JP2009167269A - High-molecular weight polyester-based resin and method of producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-molecular weight polyester-based resin having excellent optical characteristics even in a high molecular weight, and to provide a method of producing the same. <P>SOLUTION: In the high-molecular weight polyester-based resin, a fluorene-containing polyester-based resin containing a 9,9-bisarylfluorene skeleton is bound with a chain extender. The chain extender is a compound containing, in one molecule, at least two of at least one functional group selected from a hydroxy group, an amino group, an epoxy group, an oxazoline group, a carboxy group, and an acid anhydride group. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a polyester resin excellent in optical characteristics even with a high molecular weight, and a method for producing the same.

  Since optical members (for example, optical lenses) require high transparency and excellent mechanical properties (for example, mechanical strength), various resins have been conventionally used. As the resin, polymethyl methacrylate (PMMA), polycarbonate (PC) and the like are known.

  Polymethylmethacrylate is excellent in transparency and light resistance, has low birefringence, and has a large Abbe number and small optical anisotropy, so it is suitable for optical applications, but has high hygroscopicity. The form stability after molding is inferior, and the physical properties may change. Furthermore, PMMA has a lower refractive index than other optical resins, making it difficult to reduce the thickness of a molded product (for example, an optical lens), and is inferior in mechanical properties and heat resistance.

  Polycarbonate (particularly aromatic polycarbonate) has a relatively small Abbe number, but is excellent in transparency, heat resistance and hygroscopicity, and exhibits a high refractive index. However, polycarbonate is inferior in light resistance and moldability, and further, birefringence is likely to increase with molding, so it is not necessarily suitable for applications of optical members (for example, optical lenses) that require high accuracy. In addition, in order to reduce the occurrence of birefringence associated with molding, attempts have been made to reduce the molecular weight of the polycarbonate to increase the fluidity, but the mechanical properties of the molded body may be greatly degraded.

  With the demand for high-performance optical members, polyester resins having a fluorene skeleton have been proposed as transparent resins having a high refractive index and low birefringence. For example, Japanese Patent Application Laid-Open No. 7-149981 (Patent Document 1), Japanese Patent No. 2843214 (Patent Document 2) and the like disclose a polyester polymer having at least an aromatic dicarboxylic acid and a dihydroxy compound containing a fluorene skeleton as polymerization components. And the polyester polymer whose intrinsic viscosity is 0.3 or more is disclosed. JP-A-11-60706 (Patent Document 3) discloses a polyester polymer having a dicarboxylic acid component and a diol component containing a fluorene skeleton as polymerization components. This document describes that the polyester polymer has a weight average molecular weight of 1,000 or more, and in the Examples, a polyester polymer having a weight average molecular weight of 8,300 to 37,500 is produced. Japanese Unexamined Patent Publication No. 2000-319366 (Patent Document 4) discloses a polyester polymer having an alicyclic dicarboxylic acid component and a dihydroxy compound containing a fluorene skeleton as polymerization components. This document describes that the polyester polymer has a weight average molecular weight of 10,000 or more, and in the Examples, a polyester polymer having a weight average molecular weight of 30,500 to 36,600 is produced.

  However, the polyester polymer having a fluorene skeleton described in these documents is excellent in transparency and moldability and is suitable for optical applications, but depending on the application, the mechanical properties are insufficient. High molecular weight is desired.

  Note that the polyester polymers described in Patent Documents 1 to 4 are manufactured by melt polymerization. In order to produce a high molecular weight polyester resin by melt polymerization, it is necessary to carry out the reaction under vacuum conditions at a high temperature, and it is also necessary to spend a long time for the reaction. However, when the reaction is carried out under such conditions, it becomes difficult to take out the resin produced by the increase in viscosity. On the other hand, when the temperature is increased to lower the melt viscosity and increase the polymerization efficiency by stirring and to make it easier to take out the resin, thermal decomposition (depolymerization) occurs, and the molecular weight is lowered and the color is easily colored. Not suitable for. Therefore, it is difficult to produce a high molecular weight resin that is less colored and suitable for optical applications by melt polymerization.

  As a high molecular weight polyester resin, for example, JP-A-8-109249 (Patent Document 5) discloses a polyester resin having at least a dicarboxylic acid component and a dihydroxy compound containing a fluorene skeleton as a polymerization component, A polyester resin having an intrinsic viscosity of 0.6 or more in chloroform is disclosed. In the polyester resin of this document, the dicarboxylic acid component and the dihydroxy compound are polymerized by a usual method (for example, a melt polymerization method) to form a polyester copolymer, and then the polyester copolymer is used as a solvent. For example, in the examples, the polyester resins having a weight average molecular weight of 120,000 and 200,000 are produced by dissolving them in trichlorobenzene and reacting them with diisocyanate. ing.

However, in this document, since the reaction is performed in a solution, the obtained polyester resin cannot be used as it is. That is, in order to use it in a solid form, it is necessary to remove the organic solvent through a process such as precipitation, but the operation becomes complicated, and as described above, the temperature needs to be increased in order to remove the organic solvent. There is a problem of lowering the molecular weight and coloring of the resin as the temperature rises. In addition, diisocyanate may easily react with moisture in the air to reduce the activity, and is inferior in handleability.
Japanese Patent Laid-Open No. 7-149981 (Claims) Patent No. 2843214 (Claims) JP-A-11-60706 (Claims) JP 2000-319366 A (Claims, Examples)

  Accordingly, an object of the present invention is to provide a high molecular weight polyester resin excellent in optical properties even if it has a high molecular weight, and a method for producing the same.

  Another object of the present invention is to provide a high molecular weight polyester resin having excellent mechanical strength and a method for producing the same.

  Still another object of the present invention is to provide a high-molecular-weight polyester-based resin that can be produced easily and inexpensively industrially and is useful for optical applications even if it has a high molecular weight, and a method for producing the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a high-molecular-weight polyester-based resin in which a fluorene-containing polyester-based resin having a 9,9-bisarylfluorene skeleton is bound with a specific chain extender, It was found that the optical properties were excellent even with a high molecular weight, and the present invention was completed.

  That is, the high molecular weight polyester resin of the present invention is a high molecular weight polyester resin in which a fluorene-containing polyester resin containing a 9,9-bisarylfluorene skeleton is bonded with a chain extender, and the chain extender Is a compound containing at least two functional groups selected from a hydroxyl group, amino group, epoxy group, oxazoline group, carboxyl group and acid anhydride group in one molecule.

  The fluorene-containing polyester resin has at least the following formula (1)

(In the formula, Z ¹ and Z ² are the same or different and each represents an aromatic hydrocarbon group. R ^1a and R ^1b represent the same or different alkylene group, and R ^2a and R ^2b represent the same or different hydrocarbon. Group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group or substituted amino group, R ^3a and R ^3b are the same or different and carbonized A hydrogen group, an alkoxy group, a halogen atom, a nitro group, a cyano group or a substituted amino group, wherein m and n are the same or different and are 0 or an integer of 1 or more, and h1 and h2 are the same or different and represent 0-4. An integer, j1 and j2 are the same or different and are integers of 0 to 4)
The polyester-type resin which uses as a polymerization component the diol component represented by these, and the dicarboxylic acid component may be sufficient. The high molecular weight polyester resin may have a weight average molecular weight of about 35,000 to 400,000.

  In the present invention, the fluorene-containing polyester resin has a hydroxyl value of 2 to 100 mgKOH / g, and the chain extender has at least one functional group selected from a carboxyl group and an acid anhydride group in at least one molecule. A high molecular weight polyester resin having a weight average molecular weight of 50,000 to 400,000 is included.

  The present invention also includes a method for producing the high molecular weight polyester resin comprising a reaction step of reacting a fluorene-containing polyester resin containing at least a 9,9-bisarylfluorene skeleton with a chain extender.

  In the production method, the ratio of the chain extender may be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the fluorene-containing polyester resin. In the production method, the fluorene-containing polyester resin and the chain extender may be melt-kneaded and reacted in the absence of a solvent.

  In the high molecular weight polyester resin of the present invention, since a specific fluorene-containing polyester resin is bonded with a specific chain extender, the optical properties are excellent even with a high molecular weight. In addition, the high molecular weight polyester resin has a high molecular weight and is excellent in mechanical strength. Such a high molecular weight polyester resin is useful for a wide range of optical applications, and can be produced easily and inexpensively industrially because a specific fluorene-containing polyester resin and a specific chain extender may be combined. .

[High molecular weight polyester resin]
In the high molecular weight polyester resin of the present invention, a fluorene-containing polyester resin containing a 9,9-bisarylfluorene skeleton is bonded with a chain extender.

(Fluorene-containing polyester resin)
The fluorene-containing polyester resin may be a polymer having a dicarboxylic acid component containing a 9,9-bis (carboxyaryl) fluorene skeleton and a diol component as polymerization components, but usually the fluorene-containing polyester resin is , 9,9-bis (hydroxyaryl) fluorene skeleton containing a diol component and a dicarboxylic acid component as a polymer component. Such a polymer includes, for example, a polymer having at least a diol component represented by the formula (1) and a dicarboxylic acid component as polymerization components.

In Z ¹ and Z ² of the formula (1), examples of the aromatic hydrocarbon group include C _6-14 arylene groups such as a phenylene group and a naphthalenediyl group (or two corresponding to a C _6-14 aromatic hydrocarbon ring). Valent group) and the like]. Z ¹ and Z ² are preferably a phenylene group or a naphthalenediyl group (for example, a phenylene group).

In the formula (1), the alkylene group represented by R ^1a and R ^1b is a linear or branched C _2-4 alkylene group such as an ethylene group, a propylene group, a trimethylene group, or a tetramethylene group. Can be illustrated. In R ^1a and R ^1b , the types of alkylene groups may be different from each other. Further, the types of the alkylene groups R ^1a and R ^1b may be different depending on the numbers of the coefficients m and n. A preferable alkylene group is a _C2-3 alkylene group (ethylene group, propylene group), and is usually an ethylene group in many cases.

R ^2a and R ^2b are alkyl groups (eg, linear or branched C _1-8 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups). (In particular, a C _1-6 alkyl group)), a cycloalkyl group (C _5-10 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _{5- 6} cycloalkyl group), aryl group [eg, phenyl group, alkylphenyl group (methylphenyl group (or tolyl group, 2-methylphenyl group, 3-methylphenyl group, etc.), dimethylphenyl group (xylyl group), etc.) and _{C 6-10} aryl group such as a naphthyl group, an aralkyl group (benzyl group, _{C 6-10} aryl, such as phenethyl group - _1-4 such as an alkyl group) carbon atoms and the like; alkoxy group (e.g., methoxy group, an ethoxy group, a propoxy group, n- butoxy group, isobutoxy group, _{C 1-8} alkoxy (especially C, such as t- butoxy _1-6 alkoxy group)); cycloalkoxy group (C _5-10 cycloalkyloxy group such as cyclohexyloxy group); aryloxy group (C _6-10 aryloxy group such as phenoxy group); aralkyloxy group (For example, C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group); acyl group (such as C _1-6 acyl group such as acetyl group); alkoxycarbonyl group (C such as methoxycarbonyl group) _1-4, such as an alkoxycarbonyl group), a halogen atom (a fluorine atom, such as chlorine atom); nitro group; shea Group; and the like substituted amino group (such as dialkylamino group).

The substitution numbers h1 and h2 of the substituents R ^2a and R ^2b may generally be an integer of about 0 to 4 (for example, 0 to 2). The substitution positions of the substituents R ^2a and R ^2b are not particularly limited. Preferred substituents R ^2a and R ^2b are C _1-6 alkyl groups (particularly methyl groups), and preferred substitution numbers h1 and h2 are integers of about 0 to 2 (for example, 0 or 1).

Examples of R ^3a and R ^3b include the hydrocarbon groups, alkoxy groups, halogen atoms, nitro groups, cyano groups, and substituted amino groups described above.

The substitution numbers j1 and j2 of the substituents R ^3a and R ^3b may be an integer of generally 0 to 4, preferably 0 to 2 (for example, 0 or 1). The substitution positions of the substituents R ^3a and R ^3b are not particularly limited. Preferred substituents R ^3a and R ^3b are C _1-6 alkyl groups (particularly methyl groups), and preferred substitution numbers j1 and j2 are 0 or 1 (eg, 0).

  The number of repetitions m and n of the oxyalkylene unit is 0 or an integer of 1 or more, and is usually an integer of about 1 to 10, preferably 1 to 7, and more preferably about 1 to 5 (for example, 1 to 4). It may be an integer of 2 or more (for example, about 2 to 4).

  Further, the fluorene-containing polyester resin further comprises the following formula (2)

(In the formula, R ^1C represents an alkylene group.)
It may have a diol component represented by: In the formula (2), examples of the alkylene group represented by R ^1C include linear or branched C _2-10 alkylene groups such as ethylene group, propylene group, trimethylene group and tetramethylene group. A chain or branched C _2-4 alkylene group (for example, ethylene group, tetramethylene group, etc.) is preferred.

  The ratio (molar ratio) between the diol represented by the formula (1) and the diol represented by the formula (2) is the former / the latter = 100/0 to 10/90 (for example, 100/0 to 30/70). A range of about 99/1 to 50/50, preferably 99/1 to 55/45, more preferably 98/2 to 60/40, especially 97/3 to 65/35 (eg 95 / 5 to 70/30).

  On the other hand, the dicarboxylic acid component may be an aliphatic dicarboxylic acid component, but is an alicyclic dicarboxylic acid component or an aromatic dicarboxylic acid component from the viewpoint of optical properties (for example, refractive index, birefringence, etc.). Is preferred.

Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids (cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, cycloheptane dicarboxylic acid, etc. _5-10 cycloalkane-dicarboxylic acid), cycloalkene dicarboxylic acids (C _5-10 cycloalkene-dicarboxylic acid such as tetrahydrophthalic acid), polycyclic alkane dicarboxylic acids (bornane dicarboxylic acid, norbornane dicarboxylic acid, etc.) And tricyclic C _7-10 alkane-dicarboxylic acid), polycyclic alkene dicarboxylic acids (di- or tricyclo C _7-10 alkene-dicarboxylic acid such as bornene dicarboxylic acid), and the like. Usually, the alicyclic dicarboxylic acid component is C _5-10 cycloalkane-dicarboxylic acid (particularly 1,4-cyclohexanedicarboxylic acid).

Examples of the aromatic dicarboxylic acid component include C _6-14 arene-dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and C _12-14 biphenyl-dicarboxylic acid such as biphenyl-4,4′-dicarboxylic acid. Etc. can be exemplified. Usually, the aromatic dicarboxylic acid component is a C _6-12 arene-dicarboxylic acid (particularly terephthalic acid).

The dicarboxylic acid component may be an acid anhydride, a lower C _1-4 alkyl ester such as dimethyl ester, or a derivative capable of forming an ester such as an acid halide corresponding to the dicarboxylic acid. In addition, the dicarboxylic acid component includes one or more substituents such as a hydrocarbon group [for example, an alkyl group (for example, a C _1-7 alkyl group such as a methyl group), a cycloalkyl group (for example, a cyclohexyl group, etc.). C _5-10 cycloalkyl group), aryl group (for example, C _6-10 aryl group such as phenyl group)], haloalkyl group, hydroxyl group, alkoxy group (for example, C _1-10 alkoxy group such as methoxy group) ), A haloalkoxy group, a carboxyl group, an alkoxycarbonyl group (eg, a C _1-10 alkoxycarbonyl group such as a methoxycarbonyl group), an acyl group (eg, a C _2-5 acyl group such as an acetyl group), an amino group, It may have a substituted amino group, halogen atom, nitro group, cyano group, etc. Depending appropriately selected.

Preferred fluorene-containing polyester resins include, for example, (i) in the formula (1), R ^1a and R ^1b are ethylene groups, m and n are 1, and R ^2a and R ^2b are alkyl groups (for example, , A C _1-6 alkyl group such as a methyl group) or an aryl group (for example, a C _6-10 aryl group such as a phenyl group), h1 and h2 are 0 to 2, and j1 and j2 are 0 A copolymer comprising a component and a diol component in which R ^1c is an ethylene group and a dicarboxylic acid component that is terephthalic acid in the formula (2) as a polymerization component, and represented by the following formula (3a) A copolymer having a unit and a unit represented by the following formula (4a), (ii) In the formula (1), R ^1a and R ^1b are ethylene groups, m and n are 1, and R ^2a And R ^2b is a An alkyl group (eg, a C _1-6 alkyl group such as a methyl group) or an aryl group (eg, a C _6-10 aryl group such as a phenyl group), h1 and h2 are 0 to 2, and j1 and j2 are A diol component that is 0, a diol component in which R ^1c is an ethylene group in the above formula (2), and a dicarboxylic acid component that is 1,4-cyclohexanedicarboxylic acid, and the like. . For example, as an example of the copolymer contained in (i), a copolymer having a unit represented by the following formula (3a) and a unit represented by the following formula (4a) As an example of the copolymer contained, a copolymer having a unit represented by the following formula (3b) and a unit represented by the following formula (4b) can be given.

  The ratio of the unit represented by the following formula (3a) and the unit represented by the following formula (4a) is the former / the latter (unit number ratio) = 50/50 to 100/0, preferably 60/40 to 95. / 5, more preferably about 65/35 to 90/10. The ratio of the unit represented by the following formula (3b) to the unit represented by the following formula (4b) is also the former / the latter (unit number ratio) = 50/50 to 100/0, preferably 60/40. It may be about ~ 95/5, more preferably about 65/35 to 90/10.

  The fluorene-containing polyester resin may be a commercially available product or a synthetic product synthesized by a method using (or applying) a conventional method. The fluorene-containing polyester resin can be obtained by reacting a corresponding diol component with a dicarboxylic acid component. For a method for producing such a polyester resin, for example, JP-A-2004-315676 can be referred to.

  The ratio (use ratio) of the dicarboxylic acid component and the diol component can be selected from the former / the latter (molar ratio) = about 5/1 to 0.1 / 1, and usually the former / the latter = 1.5 / 1. It may be about 0.5 / 1, preferably 1.2 / 1 to 0.7 / 1 (particularly 1.1 / 1 to 0.8 / 1). In addition, you may adjust the kind of terminal group of the fluorene containing polyester-type resin to produce | generate by adjusting the ratio (or ratio of the usage-amount) of a dicarboxylic acid component and a diol component. Specifically, an excessive amount of the diol component may be reacted with the dicarboxylic acid component to prepare a fluorene-containing polyester resin whose terminal group is a hydroxyl group. Moreover, the dicarboxylic acid component may be reacted in excess with respect to the diol acid component to prepare a fluorene-containing polyester resin in which the terminal group is a carboxyl group.

  The hydroxyl value of the fluorene-containing polyester resin may be about 2 to 100 mgKOH / g, preferably about 5 to 90 mgKOH / g, and more preferably about 10 to 80 mgKOH / g.

The weight average molecular weight of the fluorene-containing polyester resin is 1 × 10 ³ or more (for example, 1 × 10 ^{3 to} 5 × 10 ⁴ ), preferably 3 × 10 ^{3 to} 4.5 × 10 ⁴ , more preferably. It may be about 5 × 10 ³ to 4 × 10 ⁴ (for example, 1 × 10 ⁴ to 4 × 10 ⁴ ).

(Chain extender)
The chain extender is a compound containing a plurality of functional groups (or reactive groups) capable of reacting with the terminal group (carboxyl group or hydroxyl group) of the fluorene-containing polyester resin in one molecule. Specifically, the chain extender is a compound containing at least two functional groups selected from hydroxyl group, amino group, epoxy group, oxazoline group, carboxyl group and acid anhydride group in one molecule. is there. The plurality of functional groups may be the same or different, but are usually the same. The chain extender may be appropriately selected according to the desired molecular weight of the high molecular weight polyester resin based on reactivity and the like.

Examples of the hydroxyl group-containing compound include diols (for example, C _2-10 aliphatic diols such as ethylene glycol and propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol). About 1000 polyalkylene glycols, alicyclic diols, aromatic diols, etc.) polyols having 3 or more hydroxyl groups (for example, aliphatic C _3-10 such as glycerin, trimethylolethane, trimethylolpropane) Triols; tetraols such as pentaerythritol and erythritol; pentaols such as arabitol, ribitol, and xylitol) are preferably used. The chain extender which has a hydroxyl group can be used individually or in combination of 2 or more types. Of these chain extenders having a hydroxyl group, polyols (eg, aliphatic C _3-10 triols (eg, trimethylolpropane)) and the like are preferable.

Examples of the amino group-containing compound include polyamines (eg, chain polyamines {eg, aliphatic diamines (C _2-20 alkane diamines such as ethylene diamine, propylene diamine, tetramethylene diamine, hexamethylene diamine)), and alicyclic rings. Diamines such as aromatic diamines (such as bis (4-amino-3-methylcyclohexyl) methane) and aromatic diamines (such as phenylenediamine and metaxylylenediamine); polyalkylenepolyamines (or polyalkylenes) imines, such as diethylenetriamine, primary polyamines such as poly C _2-4 alkylene polyamine) such as triethylene tetramine, tetraethylene pentamine}, cyclic polyamines [e.g., cyclic secondary polyamines (e.g., piperazine , 1,4,8,11-tetraazacyclotetradecane, etc.), etc.]), and others. The chain extender which has an amino group can be used individually or in combination of 2 or more types. Of these chain extenders having amino groups, chain polyamines (for example, polyalkylene polyamines (for example, diethylenetriamine, triethylenetetramine, etc.)) and the like are preferable.

Examples of the epoxy group-containing compound include polyglycidyl ethers [for example, C _2-20 alkylene glycol polyglycidyl ethers such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether; di- or tri-C _2- Polyalkylene glycol polyglycidyl ethers such as _4- alkylene glycol diglycidyl ether (eg, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, etc.); aliphatic polyol polyglycidyl ethers (eg, glycerin) Triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl Ether, pentaerythritol tetraglycidyl C _3-12 aliphatic polyol polyglycidyl ethers such as ether, etc.), etc.]; polyglycidyl esters [for example, aromatic dicarboxylic acids (phthalic acid) or its hydrogenated product (tetrahydrophthalic acid, etc. ) And epichlorohydrin, etc.]; polyglycidylamines (for example, tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, diglycidylaniline, diglycidyltoluidine, etc.); epoxy resin (bisphenol A type epoxy resin, etc.) Etc. can be exemplified. The chain extender which has an epoxy group can be used individually or in combination of 2 or more types. Among these chain extenders having an epoxy group, aliphatic polyol polyglycidyl ethers (for example, C _3-12 aliphatic polyol polyglycidyl ether such as trimethylolpropane triglycidyl ether) and the like are preferable.

Examples of the oxazoline group-containing compound include bisoxazolines [eg, phenylenebis (2-oxazolines) such as 1,3-phenylenebis (2-oxazoline), 1,4-phenylenebis (2-oxazoline); -Bis (2-oxazoline); 2,2-bis (C _1- ) such as 2,2-bis (4-methyl-2-oxazoline), 2,2-bis (4,4-dimethyl-2-oxazoline) _6- alkyl-2-oxazolines); 2,2-bis (C _5-6 cycloalkyl-2-oxazolines) such as 2,2-bis (4-cyclohexyl-2-oxazoline); 2,2-bis ( Examples include 2,2-bis (C _6-10 aryl-2-oxazoline) s such as 4-phenyl-2-oxazoline). The chain extender which has an oxazoline group can be used individually or in combination of 2 or more types. Of these chain extenders having an oxazoline group, phenylenebis (2-oxazoline) s (such as 1,4-phenylenebis (2-oxazoline)) and the like are preferable.

Examples of the carboxyl group (or acid anhydride group) -containing compound include dicarboxylic acids (for example, saturated C _2-20 aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid; 1,4 -Cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (such as 2,6-naphthalenedicarboxylic acid)), having three or more carboxyl groups Carboxylic acids such as polycarboxylic acids (eg, trimellitic acid, pyromellitic acid, etc.) or acid anhydrides thereof (eg, trimellitic anhydride, pyromellitic anhydride, etc.) are preferably used. The chain extender which has a carboxyl group can be used individually or in combination of 2 or more types. Of these chain extenders having a carboxyl group, polycarboxylic acids (for example, pyromellitic acid (or pyromellitic anhydride)) are preferable.

If necessary, diols and polyols are monools (for example, C _1-10 aliphatic monools such as methanol and ethanol; alicyclic monools such as cyclohexanol; aromatics such as phenols) Monools etc.) may be used in combination. In addition, dicarboxylic acids and polycarboxylic acids are monocarboxylic acids (for example, saturated C _1-18 aliphatic monocarboxylic acids such as acetic acid and propionic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; and aromatics such as benzoic acid. Group monocarboxylic acids).

  Further, as described above, the chain extender may be a compound having a different functional group selected from the functional groups. Such chain extenders include, for example, hydroxycarboxylic acids (eg, tartaric acid, citric acid, lactic acid, gluconic acid, etc.); amino acids (eg, aliphatic amino acids, aromatic amino acids, sulfur-containing amino acids, oxyamino acids, etc.); Hydroxylamine (for example, alkanolamines such as ethanolamine) and the like are included.

  These chain extenders may be used alone or in combination of two or more. The chain extender can be appropriately selected according to the type (carboxyl group or hydroxyl group) of the end group of the fluorene-containing polyester resin. Specifically, when the proportion of terminal carboxyl groups of the fluorene-containing polyester resin is high, a compound having a hydroxyl group, an amino group, an epoxy group and / or an oxazoline group is used as a chain extender, the high molecular weight polyester system Resin can be manufactured effectively. On the other hand, when the terminal hydroxyl group ratio of the fluorene-containing polyester resin is high, the high molecular weight polyester resin can be effectively produced by using a compound having a carboxyl group (or an acid anhydride group) as the chain extender. . For example, when the hydroxyl value of the fluorene-containing polyester resin is, for example, about 1 to 25 mgKOH / g (preferably 5 to 15 mgKOH / g), the chain extender has a carboxyl group (or an acid anhydride group). A compound may be used.

  In the high molecular weight polyester resin of the present invention, the fluorene-containing polyester resin is bonded with the chain extender. The content of the chain extender is about 0.05 to 10% by weight, preferably about 0.1 to 7.5% by weight, more preferably about 0.2 to 5% by weight in the entire high molecular weight polyester resin. There may be.

  The weight average molecular weight of such a high molecular weight polyester resin can be selected from about 10,000 to 200,000, for example, 30,000 to 150,000, preferably 35,000 to 100,000, more preferably 36. , It may be about 5,000 to 95,000. The weight average molecular weight of the high molecular weight polyester resin is, for example, 45,000 to 100,000, preferably 50,000 to 90,000, more preferably 52,000 to 88,000, and particularly 55,000 to. It may be about 85,000.

  In the present invention, the high molecular weight can be effectively increased by binding the fluorene-containing polyester resin with a chain extender. Specifically, the weight average molecular weight of the high molecular weight polyester resin is 500 to 65,000, preferably 1,000 to 60,000, more preferably 3,000 to 55,000, as compared with the fluorene-containing polyester resin. (For example, 5,000 to 50,000), particularly 10,000 to 45,000 (for example, 20,000 to 43,000).

  In addition, the high molecular weight polyester resin may be in a form containing an additive as necessary. Examples of the additive include plasticizers, softeners, colorants, dispersants, mold release agents, stabilizers (oxidants such as hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants). Inhibitors, ultraviolet absorbers, heat stabilizers, etc.), antistatic agents, flame retardants, anti-blocking agents, crystal nucleus growth agents, fillers (particulate fillers such as silica and talc, glass fibers and carbon fibers) Examples thereof include fibrous fillers. These additives can be used alone or in combination of two or more. The ratio of the additive may be selected according to the type and is not particularly limited, but can be selected from a range of about 0.01 to 100 parts by weight with respect to 100 parts by weight of the fluorene-containing polyester resin. It may be about 1 to 50 parts by weight, preferably about 0.5 to 30 parts by weight.

[Method for producing high molecular weight polyester resin]
The high molecular weight polyester resin can be produced through a reaction step (or chain extension reaction) in which the fluorene-containing polyester resin and the chain extender are reacted. Specifically, when the fluorene-containing polyester resin and the chain extender are reacted, an end group (carboxyl group or hydroxyl group) of the fluorene-containing polyester resin and two or more functional groups of the chain extender ( Or a reactive group), and the resin units are bonded to each other through a chain extender to produce the high molecular weight polyester resin.

  The amount (or ratio) of the chain extender can be appropriately selected according to the type of chain extender to be used, the desired molecular weight of the resulting high molecular weight polyester resin, the use, and the like. For example, the fluorene-containing polyester system It can be selected from about 0.1 to 10 parts by weight (for example, 0.1 to 8 parts by weight) with respect to 100 parts by weight of the resin, 0.1 to 5 parts by weight, preferably 0.3 to 4.8 parts by weight, More preferably, it may be about 0.5 to 4.5 parts by weight, particularly about 0.7 to 4.2 parts by weight (for example, 1 to 4 parts by weight).

  The ratio of the functional group of the chain extender used (for example, hydroxyl group, amino group, epoxy group, oxazoline group, etc.) to the terminal carboxyl group of the fluorene-containing polyester resin is the former / the latter (equivalent ratio) = 5 / Although it can be selected from about 1 to 0.5 / 1, usually the former / the latter (equivalent ratio) = 4.5 / 1 to 0.8 / 1, preferably 4/1 to 0.9 / 1, more preferably It may be about 3.5 / 1 to 1/1. In addition, the ratio of the functional group (for example, carboxyl group or acid anhydride group) of the chain extender used to the terminal hydroxyl group of the fluorene-containing polyester resin is also the former / the latter (equivalent ratio) = 5/1. Although it can be selected from about 0.5 / 1, usually the former / the latter (equivalent ratio) = 4.5 / 1 to 0.8 / 1, preferably 4/1 to 0.9 / 1, more preferably 3. It may be about 5/1 to 1/1.

  In addition, you may perform a reaction process in presence of a solvent. For example, the fluorene-containing polyester resin, a chain extender, and a solvent (solvent that can dissolve (or mix) the fluorene-containing polyester resin and the chain extender) may be mixed (or kneaded) and reacted. For example, the fluorene-containing polyester resin may be dissolved in a solvent to prepare a resin solution, and a chain extender may be added to the resin solution and mixed (or kneaded or stirred) to be reacted. However, in order to suppress the cyclization reaction of the fluorene-containing polyester resin, it is necessary to adjust the concentration of the resin solution, in terms of cost and environment, the reaction step is performed in the absence of a solvent. preferable. For example, when the fluorene-containing polyester resin and the chain extender are melt-kneaded in the absence of a solvent and reacted to produce a high molecular weight polyester resin, productivity, operability, cost, environment, etc. This is advantageous.

  The chain extension reaction may be performed in the air or in an inert gas (nitrogen, helium, etc.) atmosphere. Moreover, the said reaction may be performed under a normal pressure, and can also be performed under pressure reduction or pressurization. Note that when a hydroxyl group-containing compound and / or an amino group-containing compound is used as the chain extender, the reaction may be performed under reduced pressure because it may act as a depolymerizer for the fluorene skeleton-containing polyester resin. It is preferable to carry out below. Furthermore, the said reaction can be performed under the temperature of about 150-300 degreeC, for example, Preferably it is 180-290 degreeC, More preferably, it is about 200-280 degreeC.

  The reaction time can be appropriately selected according to the desired molecular weight of the resin to be produced, reaction conditions, and the like, and may be, for example, 1 to 60 minutes, preferably 2 to 30 minutes, and more preferably about 3 to 20 minutes.

  In addition, when making the high molecular weight polyester resin contain the additive, it may be added at any stage of the production process. For example, it may be added in advance before the reaction step, or may be added after the reaction step. Moreover, you may add in the suitable step of the said reaction process.

  Even if the high molecular weight polyester resin of the present invention has a high molecular weight, it is less colored and has optical properties equivalent to those of the fluorene-containing polyester resin (fluorene-containing polyester resin not chain-extended).

In the high molecular weight polyester resin of the present invention, an increase in birefringence accompanying deformation during molding is greatly suppressed. Specifically, in a molded product obtained by molding (or primary molding) the high molecular weight polyester resin, an increase in birefringence accompanying deformation during molding is greatly suppressed, and further, the molded product is further molded (or Even in the case of secondary molding), an increase in birefringence accompanying deformation is greatly suppressed. For example, in the high molecular weight polyester resin film, the amount of increase in birefringence (Δn / λ) with respect to the draw ratio (λ) is 5 × 10 ⁻⁴ / times or less (for example, 0 to 5 × 10 ⁻⁴ / times). , Preferably 1.5 × 10 ^{−6 to} 4.8 × 10 ⁻⁴ / times, more preferably 2 × 10 ^{−6 to} 4.7 × 10 ⁻⁴ / times, particularly 2.5 × 10 ⁻⁶ to 4 It is about 5 × 10 ⁻⁴ / times (for example, 3 × 10 ^{−6 to} 4.5 × 10 ⁻⁴ / times).

  The high molecular weight polyester resin is also excellent in mechanical properties. For example, the tensile strength measured using the multipurpose test piece A type according to JIS K 7113 is 3 to 15%, preferably 3.5 to 14 compared with the fluorene-containing polyester resin not chain-extended. %, More preferably about 4 to 13% (for example, 4.5 to 10%). Further, the elongation at the yield point measured using the multipurpose test piece A type according to JIS K 7113 is 3 to 150%, preferably 4 compared with the fluorene-containing polyester resin not chain-extended. It is improved by about -130%, more preferably 5-100% (for example, 7-30%).

  Furthermore, although the high molecular weight polyester resin has a high molecular weight, it has excellent moldability and is useful as a molding material. The method for molding the resin may be a conventional molding method, for example, extrusion molding, injection molding, blow molding, calendar molding, press molding, vacuum molding, or the like. The shape of the molded body produced in this way is not particularly limited, and is a 0-dimensional shape (granular, pellet-like, etc.), a one-dimensional shape (strand-like, rod-like, etc.) Or a three-dimensional shape (such as a tube or a block).

  In addition, unless the characteristic of this invention is impaired, the said high molecular weight polyester-type resin may form a molded object with the form of an alloy combining with other resin. The other resin may be a thermosetting resin (for example, phenol resin, furan resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, urethane resin, silicone resin, polyimide resin, etc.). Usually, thermoplastic resins (for example, olefin resins, styrene resins, vinyl chloride resins, vinyl acetate resins, polyvinyl alcohol resins, thermoplastic acrylic resins, polyacetal resins, polycarbonate resins, fluorine resins, Polyamide resins, polysulfone resins (polysulfone resins, polyethersulfone resins, etc.), polyphenylene ether resins, polyphenylene sulfide resins, etc.) are often used. Other resins may be used alone or in combination of two or more. The ratio of the other resin may be selected according to the type, and is, for example, 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, and more preferably 100 to 15 parts by weight of the high molecular weight polyester resin. Preferably, it may be about 0.1 to 10 parts by weight.

  The high molecular weight polyester resin (or molded article thereof) of the present invention is useful for optical applications because it is excellent in transparency and the increase in birefringence accompanying deformation (or molding) is extremely suppressed. Specifically, optical members such as CD (compact disc) [CD-ROM (compact disc-read-only memory)], CD-ROM pickup lens, Fresnel lens, fθ lens for laser printers Optical lenses such as camera lenses and rear projection television projection lenses; polarizing films and polarizing elements and polarizing plate protective films, retardation films, alignment films (alignment films), viewing angle expansion (compensation) films, diffusion films Plate (film), prism sheet, light guide plate, brightness enhancement film, near infrared absorption film, reflection film, antireflection (AR) film, antireflection (LR) film, antiglare (AG) film, transparent conductive (ITO) film , Anisotropic conductive (ACF) film, electric It can be used for applications such as magnetic wave shielding (EMI) film, electrode substrate film, color filter substrate film, barrier film, color filter layer, black matrix layer, optical film such as an adhesive layer or a release layer between optical films.

  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 symbol of each evaluation method and component in an Example, a reference example, and a comparative example is as follows.

[Evaluation methods]
(Average molecular weight)
The number average molecular weight and the weight average molecular weight were measured using gel permeation chromatography (GPC) [manufactured by JASCO, “Intelligent HPLC”]. The measurement was performed using tetrahydrofuran as an eluent under conditions of a column temperature of 40 ° C. and a flow rate of 1.0 ml / min, and a measured value in terms of polystyrene was obtained. As for the column, two “KF-804L” manufactured by Shodex were connected in series.

(Birefringence)
Birefringence was evaluated using a polarizing microscope (manufactured by NIKON, “Senarum Compensator”).

(Tensile strength)
The tensile strength was measured using a multipurpose test piece A type according to JIS K 7113.

(Elongation at yield point)
The elongation at the yield point was measured using a multi-purpose specimen A type according to JIS K7113.

[Component abbreviations]
FBP1: fluorene-containing polyester resin [manufactured by Osaka Gas Chemical Co., Ltd., a block copolymer having a unit represented by the above formula (3a) and a unit represented by the following formula (4a) (in the formula (3a) , H1 and h2 are 0, a copolymer represented by the unit represented by formula (3a) / unit represented by formula (4a) (unit number ratio) = 70/30, weight average molecular weight: 34,685 ), Tensile strength 76.9 MPa, elongation at yield point 12.6%]
FBP2: fluorene-containing polyester resin [manufactured by Osaka Gas Chemical Co., Ltd., a block copolymer having a unit represented by the above formula (3b) and a unit represented by the following formula (4b) (in the formula (3b) , H1 and h2 are 0, a unit represented by formula (3b) / unit represented by formula (4b) (unit number ratio) = 80/20, weight average molecular weight: 33,850 ), Tensile strength 66.6 MPa, elongation at yield point 11.7%]
PDA: pyromellitic dianhydride (Sigma Aldrich)
TGE: Trimethylolpropane triglycidyl ether (manufactured by Sigma-Aldrich)
DMDI: dicyclohexylmethane 4,4′-diisocyanate (manufactured by Sigma-Aldrich).

Example 1
100 parts by weight of a fluorene-containing polyester resin (FBP1) and 2.4 parts by weight of pyromellitic dianhydride (PDA) are dry-blended, and a twin-screw kneading extruder (manufactured by Technobel, “KZW15-30MG” L / D = 30: Cylinder temperature: 280 ° C.) and kneaded and extruded. The extruded strand was cooled in the air and cut with a pelletizer to obtain high molecular weight polyester resin pellets. The number average molecular weight, weight average molecular weight, tensile strength, and elongation at yield point of the obtained pellets were measured. The tensile strength was 81.7 MPa and the elongation at the yield point was 17.4%.

(Example 2)
Except for using FBP2 instead of FBP1, pellets were obtained in the same manner as in Example 1, and the number average molecular weight, weight average molecular weight, tensile strength, and elongation at yield point of the obtained pellets were measured. The tensile strength was 74.6 MPa, and the elongation at the yield point was 12.4%.

(Examples 3 to 4)
A pellet was obtained in the same manner as in Example 1 except that 3.3 parts by weight of trimethylolpropane triglycidyl ether (TGE) was used instead of 2.4 parts by weight of pyromellitic dianhydride (PDA). The number average molecular weight and the weight average molecular weight were measured. In Example 3, FBP1 was used as the fluorene-containing polyester resin, and in Example 4, FBP2 was used.

(Reference Examples 1-2)
A pellet was obtained in the same manner as in Example 1 except that 2.9 parts by weight of dicyclohexylmethane 4,4′-diisocyanate (DMDI) was used instead of 2.4 parts by weight of pyromellitic dianhydride (PDA). The number average molecular weight, weight average molecular weight, tensile strength, and elongation at yield point of the pellet were measured. In Reference Example 1, FBP1 was used as the fluorene-containing polyester resin, and in Reference Example 2, FBP2 was used. In Reference Example 1, the tensile strength was 84.2 MPa, and the elongation at the yield point was 13.3%. In Reference Example 2, the tensile strength was 72.3 MPa, and the elongation at the yield point was 15.4%. The results of Examples 1 to 4 and Reference Examples 1 to 2 are shown in Table 1.

  As is clear from Table 1, the high-molecular-weight polyester resins obtained in the examples are not chain-extended FBP1 (weight average molecular weight: 34,685, Mw / Mn = 2.5), FBP2 (weight average molecular weight). : 33,850, Mw / Mn = 3.5), the molecular weight was increased.

(Examples 5-6)
In Examples 5 to 6, the pellets obtained in Examples 1 and 2 were dried at 95 ° C. for 5 hours using a ventilating dryer, and then hot-pressed (“TDR100-500 × 3 type” manufactured by Toshin Co., Ltd.). The film was pressed at 220 ° C. and 20 MPa to prepare a film having a thickness of about 0.2 mm. The obtained film was stretched at the stretch ratio shown in Table 2 on the hot press (160 ° C.), and then the birefringence of the film (stretched film) was measured.

(Comparative Examples 1-2)
A film was prepared in the same manner as in Example 5 except that FBP1 and FBP2 that were not chain-extended were used instead of using the pellets obtained in Examples 1 and 2, and the birefringence of the obtained film was measured.

(Reference Examples 3-4)
Instead of using the pellets obtained in Examples 1 and 2, a film was prepared in the same manner as in Example 5 except that the pellets obtained in Reference Examples 1 and 2 were used, and the birefringence of the obtained films was measured. . Table 2 shows the results of Examples 5-6, Comparative Examples 1-2, and Reference Examples 3-4.

  As is clear from Table 2, in Examples 5 to 6, although the chain extender was contained, almost no increase in birefringence was observed, and the birefringence was low. Moreover, even if it deform | transformed at the time of shaping | molding, the raise of birefringence was suppressed.

Claims (7)

  A high molecular weight polyester resin in which a fluorene-containing polyester resin containing a 9,9-bisarylfluorene skeleton is bonded with a chain extender, wherein the chain extender is a hydroxyl group, an amino group, an epoxy group, or an oxazoline A high molecular weight polyester resin which is a compound containing at least two functional groups selected from a group, a carboxyl group and an acid anhydride group in one molecule. The fluorene-containing polyester resin has at least the following formula (1)

(In the formula, Z ¹ and Z ² are the same or different and each represents an aromatic hydrocarbon group. R ^1a and R ^1b represent the same or different alkylene group, and R ^2a and R ^2b represent the same or different hydrocarbon. Group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group or substituted amino group, R ^3a and R ^3b are the same or different and carbonized A hydrogen group, an alkoxy group, a halogen atom, a nitro group, a cyano group or a substituted amino group, wherein m and n are the same or different and are 0 or an integer of 1 or more, and h1 and h2 are the same or different and represent 0-4. An integer, j1 and j2 are the same or different and are integers of 0 to 4)
The high molecular weight polyester resin according to claim 1, which is a polyester resin having a diol component represented by formula (I) and a dicarboxylic acid component as polymerization components.   The high molecular weight polyester resin according to claim 1 or 2, having a weight average molecular weight of 35,000 to 400,000.   The hydroxyl value of the fluorene-containing polyester resin is 2 to 100 mgKOH / g, and the chain extender is a compound containing at least two functional groups selected from a carboxyl group and an acid anhydride group in one molecule. The high molecular weight polyester resin according to claim 1, having a weight average molecular weight of 50,000 to 400,000.   The method for producing a high molecular weight polyester resin according to any one of claims 1 to 4, further comprising a reaction step of reacting a fluorene-containing polyester resin containing at least a 9,9-bisarylfluorene skeleton with a chain extender.   The production method according to claim 5, wherein the ratio of the chain extender is 0.1 to 10 parts by weight with respect to 100 parts by weight of the fluorene-containing polyester resin.   The production method according to claim 5 or 6, wherein the fluorene-containing polyester resin and the chain extender are melt-kneaded and reacted in the absence of a solvent.