation adjusting agent) and a resin composition containing the birefringence adjusting agent.

  Various compounds are known as components (birefringence adjusting agents) for adjusting birefringence (or retardation). For example, JP 2009-227871 A (Patent Document 1) discloses a photosensitivity containing a liquid crystal material having a polymerizable functional group, a polymerization initiator, and isocyanuric acid and / or an isocyanuric acid derivative as a birefringence adjusting agent. A composition is disclosed.

  JP 2009-282482 (Patent Document 2) discloses a water-soluble resin having positive orientation birefringence (for example, polyvinyl alcohol-based resin) and a water-soluble resin having negative orientation birefringence (for example, , Polystyrene sulfonate, and the like).

  Furthermore, JP 2012-31276 A (Patent Document 3) discloses a pigment dispersion for a color filter containing a colorant, a resin, and an organic solvent capable of dissolving the resin, and the pigment is used as the colorant. (A) A pigment dispersion composition for a color filter using a modified pigment (D) formed by coating a surface with a retardation adjusting agent is disclosed. This document describes that a specific modified polyamine can be used as a retardation adjusting agent, and that the retardation value can be adjusted in the positive or negative direction by this modified polyamine.

  Various birefringence modifiers are known in this way, but from the viewpoints of compatibility and bleed-out, affinity for the resin component to be added is required, so that in practice, the applicable resins are limited. Cheap. Moreover, depending on the kind of additive, the characteristic of resin may be reduced (for example, low refractive index).

  On the other hand, it is known that compounds having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) 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.

  And the birefringence characteristics of the resin having such a fluorene skeleton are also being studied. For example, JP-A-2006-335974 (Patent Document 4) discloses a dicarboxylic acid compound mainly containing naphthalenedicarboxylic acid and / or an ester-forming derivative thereof, and 9,9-bis [4- (2-hydroxyethoxy). It is disclosed that a molded product having positive birefringence was obtained using a polyester polymer composed of a dihydroxy compound such as phenyl] fluorene.

  JP 2011-21139 (Patent Document 5) discloses 9,9-bis (4-hydroxy-3-sec-butylphenyl) fluorene and 9,9-bis (4-hydroxy-3-cyclohexyl). It is described that a film having negative birefringence was obtained using a polycarbonate having a diol as a specific compound having a branched alkyl group such as phenyl) fluorene or a cyclohexyl group.

JP-A 2008-69224 (Patent Document 6) 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. This document describes that a specific polyester resin having a dicarboxylic acid component having a fluorene skeleton as a polymerization component has low birefringence, but there is no specific description.

JP 2009-227871 A (Claims) JP 2009-282482 A (Claims) JP 2012-31276 A (Claims) JP 2006-335974 A (Claims, Examples) JP 2011-21139 (Claims, Examples) JP 2008-69224 A (Claims, Examples)

  Accordingly, an object of the present invention is to provide a novel birefringence modifier and a resin composition containing the birefringence modifier.

  Another object of the present invention is to provide a birefringence adjusting agent capable of adjusting birefringence without impairing properties such as refractive index and heat resistance, and a resin composition containing the birefringence adjusting agent.

  Still another object of the present invention is to provide a birefringence modifier having excellent affinity for a resin and a resin composition containing the birefringence modifier.

  As described above, the birefringence of a resin having a fluorene skeleton has been studied for only a small part of polyester resins. There are many unclear parts such as negative birefringence, and no investigation has been made as to whether or not it can be used as a birefringence adjusting agent mixed with a resin. For example, even if a certain compound has negative birefringence, when the compatibility with the resin is not good in a mixed system with the resin, the birefringence of the resin is not reduced to negative birefringence, etc. There is a need for trial and error in examining whether it can be applied as a birefringence adjusting agent even if it simply has negative birefringence or positive birefringence.

  Under such circumstances, as a result of intensive studies to solve the above problems, the present inventors have found that a specific polyester resin having at least a fluorene-based dicarboxylic acid component as a polymerization component has negative birefringence (inherent birefringence) and the like. The polyester resin has excellent affinity for the resin, and when mixed with the resin, the birefringence of the resin is actually adjusted (for example, positive) The birefringence of the resin having birefringence can be reduced in the negative direction) and can be applied as a birefringence adjusting agent, and the birefringence can be adjusted without impairing the resin properties such as heat resistance and refractive index. The headline and the present invention were completed.

  That is, the additive of the present invention is an additive for adjusting the birefringence of a resin (for example, a resin having positive intrinsic birefringence), and includes a dicarboxylic acid component (A1) containing a fluorene-based dicarboxylic acid component (A1). A birefringence adjusting agent (birefringence reducing agent, retardation adjusting agent, retardation reducing agent) composed of a polyester resin having A) and a diol component (B) as polymerization components.

  Such a birefringence adjusting agent may be an additive for reducing intrinsic birefringence in the negative direction.

In the birefringence regulator, the fluorene-based dicarboxylic acid component (A1) is, for example, 9,9-bis (carboxyalkyl) fluorenes (for example, 9,9-bis (carboxyC _2-5 alkyl) fluorenes) and the like It may be at least one selected from ester-forming derivatives.

The dicarboxylic acid component (A) may contain 10 mol% or more (particularly 50 mol% or more) of the fluorene dicarboxylic acid component (A1). The dicarboxylic acid component (A) is a non-fluorene arene dicarboxylic acid (for example, C _6-10 arene-dicarboxylic acid), cycloalkane dicarboxylic acid (for example, C _5-8 cycloalkane-dicarboxylic acid), bi- or tri- Including another dicarboxylic acid component (A2) composed of at least one selected from cycloalkanedicarboxylic acids (for example, bi- or tri-C _5-10 cycloalkane-dicarboxylic acids) and ester-forming derivatives thereof. The ratio of the fluorene-based dicarboxylic acid component (A1) to the other dicarboxylic acid component (A2) is the dicarboxylic acid component (A) in which the former / the latter (molar ratio) = about 100/0 to 50/50. There may be.

  In the birefringence modifier, the diol component (B) is, for example, an aliphatic diol (for example, alkane diol), an alicyclic diol [for example, cycloalkane diol, di (hydroxyalkyl) cycloalkane, di (hydroxyalkyl) crosslinking. (Bridged cyclic) cycloalkanes, di (hydroxycycloalkyl) alkanes, di (hydroxyalkyl) oxaspiroalkanes] and araliphatic diols [eg di (hydroxyalkyl) arene, 9,9-bis (hydroxy (poly) Alkoxyaryl) fluorenes] may be included. The diol component (B) may contain an aliphatic diol and a non-aliphatic diol (for example, at least one non-aliphatic diol selected from an alicyclic diol and an araliphatic diol). These ratios may be, for example, the former / the latter (molar ratio) = about 50/50 to 1/99.

The birefringence modifier of the present invention may typically have a negative intrinsic birefringence. In particular, the birefringence modifier of the present invention may have an intrinsic birefringence of −10 × 10 ⁻⁴ or less, 20 ° C., a refractive index at a wavelength of 589 nm of 1.56 or more, and a glass transition temperature of 70 ° C. or more.

  The present invention includes a resin composition containing a resin (particularly a resin having positive intrinsic birefringence) and a birefringence modifier. In such a resin composition, the resin may be a resin having an aromatic ring (for example, a resin having a 9,9-bisarylfluorene skeleton). In particular, the resin may contain at least one selected from polycarbonate resins and polyester resins.

  In such a resin composition, the ratio of the birefringence adjusting agent may be, for example, about 1 to 500 parts by weight with respect to 100 parts by weight of the resin.

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

  In the present invention, a novel birefringence modifier can be provided. Such a birefringence regulator of the present invention is made of a polyester resin having a dicarboxylic acid component having a fluorene skeleton as a polymerization component, and has, for example, a negative birefringence, and thus has a positive birefringence. Can be used as a birefringence adjusting agent (birefringence reducing agent) or the like for adjusting (reducing in the negative direction) the birefringence. In addition, the birefringence adjusting agent of the present invention includes those having reverse wavelength dispersion [characteristic that the phase difference (or birefringence) increases as the wavelength increases]. Therefore, the birefringence regulator of the present invention can also be used as an additive for imparting (or expressing) reverse wavelength dispersion.

  Further, even when the birefringence modifier of the present invention is applied to a resin, it does not impair the resin properties (refractive index, heat resistance, mechanical properties, moisture resistance, etc.) and is combined in the type of resin to be applied and polyester. Such characteristics can also be improved or improved by adjusting the types and ratios of other dicarboxylic acid components and diol components.

  Furthermore, the birefringence modifier of the present invention is excellent in affinity (such as compatibility) for the resin. Therefore, the birefringence adjusting function can be efficiently expressed in the resin. Therefore, it can be applied to a wide range of resins, and bleeding out and the like can be suppressed at a high level. The birefringence modifier of the present invention can exhibit a birefringence function even in a small amount, and even when added in a high ratio, it does not impair the resin properties as described above, but rather can improve the resin properties. Therefore, it can be applied in a wide variety of modes depending on the application, and is extremely useful. A resin containing such a birefringence modifier (or a resin modified by the birefringence modifier of the present invention) has excellent characteristics as described above, and is used for optical molding such as optical films and optical lenses. It can be suitably used for the body.

  The birefringence adjusting agent (birefringence reducing agent, retardation adjusting agent, retardation reducing agent) of the present invention is composed of a polyester resin having a specific dicarboxylic acid component and a 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. Depending on the melt polymerization method, a dicarboxylic acid having a fluorene skeleton, a dicarboxylic acid ester having a fluorene skeleton, and the like are often used (hereinafter the same).

  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 birefringence adjusting function is 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. The aromatic dicarboxylic acid component usually tends to increase birefringence, but can be surprisingly reduced in birefringence when combined with a fluorene-based dicarboxylic acid component (and a diol component described later). Therefore, it is preferable.

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, alkyl isophthalic acid (for example, C _1-4 alkyl terephthalic acid such as 4-methylisophthalic acid), These ester-forming derivatives are exemplified. 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 particular, when used as a birefringence adjusting agent (preparation agent that reduces in the negative direction) of a resin having positive birefringence (intrinsic birefringence) (for example, polyester resin), the effect of reducing birefringence in the negative direction Is expensive.

  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 such as 2,6-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid ester) 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. In particular, when a polyester resin reacted with a condensed polycyclic aromatic dicarboxylic acid is added to the resin having positive birefringence (intrinsic birefringence), birefringence can be effectively reduced.

  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.

In particular, as other carboxylic acid component (A2), non-fluorene aromatic dicarboxylic acid (for example, C _6-10 arene-dicarboxylic acid such as terephthalic acid), alicyclic dicarboxylic acid (for example, C _5-8 cyclohexane) Alkane-dicarboxylic acid, bi- or tri-C _5-10 cycloalkane-dicarboxylic acid and the like) and ester-forming derivatives thereof are preferable.

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

  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 not particularly limited, and is an aliphatic diol (or aliphatic diol component), an alicyclic diol (or alicyclic diol component), an aromatic diol (or Any of aromatic diol components) may be used. Aliphatic diols and alicyclic diols can be preferably used particularly from the viewpoint of the birefringence adjusting function. The alicyclic diol is also suitable from the viewpoint of heat resistance. Furthermore, aromatic diols are suitable from the viewpoints of refractive index and heat resistance. In general, aromatic diols are often easy to increase birefringence, but are surprisingly suitable for combining with a fluorene-based dicarboxylic acid component, because they can lower birefringence.

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 Of alkylene oxide adducts (such as compounds described below) {e.g., di (hydroxycycloalkyl) alkanes [e.g., di (hydroxy C _4-10 such as 2,2-bis (4-hydroxycyclohexyl) propane] Cycloalkyl) C _1-10 alkane, preferably di ( _{hydroxyC 5-8} Cycloalkyl) C _1-4 alkane and the like], diol having a heterocycloalkane skeleton {eg, oxamono or polycycloalkane diol (isosorbide etc.), diol having an oxaspiro ring 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.

Among the alicyclic diols, cycloalkanediol (eg, C _5-8 cycloalkanediol etc.), 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], di (hydroxycycloalkyl) alkane [eg di ( _{hydroxyC 5-8} cycloalkyl) C _1-4 alkane], di (hydroxyalkyl) oxaspiroalkane [for example, di (hydroxyC _1-6 alkyl) tetraoxaspiroalkane] and the like are preferable. In particular, di (hydroxyalkyl) cycloalkane and di (hydroxyalkyl) bridged cycloalkane seem to have a high effect of reducing birefringence in the negative direction in combination with a fluorene-based dicarboxylic acid component. Therefore, these components are preferable as the diol component (B) constituting the birefringence adjusting agent because they can greatly reduce the birefringence in the negative direction in a small amount.

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

Examples of the aromatic diol include dihydroxyarene (hydroquinone, resorcinol, etc.), bisphenols {biphenol, bis (hydroxyphenyl) alkanes [for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy Bis (hydroxyphenyl) C _1-10 alkane such as phenyl) ethane and bisphenol A], bis (hydroxyaryl) fluorenes [eg, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4 9,9-bis (hydroxyphenyl) fluorenes such as -hydroxy-3-methylphenyl) fluorene and 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene; 9,9- (6-hydroxy-2 -9,9-bi, such as naphthyl) fluorene Etc.], araliphatic diols {eg, di (hydroxyalkyl) arene [eg, benzenedimethanol (1,4-benzenedimethanol, 1,3-benzenedimethanol, etc.), etc. Di (hydroxyC _1-4 alkyl) C _6-10 arene; 9,9-bis (hydroxyalkyl) fluorene (eg, 9,9-bis (3-hydroxypropyl) fluorene, etc.)], di (9- Hydroxyalkylfluorenyl) alkane [eg, di [9- (3-hydroxypropyl) -9-fluorenyl) methane, 1,2-di [9- (3-hydroxypropyl) -9-fluorenyl] ethane, etc.] ], Alkylene oxide adducts of bisphenols [for example, 2,2-di [4- (2-hydro Shietokishi) phenyl] propane (bisphenol A1 2 moles of ethylene oxide are added adduct moles) C _2-4 alkylene oxide adduct the exemplary bisphenols etc.], 9,9-bis (hydroxy ( Poly) alkoxyaryl) fluorenes, etc.}. Aromatic diols may be used alone or in combination of two or more.

  9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes [compound having 9,9-bis (hydroxy (poly) alkoxyaryl) fluorene skeleton] is a compound represented by the following formula (2): Also good.

(In the formula, ring Z is an aromatic hydrocarbon ring, R ² is an alkylene group, R ³ is a substituent that is not a carboxyl group, m is an integer of 1 or more, p is an integer of 0 or more, and R ¹ And k are the same as above.)
In the above formula (2), examples of the aromatic hydrocarbon ring represented by ring Z include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, indene, naphthalene, etc. C _8-20 condensed bicyclic hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic hydrocarbon rings (eg, anthracene, phenanthrene, etc.) Formula hydrocarbon ring and the like]. The two rings Z may be the same or different rings, and may usually be the same ring. Preferred ring Z includes a benzene ring and a naphthalene ring, and may be a benzene ring. Incidentally, the radicals R ¹ and k, including the preferred embodiments, are the same as those in Formula (1).

In the formula (1), examples of the alkylene group represented by the group R ² include C _2-6 alkylene groups such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group. , Preferably a _C2-4 alkylene group, More preferably, a _C2-3 alkylene group is mentioned. When m is 2 or more, the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group. In the two aromatic hydrocarbon rings Z, the groups R ² may be the same or different, and may usually be the same.

The number (number of moles added) m oxyalkylene groups (OR ²⁾ may be one or more, e.g., 1 to 10 (e.g., 1-6), preferably 1 to 4, more preferably 1 to 2, In particular, it may be 1. The number of substitutions m may be the same or different for different rings Z.

In the formula (2), the substitution position of the hydroxy (poly) alkoxy group [namely, —O— (R ² O) _m —H] is not particularly limited, and the substitution position on the ring Z is substituted. It only has to be. For example, when the ring Z is a benzene ring, the hydroxyl group-containing group may be substituted at the 2-6 position of the phenyl group, and may preferably be substituted at the 4 position. Further, when the ring Z is a condensed polycyclic hydrocarbon ring, the hydroxyl group-containing group is a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of fluorene in the condensed polycyclic hydrocarbon ring (for example, In most cases, it is substituted at the 5-position, 6-position, etc. of the naphthalene ring.

The substituent R ³ substituted on the ring Z is usually a non-reactive substituent, for example, an alkyl group (for example, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, C _1-8 alkyl group etc.), cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group), aryl group (eg, phenyl group, tolyl group, xylyl group, naphthyl group etc.) _6-10 an aryl group), a hydrocarbon group such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group); an alkoxy group (methoxy group, _{C 1} such as ethoxy groups _-8 an alkoxy group), such as C _5-10 cycloalkyl group such as a cycloalkoxy group (hexyloxy group cyclohexylene), an aryloxy group (Fe _{C 6-10} aryloxy groups such as alkoxy groups), the radical -OR [expression such aralkyloxy groups _{(C 6-10} aryl _{-C 1-4} alkyl group such as a benzyl group), R is a hydrocarbon radical (Such as the hydrocarbon groups exemplified above). A group such as an alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group) —SR (wherein R is as defined above); an acyl group (such as a C _1-6 acyl group such as an acetyl group); Alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group; substituted amino group (for example, dimethyl) And a dialkylamino group such as an amino group).

Preferred group R ³ includes a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _6-10 Aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group and the like), alkoxy group (C _1-4 alkoxy group and the like) and the like. More preferable group R ³ is an alkyl group [C _1-4 alkyl group (particularly methyl group) and the like], an aryl group [eg C _6-10 aryl group (particularly phenyl group) and the like], and particularly an aryl group. Is preferred.

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

  Specific 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes (or the compound represented by the formula (2)) include 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes [ Or a compound having 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorene skeleton], 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes [or 9,9-bis (hydroxy (poly) alkoxynaphthyl) ) A compound having a fluorene skeleton] and the like.

9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes include, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) phenyl] 9,9-bis (hydroxyC _2-4 alkoxyphenyl) fluorene} such as fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene}, 9,9-bis (alkyl-hydroxyalkoxyphenyl) Fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 9, Such as 9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene 9,9-bis (mono or di C _1-4 alkyl-hydroxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- 9,9-bis (mono or di C _6-10 ) such as (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-phenylphenyl] fluorene 9,9-bis (hydroxyalkoxyphenyl) fluorenes such as aryl- _{hydroxyC 2-4} alkoxyphenyl) fluorene} (a compound in which m is 1 in the formula (2)); 9,9-bis (hydroxydi) Alkoxyphenyl) fluorene {eg, 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] phenyl Eniru} 9,9-bis (hydroxy polyalkoxy phenyl) fluorene such as 9,9-bis fluorene _{(hydroxy-di-C 2-4} alkoxyphenyl) fluorene} (In Formula (2), with m is 2 or more A certain compound) and the like.

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

Among these 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes, in particular, 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes {for example, 9,9-bis [4- (2 - hydroxyethoxy) phenyl] fluorene such as 9,9-bis (hydroxy _{(poly) C 2-4} alkoxyphenyl) fluorene}, 9,9-bis (hydroxy (poly) alkoxy - aryl aryl) fluorenes {e.g., 9 9,9-bis (aryl-hydroxy (poly) C _2-4 alkoxyphenyl) fluorene}, such as 1,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene}.

  The diol component (B) may be used alone or in combination of two or more.

  Among these diol components (B), aliphatic diols (for example, alkane diols), alicyclic diols [for example, di (hydroxyalkyl) cycloalkanes, di (hydroxyalkyl) -bridged cycloalkanes, etc.], aromatic aliphatics Diols [for example, di (hydroxyalkyl) arene) and the like are preferable.

  Among these, alicyclic diols and araliphatic diols are preferable from the viewpoint of heat resistance and the like. In particular, from the viewpoint of refractive index and heat resistance, araliphatic diols [for example, di (hydroxyalkyl) arene, 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes, etc.] are preferable. Therefore, the diol component (B) may be composed of at least these diol components.

  The diol component (B) may be composed of at least an aliphatic diol (for example, alkane diol) from the viewpoint of polymerizability. In this case, the diol component (B) can be composed only of an aliphatic diol, and as described above, from the viewpoint of refractive index and heat resistance, a non-aliphatic diol [for example, an alicyclic diol, aromatic Diols (such as araliphatic diols)] may be combined.

  Furthermore, alicyclic diols and araliphatic diols seem to have a high effect of reducing birefringence in the negative direction in combination with the fluorene-based dicarboxylic acid component (A1). It is preferable as a regulator that reduces in the negative direction.

  In a preferred embodiment, the diol component (B) is a cycloalkanediol, di (hydroxyalkyl) cycloalkane, di (hydroxyalkyl) bridged cycloalkane, di (hydroxycycloalkyl) alkane, di (hydroxyalkyl) oxaspiroalkane, di (Hydroxyalkyl) arene, at least one selected from 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes [eg, cycloalkanediol, di (hydroxyalkyl) cycloalkane, di (hydroxyalkyl) arene)] And alkanediol if necessary. Further, even if the diol component (B) is an aliphatic diol (alkanediol), it functions as a birefringence adjusting agent (adjusting agent that reduces birefringence in the negative direction).

  When combining an aliphatic diol and a non-aliphatic diol, these ratios are the former / the latter (molar ratio) = 99/1 to 1/99 (eg 97/3 to 3/97), preferably 95/5. ˜5 / 95 (for example, 93/7 to 7/93), more preferably about 90/10 to 10/90 (for example, 85/15 to 15/85). In particular, the ratio of the aliphatic diol to the non-aliphatic diol is the former / the latter (molar ratio) = 90/10 to 1/99 (for example, preferably 80/20 to 3/97), preferably 70/30 to It may be about 5/95 (for example, 60/40 to 7/93), more preferably about 50/50 to 10/90 (for example, 40/60 to 15/85), and usually 50/50 to 1 / It may be about 99 (for example, 40/60 to 3/97, preferably 30/70 to 5/95, more preferably 25/75 to 10/90).

  When the diol component (B) is composed of a non-aliphatic diol [alicyclic diol and / or aromatic diol], the ratio of the non-aliphatic diol to the entire 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), more preferably 50 mol% or more (for example, 60 mol% or more), or 70 mol% or more ( For example, it may be 75 mol% or more.

[Polyester resin]
The polyester resin (birefringence adjusting agent) is a polyester resin having a dicarboxylic acid component (A) and a diol component (B) as polymerization components. And this polyester resin can be used as a birefringence adjusting agent and may be either positive birefringence or negative birefringence, but is usually positive birefringence with a small absolute value or negative birefringence. It has birefringence, especially negative birefringence in many cases. Such a polyester resin can be suitably used as a birefringence adjusting agent (birefringence reducing agent) for reducing the birefringence of a resin having positive birefringence in the negative direction.

The intrinsic birefringence value of the polyester resin can be selected from a range of about + 40 × 10 ⁻⁴ or less (for example, −150 × 10 ⁻⁴ to + 30 × 10 ⁻⁴ ), for example, + 10 × 10 ⁻⁴ or less (for example, −120 × 10 ⁻⁴ to + 5 × 10 ⁻⁴ ), preferably a negative value [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, -20 × ^{10 -4} or less (e.g., -30 × ^{10 -4} or less, Preferably, it can also be set to −40 × 10 ⁻⁴ or less.

  Polyester resins often have a relatively high refractive index, and even when used as a birefringence regulator, the refractive index of the resin can be maintained at a relatively high level. It 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, 1.605 to 1.7), particularly 1.61 or more (for example, 1.615 to 1.68), particularly preferably 1.62 or more. (For example, 1.625 to 1.66)].

  The glass transition temperature (Tg) of the polyester resin can be selected from a range of 50 ° C. or higher (for example, 60 ° C. or higher), for example, 70 ° C. or higher (for example, about 70 to 200 ° C.), preferably 75 ° C. or higher (for example, It may be about 75 to 180 ° C., 80 ° C. or higher [for example, 80 to 180 ° C., preferably 85 ° C. or higher (for example, about 90 to 160 ° C.), more preferably 100 ° C. or higher (for example, 105 to 150 ° C.). Or about 110 ° C. (for example, about 115 to 140 ° 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 component may be used in excess of a desired ratio of the skeleton derived from the aliphatic diol component 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. In particular, when a non-fluorene-based dicarboxylic acid component and a fluorene-based dicarboxylic acid component are combined, the viscosity is relatively low and it is easy to produce by melt polymerization. In addition, melt polymerization may be carried out under reduced pressure to remove by-product water, etc., but even under such reduced pressure, a polyester resin reflecting the preparation can be efficiently obtained without distilling. Can do.

[Birefringence adjusting agent and resin composition]
The birefringence adjusting agent of the present invention is composed of the above polyester resin, and can be used as an additive for adjusting the birefringence of the resin. Such a birefringence modifier may be a component that reduces the birefringence of the resin in the positive direction, but is usually an additive that reduces the birefringence (intrinsic birefringence) of the resin in the negative direction. May be.

The intrinsic birefringence of the resin is positive intrinsic birefringence, for example, + 10 × 10 ⁻⁴ or more (for example, + 20 × 10 ⁻⁴ to + 300 × 10 ⁻⁴ ), preferably + 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 ).

The resin is not particularly limited as long as it is a resin that can be adjusted by a birefringence modifier (the polyester resin). For example, a wide range of resins can be used, and any of a thermoplastic resin and a curable resin (thermal or photocurable resin) can be used. It may be. 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. Preferred resins include polycarbonate resins (such as bisphenol A polycarbonate) and polyester resins (such as polyalkylene arylate resins). 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 a bisphenol A type polycarbonate), an aromatic polyester resin (such as the polyalkylene arylate resin), or a polysulfone resin. , Polyphenylene ether resin, polyphenylene sulfide resin, phenol resin, and the like].

  In particular, the resin may be a resin having a 9,9-bisarylfluorene skeleton among the resins having an aromatic ring. The birefringence modifier of the present invention is excellent in affinity for a wide range of resins, but is also excellent in affinity for resins having a 9,9-bisarylfluorene skeleton, and has a high function of 9,9-bisarylfluorene. Birefringence of the resin having a skeleton 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 birefringence modifier (the polyester resin) can be selected from a range of about 0.1 parts by weight or more (for example, 0.5 to 1500 parts by weight) with respect to 100 parts by weight of the resin. 5 parts by weight or more (for example, 0.7 to 1000 parts by weight), preferably 1 part by weight or more (for example, 2 to 800 parts by weight), more preferably 3 parts by weight or more (for example, 4 to 600 parts by weight), particularly It may be about 5 parts by weight or more (for example, 7 to 500 parts by weight), and may be usually about 1 to 500 parts by weight (for example, 3 to 300 parts by weight).

  Since the birefringence adjusting agent of the present invention can obtain a birefringence adjusting effect efficiently even in 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).

  In addition, since the birefringence modifier of the present invention often has excellent characteristics, the use ratio of the birefringence modifier is 70 parts by weight with respect to 100 parts by weight of the resin. Or more (for example, 80 to 1000 parts by weight), preferably 100 parts by weight or more (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, it may be 200 to 500 parts by weight.

  Thus, the resin (resin composition) in which the birefringence is adjusted is obtained by the birefringence adjusting agent of the present invention. The present invention also includes such a resin composition, that is, a resin composition containing a resin and a birefringence modifier. In such a resin composition, the types and mixing ratios (use ratios) of the resin and the birefringence adjusting agent are as described above.

  The resin composition may contain various additives [for example, fillers or reinforcing agents, colorants (dye pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet rays). Absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents, carbon materials, etc.] Good. These additives may be used alone or in combination of two or more.

  Moreover, the molded object formed with such a 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 resin composition of the present invention is excellent in optical characteristics, an optical material or a molded article for optics (in particular, 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 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 produced by film-forming (or molding) the resin composition using a conventional film-forming method, casting method (solvent casting method), melt extrusion method, calendar method, or the like. it can.

  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 transverse direction). Stretching). In the case of uniaxial stretching, the stretching may be longitudinal stretching (for example, 2.5 to 8 times stretching in the longitudinal direction) or lateral stretching (for example, 1.2 to 5 times stretching in the transverse direction).

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

  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”.

(Water absorption)
A test piece was obtained by cutting a 1 mm thick film prepared by press molding the resin at 160 to 240 ° C. into a 30 × 30 mm square. The obtained test piece was dried in a vacuum state at 80 ° C. for 8 hours, and then allowed to cool to room temperature. After allowing to cool, the weight of the test piece was measured and then immersed in water at 23 ° C. After the elapse of 24 hours, the water on the surface of the test piece was wiped off, the weight was measured, and the water absorption was determined from the change in weight before and after immersion.

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 in Example 1 was changed to methyl acrylate (37.9 g (0.44 mol)). 1.00 mol, ethylene glycol (hereinafter, EG) (3.0 mol), manganese acetate tetrahydrate 2 × 10 ⁻⁴ mol and calcium acetate monohydrate 8 × 10 ⁻⁴ mol as a transesterification catalyst, and gradually heated and melted while stirring. After the temperature was raised to 230 ° C., 14 × 10 ⁻⁴ mol of trimethyl phosphate and 20 × 10 ⁻⁴ mol of germanium oxide were added, and 270 ° C., 0.13 kPa. Ethylene glycol was removed while gradually raising the temperature and reducing the pressure until the following was reached. After reaching a predetermined stirring torque, the contents were taken out of the reactor to obtain polyester resin pellets.

  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, an Abbe number of 26.2, and a water absorption of 0.22%.

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.

(Example 2)
In Example 1, instead of EG 3.0 mol, EG 2.20 mol and 1,4-cyclohexanedimethanol (hereinafter referred to as CHDM) 0.80 mol were used in the same manner as in Example 1, Polyester resin pellets were obtained.

  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, 80 mol% of the diol component introduced into the polyester resin was derived from CHDM, and 20 mol%. Was derived from EG.

  The obtained polyester resin had a weight average molecular weight Mw of 56,700, a glass transition temperature Tg of 83.4 ° C., a refractive index of 1.5961, an Abbe number of 30.4, and a water absorption of 0.22%.

The intrinsic birefringence of the obtained polyester resin, -88.6 × ^{10 -4,} 3 Baifuku refraction is -43.0 × ^{10 -4,} confirmed to have a negative birefringence did.

(Example 3)
In Example 1, instead of EG 3.0 mol, EG 2.20 mol and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEF) 0 A polyester resin pellet was obtained in the same manner as in Example 1 except that 80 mol was used.

  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 BPEF, 20 mol%. Was derived from EG.

  The obtained polyester resin had a weight-average molecular weight Mw of 45800, a glass transition temperature Tg of 122.6 ° C., a refractive index of 1.6363, an Abbe number of 23.7, and a water absorption of 0.25%.

Moreover, the intrinsic birefringence of the obtained polyester resin is −45.0 × 10 ⁻⁴ , and the triple birefringence is −25.6 × 10 ⁻⁴ , confirming that it has negative birefringence. did.

Example 4
In Example 1, 0.80 mol of FDPM and 0.20 mol of dimethyl terephthalate (hereinafter referred to as DMT) were used instead of 1.0 mol of FDPM, and EG 2.20 mol and BPEF 0. A polyester resin pellet was obtained in the same manner as in Example 1 except that 80 mol was used.

  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 BPEF and 20 mol% was derived from EG.

  The obtained polyester resin had a weight average molecular weight Mw of 46200, a glass transition temperature Tg of 126.4 ° C., a refractive index of 1.6351, and an Abbe number of 23.5.

The polyester resin obtained had a double birefringence of −24.3 × 10 ⁻⁴ and was confirmed to have negative birefringence.

(Example 5)
In Example 1, 0.90 mol of FDPM and 0.10 mol of dimethyl 2,6-naphthalenedicarboxylate (hereinafter referred to as DMN) were used instead of 1.0 mol of FDPM, and EG2. A polyester resin pellet was obtained in the same manner as in Example 1 except that 20 mol and 0.80 mol of BPEF were used.

  When the obtained pellets were analyzed by NMR, 90 mol% of the dicarboxylic acid component introduced into the polyester resin was derived from FDPM, 10 mol% was derived from DMN, and 80 mol% of the diol component introduced into the polyester resin. Was BPEF and 20 mol% was EG-derived.

  The obtained polyester resin had a weight average molecular weight Mw of 46100, a glass transition temperature Tg of 125.4 ° C., a refractive index of 1.637 and an Abbe number of 23.2.

The intrinsic birefringence of the obtained polyester resin, -26.6 × ^{10 -4,} 3 Baifuku refraction is -22.4 × ^{10 -4,} confirmed to have a negative birefringence did.

(Examples 6 to 12, Comparative Example 1)
It was confirmed by the following method that the polyester resin obtained in the above example actually has a birefringence adjusting function.

  That is, the resin and the polyester resin (birefringence adjusting agent) obtained in Examples 1 to 5 were used at various ratios shown in Table 1 using a twin-screw extruder (manufactured by Technobel Co., Ltd., KZW15-30MG). The mixture was melt-extruded (extruded and kneaded) at 240 to 280 ° C. to obtain pellets (Comparative Example 1 used only a resin for comparison). All pellets were transparent and had good compatibility.

  And various characteristics were measured about the obtained pellet.

  In addition, in the resin to which the birefringence adjusting agent is added, in order to confirm the influence of the birefringence adjusting agent obtained in Examples on the refractive index and the heat resistance, a high refractive index, high heat resistant polyester resin, that is, Polyester resin in which 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and ethylene glycol are used as the diol component and dimethyl terephthalate is used as the dicarboxylic acid component (Example 1 of JP-A-7-198901) Prepared according to the above method).

  The results are shown in Table 1. In the table, “Tg” represents the glass transition temperature, and “Mw” represents the weight average molecular weight.

  As is clear from the results in Table 1, the polyester resins obtained in Examples 1 to 5 have negative birefringence and a birefringence regulator (birefringence regulator that reduces birefringence in the negative direction). Confirmed to function as. In addition, while having a birefringence adjusting function, there are some which can maintain the Tg and refractive index of the base resin at a high level and can improve the refractive index. Furthermore, the water absorption rate could be reduced.

(Examples 13 to 16)
In addition, using the resin obtained in Example 3, the polyester resin of the present invention has a birefringence adjusting function with respect to other resins (polycarbonate resins) having high heat resistance and high refractive index. I checked.

  Table 2 shows the resins shown in Table 2 (polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name “Iupilon H-4000”) and the polyester resin (birefringence adjusting agent) obtained in Example 3. At the indicated ratio, melt extrusion (extrusion kneading) was performed at 240 to 280 ° C. using a twin-screw extruder (manufactured by Technobel, KZW15-30MG) to obtain pellets.

  And various characteristics were measured about the obtained pellet.

  The results are shown in Table 2. In Table 2, “Tg” indicates a glass transition temperature.

  As shown in Examples 13 to 16, the polyester resin obtained in Example 3 has a birefringence regulator (negative) even with respect to other resins (polycarbonate resins) having high heat resistance and high refractive index. It was found that the compound functions as a birefringence modifier that reduces birefringence in the direction of. In addition, while having a birefringence adjusting function, the Tg and refractive index of the base resin can be maintained at a high level.

  Thus, since the effect of the polyester resin having the fluorene-based dicarboxylic acid component as the dicarboxylic acid component was confirmed, a polyester resin was synthesized by changing the type of diol as follows, and negative birefringence was similarly produced. I confirmed that I have it.

(Example 17)
In Example 1, it replaced with EG3.0 mol, and was similar to Example 1 except having used EG 2.20 mol and 1,4-benzenedimethanol (1,4-dihydroxymethylbenzene) 0.80 mol. Thus, polyester resin pellets were obtained.

  When the obtained pellets were 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 1,4-benzenediene. Methanol origin, 20 mol% was EG origin.

  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.

Moreover, the intrinsic birefringence of the obtained polyester resin was −39.8 × 10 ⁻⁴ , and the triple birefringence was −19.4 × 10 ⁻⁴ , confirming that it had negative birefringence. .

(Example 18)
In Example 1, instead of 3.0 mol of EG, 2.20 mol of EG and 0.80 mol of tricyclodecane dimethanol (tricyclo [5.2.1.0 (2,6)] decanedimethanol) were used. Except for this, polyester resin pellets were obtained in the same manner as in Example 1.

  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 tricyclodecane dimethanol. 20 mol% was derived from EG.

  The resulting polyester resin had a weight average molecular weight Mw of 48600, a glass transition temperature Tg of 91.3 ° C., a refractive index of 1.5877, and an Abbe number of 30.5.

Moreover, the intrinsic birefringence of the obtained polyester resin was −31.3 × 10 ⁻⁴ , and the triple birefringence was −17.5 × 10 ⁻⁴ , and it was confirmed to have negative birefringence. .

(Example 19)
In Example 1, 0.80 mol of FDPM and 0.20 mol of DMT were used instead of 1.0 mol of FDPM, and 2.20 mol of EG and 9,9-bis [4- (2- Hydroxyethoxy) -3-phenylphenyl] fluorene (hereinafter referred to as BOPPEF, synthesized in the same manner as in Example 4 of JP-A-2001-206863) Except that 0.80 mol was used, Example 1 and Similarly, pellets of polyester resin 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 BOPPEF and 20 mol% was derived from EG.

  The obtained polyester resin had a weight average molecular weight Mw of 38400, a glass transition temperature Tg of 133.3 ° C., a refractive index of 1.6463, and an Abbe number of 22.0.

Moreover, the intrinsic birefringence of the obtained polyester resin was −22.8 × 10 ⁻⁴ , the triple birefringence was −13.0 × 10 ⁻⁴ , and it was confirmed to have negative birefringence. .

(Example 20)
In Example 1, in place of 3.0 mol of EG, 2.20 mol of EG and 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5. 5] Polyester resin pellets were obtained in the same manner as in Example 1 except that 0.80 mol of undecane (hereinafter referred to as spiroglycol) 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 65 mol% of the diol component introduced into the polyester resin was derived from spiroglycol, 35 mol. % Was from EG.

  The obtained polyester resin had a weight average molecular weight Mw of 51700, a glass transition temperature Tg of 93.3 ° C., a refractive index of 1.5695, and an Abbe number of 29.3.

Further, the intrinsic birefringence of the obtained polyester resin was −17.9 × 10 ⁻⁴ , and the triple birefringence was −10.8 × 10 ⁻⁴ , and had negative birefringence.

(Example 21)
In Example 1, polyester resin pellets were obtained in the same manner as in Example 1 except that EG 2.20 mol and spiroglycol 0.50 mol were used instead of EG 3.0 mol.

  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 40 mol% of the diol component introduced into the polyester resin was derived from spiroglycol, 60 mol. % Was from EG.

  The weight average molecular weight Mw of the obtained polyester resin was 74100, the glass transition temperature Tg was 90.5 ° C., the refractive index was 1.5656, and the Abbe number was 29.2.

Moreover, the intrinsic birefringence of the obtained polyester resin was −31.5 × 10 ⁻⁴ , and the triple birefringence was −19.0 × 10 ⁻⁴ , and had negative birefringence.

(Example 22)
In Example 1, polyester resin pellets were obtained in the same manner as in Example 1 except that instead of EG 3.0 mol, 1,2-butanediol 2.20 mol and CHDM 0.80 mol were used. .

  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, 80 mol% of the diol component introduced into the polyester resin was derived from CHDM, and 20 mol%. Was derived from 1,2-butanediol.

  The obtained polyester resin had a weight average molecular weight Mw of 46200, a glass transition temperature Tg of 83.0 ° C., a refractive index of 1.5814, and an Abbe number of 28.8.

Moreover, the intrinsic birefringence of the obtained polyester resin was −29.5 × 10 ⁻⁴ , and the triple birefringence was −20.5 × 10 ⁻⁴ , and had negative birefringence.

  The polyester resins of Examples 1, 2, 4, 5 and 17 to 22 also exhibit negative birefringence and function as a birefringence adjusting agent in the same manner as the polyester resin of Example 3.

  The birefringence adjusting agent of the present invention can be used as an additive for adjusting (reducing) the birefringence of the resin. 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 resin modified with the birefringence adjusting agent of the present invention (or a resin composition containing a resin and a birefringence adjusting agent) has, for example, a high refractive index, high heat resistance, low birefringence, and high transparency. It has excellent optical characteristics such as heat resistance and various characteristics such as heat resistance. Such a resin composition can be suitably used for an optical lens, an optical film, an optical sheet, a pickup lens, a hologram, a liquid crystal film, an organic EL film, and the like. Resin compositions include paints, antistatic agents, inks, adhesives, pressure-sensitive adhesives, resin fillers, charging trays, conductive sheets, protective films (protective films for electronic equipment, liquid crystal members, etc.), electrical / electronic materials (Carrier transport agent, luminous body, organic photoreceptor, thermal recording material, hologram recording material), electrical / electronic component or equipment (optical disk, inkjet printer, digital paper, organic semiconductor laser, dye-sensitized solar cell, EMI shield film) Resin for photochromic materials, organic EL elements, color filters, etc.), resin for mechanical parts or equipment (automobiles, aerospace materials, sensors, sliding members, etc.) and the like.

  In particular, since the resin composition is excellent in optical characteristics, it is useful for constituting (or forming) a molded product for optical use (optical molded product). Examples of the optical molded body formed (configured) with such a resin composition 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 (19)

An additive for adjusting the birefringence of a resin, which is at least one fluorene-based dicarboxylic acid component (A1) selected from a compound represented by the following formula (1a) or (1b) and an ester-forming derivative thereof: A birefringence regulator comprising a polyester resin having a dicarboxylic acid component (A) containing diol and a diol component (B) as polymerization components.

(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.) Fluorene dicarboxylic acid component (A1) is 9,9-bis (carboxyalkyl) fluorenes and birefringence adjusting agent according to claim 1 Symbol placement is at least one selected from an ester-forming derivative thereof. 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 birefringence regulator according to claim 1 or 2 , comprising an acid component (A2). The fluorene-based 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 other dicarboxylic acid component (A2) is C _6-10 arene - dicarboxylic _{acid, C 5-8} cycloalkane - dicarboxylic acid, bi- or _{tri-C 5-10} cycloalkane - claim 3 is a dicarboxylic acid and at least one member selected from ester-forming derivatives thereof The birefringence adjusting agent as described. The birefringence regulator according to any one of claims 1 to 4 , wherein the dicarboxylic acid component (A) contains 10 mol% or more of the fluorene-based dicarboxylic acid component (A1). The birefringence regulator according to any one of claims 1 to 5 , wherein the dicarboxylic acid component (A) contains 50 mol% or more of the fluorene-based dicarboxylic acid component (A1). Ratio of fluorene-based dicarboxylic acid component (A1) and with the other dicarboxylic acid component (A2) is, according to any one of claims 1 to 6 the former / the latter (molar ratio) is a = 100 / 0-50 / 50 Birefringence modifier. The birefringence regulator according to any one of claims 1 to 7 , wherein the diol component (B) contains at least one selected from an aliphatic diol, an alicyclic diol, and an araliphatic diol. The diol component (B) is an alkanediol, cycloalkanediol, di (hydroxyalkyl) cycloalkane, di (hydroxyalkyl) bridged cycloalkane, di (hydroxycycloalkyl) alkane, di (hydroxyalkyl) oxaspiroalkane, di ( The birefringence regulator according to any one of claims 1 to 8 , which is at least one selected from hydroxyalkyl) arene and 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes. The diol component (B) comprises an aliphatic diol and at least one non-aliphatic diol selected from an alicyclic diol and an araliphatic diol, the former / the latter (molar ratio) = 50/50 to 1 / The birefringence modifier according to claim 8 or 9, which is contained at a ratio of 99. The birefringence adjusting agent according to any one of claims 1 to 10 , which has negative intrinsic birefringence. The birefringence adjusting agent according to any one of claims 1 to 11 , which has an intrinsic birefringence of -10 x ^10-4 or less, 20 ° C, a refractive index at a wavelength of 589 nm of 1.56 or more, and a glass transition temperature of 70 ° C or more. . A resin composition comprising a resin having positive intrinsic birefringence and the birefringence regulator according to any one of claims 1 to 12 . The resin composition according to claim 13 , wherein the resin is a resin having an aromatic ring. The resin composition according to claim 13 or 14 , wherein the resin contains at least one selected from polyester resins and polycarbonate resins. The resin composition according to any one of claims 13 to 15 , wherein the resin is a resin having a 9,9-bisarylfluorene skeleton. The resin composition according to any one of claims 13 to 16 , wherein the ratio of the birefringence modifier is 1 to 500 parts by weight with respect to 100 parts by weight of the resin. The optical molded object formed with the resin composition in any one of Claims 13-17 . The optical molded body according to claim 18, which is an optical film.