JP6892648B2 - Polyester resin, its manufacturing method, and its uses - Google Patents

Description

The present invention relates to a polyester resin containing at least a biomass-derived flange carboxylic acid as a dicarboxylic acid component, a method for producing the same, and a molded product of the polyester resin.

In order to aim for a sustainable resource-recycling society from the viewpoint of carbon neutrality, a polyester resin has been proposed in which the raw material is replaced with a raw material derived from biomass, which is a renewable resource, from petroleum, which is a non-renewable resource.

Japanese Patent Application Laid-Open No. 2011-520005 (Patent Document 1) describes a dicarboxylic acid (2,5-furandylic acid) obtained from an aliphatic dicarboxylic acid, a polyfunctional aromatic acid and a diol, and the aromatic acid is derived from a renewable resource. A fat-aromatic type biodegradable polyester (carboxylic acid and derivatives thereof) is described, and in Examples, dimethyl 2,5-furandicarboxylic acid, sebacic acid, and 1,4-butanediol are esterified. A copolymerized polyester is prepared for the reaction.

Japanese Patent Application Laid-Open No. 2016-102173 (Patent Document 2) describes units produced by the reaction of 2,5-furandicarboxylic acid with alkanes or cycloalkanediols (cyclohexanedimethanol, etc.) and 2,5-furandicarboxylic acids. A polyester resin containing, as a repeating unit, a unit produced by a reaction with a polyoxyalkylene glycol having a number average molecular weight of 200 to 6000 (polytetramethylene glycol or the like) is described.

Japanese Patent Application Laid-Open No. 2015-160871 (Patent Document 3) describes a polyester composition having a unit produced by the reaction of 2,5-furandicarboxylic acid and an alkylene glycol having 2 to 6 carbon atoms as a main constituent unit. , 2,5-Flange carboxylic acid contains a unit produced by the reaction of oxyalkylene glycol having 10 or less carbon atoms in a proportion of 3.5 mol% or less, and also contains a predetermined phosphorus compound, an element such as antimony, and is predetermined. Polyester compositions having a carboxyl-terminal group concentration of are described.

However, all of these polyesters have a low glass transition temperature and cannot improve heat resistance and mechanical strength.

In Japanese Patent Application Laid-Open No. 2002-512315 (Patent Document 4) and Japanese Patent Application Laid-Open No. 2002-512279 (Patent Document 5), polyester is a terephthaloyl moiety; in some cases, one or more other aromatic carboxylic acid moieties; ethylene. A fiber comprising a glycol moiety; an isosorbide moiety; and optionally one or more other diol moieties, wherein the polyester exhibits a predetermined intrinsic viscosity, is described as one or more other diol moieties. , 9-Bis [4- (2-hydroxyethoxy) -phenyl] fluorene is exemplified, and 2,5-furandicarboxylic acid is exemplified as one or more aromatic diic acid moieties. In the examples, dimethyl terephthalate is exemplified. , Isosorbide and ethylene glycol are transesterified to produce polyester.

However, in order to increase the glass transition temperature of the polyesters described in this document, it is necessary to copolymerize isosorbide with terephthalic acid. Moreover, in Patent Document 4, in order to increase the molecular weight, it is necessary to contain a large amount of ethylene glycol units in the polymer at a ratio of 33 to 49.9 mol% (mol% of the entire polymer).

Japanese Patent Application Laid-Open No. 2011-520005 (Claim 1, Example) JP-A-2016-102173 (Claims, Examples) JP-A-2015-160871 (Claims) JP-A-2002-512315 (Claims 1, 4, 6, [0009] [0022], Examples) JP-A-2002-512279 (Claims 1, 9, 10, [0006] [0019], Examples)

Therefore, an object of the present invention is to provide a polyester resin having excellent mechanical properties, thermal properties and optical properties, a method for producing the same, and a molded product thereof by utilizing renewable resources.

Another object of the present invention is to provide a polyester resin which is amorphous even if it contains an aromatic unit and has high solubility in an organic solvent, a method for producing the same, and a molded product thereof.

As a result of diligent studies to solve the above problems, the present inventors have conducted a dicarboxylic acid component containing a 2,5-furandicarboxylic acid component as a renewable resource, and a diol component having a 9,9-bisarylfluorene skeleton. It was found that by esterification with a diol component containing, a polyester resin having excellent mechanical properties, thermal properties and optical properties (aromatic polyester resin which may belong to engineering plastics or super engineering plastics) is produced. The invention was completed.

That is, the polyester resin of the present invention is a polyester resin having a repeating unit of a diol unit and a dicarboxylic acid unit, wherein the diol unit contains a diol unit having at least a 9,9-bisarylfluorene skeleton and is a dicarboxylic acid. The unit comprises at least 2,5-furandicarboxylic acid units.

The diol unit may contain the diol unit represented by the following formula (1) in a proportion of about 10 to 100 mol% (for example, 25 to 100 mol%).

(In the formula, rings Z ¹ , Z ² , Ar ¹ and Ar ² indicate the same or different arene rings (or monocyclic arene rings or polycyclic arene rings), respectively, and R ^{1a and R 1b} are the same or different, respectively. Different alkylene groups, m1 and m2 are the same or different integers of 0 or 1 or more, R ^2a , R ^2b , R ^3a and R ^3b are the same or different substituents, respectively, n1, n2, k1 and k2 are the same or different, respectively. Same or different, indicating an integer of 0 or 1-4).

In the formula (1), rings Z ¹ and Z ² are the same or different, benzene ring or naphthalene ring; rings Ar ¹ and Ar ² are the same or different, benzene ring or naphthalene ring; R. ^1a and ^R1b are the same or different C _2-4 alkylene groups; m1 and m2 may be the same or different integers of 0 or 1-10.

Further, in the formula (1), the rings Z ¹ and Z ² are benzene rings or naphthalene rings; the rings Ar ¹ and Ar ² are benzene rings; and R ^2a and R ^2b are the same or different, C _{1-. 4} Alkyl group (eg, methyl group) or C _6-10 aryl group (eg, benzene ring), n1 and n2 are integers 0-2; k1 and k2 may be 0.

In such a polyester resin, the dicarboxylic acid unit may contain 2,5-furandicarboxylic acid units in a proportion of about 10 to 100 mol% (for example, 25 to 100 mol%).

The ratio of the diol unit having a 9,9-bisarylfluorene skeleton to the 2,5-furandicarboxylic acid unit may be about 10/90 to 90/10 (molar ratio), and may be about 20/80 to 80/80. It may be about 20 (molar ratio).

The present invention also includes a method for producing a polyester resin by reacting a diol component with a dicarboxylic acid component. In this method, the diol component contains a diol component having at least a 9,9-bisarylfluorene skeleton, and the dicarboxylic acid component contains at least a 2,5-flangecarboxylic acid component. Further, the diol component having a 9,9-bisarylfluorene skeleton and the 2,5-furandicarboxylic acid component are mixed with the former / latter = 10/90 to 90/10 (molar ratio) (for example, 20/80 to 80/). It may be used at a ratio of 20 (molar ratio)).

Furthermore, the present invention also includes a molded product made of the polyester resin.

In the present specification and the scope of patent claims, the "unit" means a residue excluding the hydrogen atom and the hydroxyl group desorbed by esterification, and the diol unit is the hydroxyl group-OH of the diol to hydrogen. The residue in which the atom -H is eliminated means the residue in which the hydroxyl group-OH is eliminated from the carboxyl group-COOH of the dicarboxylic acid. Further, the "component" of the dicarboxylic acid component and the diol component is used in the sense of including a reactive derivative (or an ester-forming derivative).

In the present invention, since the diol having a 9,9-bisarylfluorene skeleton and the 2,5-furandicarboxylic acid component which is a renewable resource are esterified, the diol is excellent in mechanical properties, thermal properties and optical properties. A polyester resin can be obtained. Further, it is possible to obtain a polyester resin which is amorphous and has high solubility in an organic solvent, probably because a cardo structure can be formed even if it contains an aromatic unit.

FIG. 1 shows a powder X-ray diffraction spectrum of the polyester resin obtained in Example 1.

[Polyester resin]
The polyester resin is formed by repeating units of a diol unit containing a diol unit having at least a 9,9-bisarylfluorene skeleton and a dicarboxylic acid unit containing at least a 2,5-furandicarboxylic acid unit. In the following description, since the diol unit is derived from the diol component (A) and the dicarboxylic acid unit is derived from the dicarboxylic acid component (B), the dicarboxylic acid unit is synonymous with the dicarboxylic acid component except for the esterification reaction. In some cases, the diol unit is used synonymously with the diol component.

[Diol unit (or component)]
The diol unit (or component) may contain at least a diol unit (or component) having a 9,9-bisarylfluorene skeleton, and such a diol unit can be represented by, for example, the following formula (1). The diol component corresponding to this diol unit can be represented by the following formula (1a).

(In the formula, rings Z ¹ , Z ² , Ar ¹ and Ar ² indicate the same or different arene rings, ^{respectively, R 1a} and R ^{1 b} are the same or different, respectively, and alkylene groups, m 1 and m 2 are the same or different, respectively. Integers greater than or equal to 0 or 1, R ^2a , R ^2b , R ^3a and R ^3b represent the same or different substituents, respectively, and n1, n2, k1 and k2 represent the same or different integers 0 or 1 to 4, respectively). ..

In the unit represented by the above formula (1), the ^{arene rings represented by the rings Z 1} and Z ² include a monocyclic or polycyclic arene ring, and the polycyclic arene ring includes many fused compounds. Includes cyclic arene rings and ring-assembled arene rings.

Examples of the monocyclic arene ring include a benzene ring, and examples of the fused polycyclic arene ring include a fused dicyclic arene ring (for example, a fused dicyclic C _10-16 arene ring such as naphthalene). , Condensed tricyclic arene ring (for example, fused tricyclic C _12-16 arene ring such as anthracene and phenanthrene) and the like fused two to four ring type C _10-20 arene ring. The preferred fused polycyclic aromatic hydrocarbon ring may be a condensed two- or tricyclic C _10-16 allene ring, such as a naphthalene ring, an anthracene ring, in particular a naphthalene ring.

Examples of the ring-assembled aromatic hydrocarbon ring (ring-assembled arene ring) include bi-C such as a bi-lane ring, for example, a biphenyl ring, a binaphthyl ring, and a phenylnaphthalene ring (1-phenylnaphthalene ring, 2-phenylnaphthalene ring, etc.). _{Examples thereof include a 6-12} arene ring, a tellarene ring, for example, a tell C _6-12 arene ring such as a terphenylene ring. The preferred ring-assembled aromatic hydrocarbon ring may be a ring-assembled C _12-18 arene ring, such as a bi-C _6-10 arene ring, particularly a biphenyl ring.

Preferred rings Z ¹ and Z ² include a benzene ring and a polycyclic C _10-20 arene ring (for example, a C _10-14 arene ring, particularly a naphthalene ring and a biphenyl ring). Rings Z ¹ and Z ² are often the same or different and are benzene rings or naphthalene rings. The two rings Z ¹ and Z ² may be the same or different rings, and usually may be the same ring.

The ^{alkylene group represented by R 1a} and R ^1b may be a linear or branched alkylene group, and examples of the linear alkylene group include an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group. _{Examples thereof include C 2-6} alkylene groups such as groups, preferably C _2-4 alkylene groups, more preferably C _2-3 alkylene groups, and particularly ethylene groups. _{Examples of the branched chain alkylene group include a C 3-6} alkylene group such as a propylene group, a 1,2-butandyl group and a 1,3-butanjiyl group, preferably a C _3-4 alkylene group, particularly a propylene group. .. Preferred alkylene groups may be linear or branched C _2-6 alkylene groups, for example linear or branched C _2-4 alkylene groups.

The groups R ^1a and R ^1b may be composed of the same or different types of alkylene groups (having different carbon numbers or structures), and may usually be the same.

The number of repeating units m1 and m2 of the groups OR ^1a and OR ^1b is an integer of 0 or 1 to 10, for example, about 1 to 10 (for example, 1 to 7), preferably 1 to 5 (for example, 1 to 4). More preferably, it may be 1 to 3 (for example, 1 to 2), particularly 1. In addition, m1 and m2 may be the same or different.

The average value of the sum of m1 and m2 (m1 + m2) can be selected from the range of 0 to 20 (for example, 1 to 20), and is usually 2 to 15 (for example, 2 to 13), preferably 2 to 12. (For example, 2 to 10), more preferably 2 to 8 (for example, 2 to 6), particularly about 2 to 5, 2 to 4 (for example, 2 to 3), especially about 2. May be good. If the above m1 and m2 are too large, there is a risk that both heat resistance and high refractive index cannot be achieved at the same time.

When m1 and m2 are 2 or more, the ^{alkylene groups represented by the groups R 1a} and R ^1b are composed of the same or different types of alkylene groups (types having different carbon numbers or structures) in each repeating unit. It may be, and usually, it may be the same.

In the formula (1), the groups [-(OR ^1a ) _m1- ] and [-(OR ^1b ) _m2- ] can be replaced with appropriate positions of rings Z ¹ and Z ^{2 , for example, rings Z 1} and Z. ^{When 2} is a benzene ring, it may be at any of the 2nd to 4th positions, and may be at the 3rd or 4th position. Further, when the rings Z ¹ and Z ² are naphthalene rings, they are often at the 5th to 8th positions of the naphthyl group, and depending on the positional relationship with the fluorene ring, the 1,5-position, the 2,5-position, It may be replaced by a relationship such as 1,6-position, 2,6-position, and for example, a positional relationship such as 1,5-position, 2,6-position (particularly, a positional relationship of 2,6-position). ) In many cases. Further, in the ring-aggregated arene rings Z ¹ and Z ² , the substitution position is not particularly limited, and for example, it may be substituted with an arene ring bonded to the 9-position of fluorene or an arene ring adjacent to this arene ring. .. For example, when the rings Z ¹ and Z ² are biphenyl rings, the 3- or 4-position of the biphenyl ring is often bonded to the 9-position of fluorene, for example, the 3,5-position, It may be replaced with replacement positions such as 3,6-position, 3,3'-position, 3,4'-position, 4,2-position, 4,3'-position, and 4,4'-position. , Preferably 3,5-, 3,6-, 3,4'-, 4,2-, 4,4'-, and more preferably 3,6-, 4,2-. It may be replaced at the replacement position.

The substituents R ^2a and R ^2b may be any substituent which is inactive in the reaction with the dicarboxylic acid component described later, and may be a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or an alkyl group (methyl). _{Linear or branched C 1-10} alkyl groups such as groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, s-butyl groups, t-butyl groups, preferably linear or branched C _{1 -6} alkyl groups, more preferably linear or branched C _1-4 alkyl groups), cycloalkyl groups (such as C _5-10 cycloalkyl groups such as cyclopentyl and cyclohexyl groups), aryl groups [ phenyl group, alkylphenyl group (methylphenyl (tolyl) group, dimethylphenyl (xylyl) group), C _6, such as a biphenyl group, C _6-12 aryl group such as a naphthyl group, an aralkyl group (benzyl group, phenethyl group _-10 and aryl _{-C 1-4} alkyl group), an alkoxy group (e.g., methoxy group, an ethoxy group, a propoxy group, n- butoxy group, isobutoxy group, linear or branched _{C 1} such as t- butoxy _-10 alkoxy groups, cycloalkoxy groups (eg, C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryloxy groups (eg, C _6-10 aryloxy groups such as phenoxy groups), Aralkyloxy group (eg, C _6-10aryl- C _1-4 alkyloxy group such as benzyloxy group), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, n-butylthio group, t-butylthio group) _{C 1-10} alkylthio groups such as C 1-10 alkylthio groups, cycloalkylthio groups (eg, C _5-10 cycloalkylthio groups such as cyclohexylthio groups), arylthio groups (eg, C _6-10 arylthio groups such as thiophenoxy groups, etc.) ), Aralkylthio group (for example, C _6-10aryl- C _1-4 alkylthio group such as benzylthio group), carboxyl group, alkoxycarbonyl group (methoxycarbonyl group, C _1-6 alkyl-carbonyl such as ethoxycarbonyl group) Groups, etc.), acyl groups (eg, C _1-6 acyl groups such as acetyl groups), nitro groups, cyano groups, dialkylamino groups (eg, diC _1-4 alkylamino groups such as dimethylamino groups), Dialkylcarbonylamino group (eg, diC _{1- such as diacetylamino group (4} Alkyl-carbonylamino group, etc.) can be exemplified.

Among these groups R ^2a and R ^2b , typical groups R ^2a and R ^2b include halogen atoms, alkyl groups, aryl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, substituted amino groups and the like. Be done. Preferred groups R ^2a and R ^2b include alkyl groups (linear or branched C _1-6 alkyl groups such as methyl groups), aryl groups (C _6-10 aryl groups such as phenyl groups), and alkoxy groups. In particular, a C _1-4 alkyl group (for example, a methyl group) can be exemplified, such as (a linear or branched C _{1-4 alkoxy group such as a methoxy group).} When the groups R ^2a and R ^2b are aryl groups, the groups R ^2a and R ^2b may form the ring-aggregated arene ring together with the rings Z ¹ and Z ^{2, respectively.} The types of groups R ^2a and R ^2b may be the same or different in the same or different ^{rings Z 1} and Z ^2.

Substituents which n1 and n2 are, depending on the type of ring ^{Z 1} and ^{Z 2,} 0 or an integer of 1 to 4, for example, 0-3 (e.g., 0-2), preferably 0 or 1 (e.g., 0 ) May be. In particular, if n1 and n2 is 1 or 2, a benzene ring ring ^{Z 1} and ^{Z 2, R 2a} and ^{R 2b} is may be a methyl group, when n1 and n2 are 1, ring ^{Z 1} and Z ² may be a naphthalene ring or a biphenyl ring, and R ^2a and R ^2b may be a methyl group. The substitution positions of the groups R ^2a and R ^2b are not particularly limited.

Examples of the arene ring represented by the rings Ar ¹ and Ar ² include a monocyclic arene ring (benzene ring and the like), a condensed polycyclic arene ring (C _10-16 arene ring such as a naphthalene ring, and the like) and the like. Preferred rings Ar ¹ and Ar ² are a benzene ring or a naphthalene ring (particularly a benzene ring).

A compound in which ring Ar ¹ is a benzene ring and ring Ar ² is a naphthalene ring may form a benzo [a] fluorene compound, a benzo [b] fluorene compound, or a benzo [c] fluorene compound.

The groups R ^3a and R ^3b include a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) and an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, t- _{C 1-6} alkyl group such as butyl group), aryl group (for example, C _6-10 aryl group such as phenyl group) and the like. Of these groups R ^3a and R ^3b , a C _1-4 alkyl group (particularly a methyl group) is preferable. The types of groups R ^3a and R ^3b may be the same or different, and when the number of substitutions k1 and k2 is 2 or more, ^{the types of groups R 3a} and R ^3b are on the benzene ring of the fluorene ring, respectively. May be the same or different.

The substitution numbers k1 and k2 can be selected from integers from 0 to 4, preferably 0 to 1, especially 0. The substitution numbers k1 and k2 may be the same or different from each other. The substitution positions of the groups R ^3a and R ^3b are not particularly limited, and are, for example, the 2-position to the 7-position (2-position, 7-position, 2- and 7-position, etc.) of the fluorene ring. May be good.

The following compounds can be exemplified as a typical diol component represented by the formula (1a).

(A) the ring Ar ¹ and Ar ² are represented by compounds formula is a benzene ring (1a), the ring Ar ¹ and Ar ² in the compound is a benzene ring, 9,9-bis (hydroxyaryl) fluorenes are included. Such representative compounds, in the formula (1a), (a1) a ring ^{Z 1} and ^{Z 2} is a benzene ring, m1 and m2 is 1 9,9-bis (hydroxyalkoxy phenyl) fluorene s; (a2) ring ^{Z 1} and ^{Z 2} is a naphthalene ring, m1 and m2 is 1 9,9-bis (hydroxyalkoxy naphthyl) fluorenes; in the compound of (a3) the (a1) (a2) , 9,9-bis (hydroxypolyalkoxyaryl) fluorenes having m1 and m2 of 2 or more are included.

(A1) 9,9-bis (hydroxyalkoxyphenyl) fluorenes As the 9,9-bis (hydroxyalkoxyphenyl) fluorenes, R ^2a and R ^2b are hydrocarbon groups, and n1 and n2 are 0 or 1. Certain compounds are preferably used.

Specifically, examples of the 9,9-bis (hydroxyalkoxyphenyl) fluorene include 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 9,9-bis (4- (2). -Hydroxypropoxy) phenyl) fluorene, 9,9-bis (4- (4-hydroxybutoxy) phenyl) fluorene, etc. 9,9-bis (hydroxy C _2-6 alkoxyphenyl) fluorene, etc .; 9,9-bis (4- (4-hydroxybutoxy) phenyl) fluorene, etc. 4- (2-Hydroxyethoxy) -2-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (3- (2-hydroxy) Ethoxy) -6-methylphenyl) fluorene, 9,9-bis (2- (2-hydroxyethoxy) -4-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-t 9,9-bis (C _1-6 alkylhydroxy C _2-6 alkoxyphenyl) fluorene such as −butylphenyl) fluorene; 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) ) Fluorene, 9,9-bis (4- (2-hydroxyethoxy) -2,6-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-di-t- 9,9-bis (di C _1-6 alkylhydroxy C _2-6 alkoxyphenyl) fluorene such as butylphenyl) fluorene; 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, etc. 9,9-Bis (C _5-10 cycloalkylhydroxy C _2-6 alkoxyphenyl) fluorene, etc .; 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, etc. 9, Examples thereof include 9-bis (C _6-10 arylhydroxy C _2-6 alkoxyphenyl) fluorene.

(A2) 9,9-bis (hydroxyalkoxynaphthyl) fluorenes The 9,9-bis (hydroxyalkoxynaphthyl) fluorenes include the ring Z ^{1 of the 9,9-bis (hydroxyalkoxyphenyl) fluorenes exemplified above.} And ^{9,9-bis (hydroxyalkoxynaphthyl) fluorenes in which Z 2} is a naphthalene ring {for example, 9,9-bis (2- (2-hydroxyethoxy) -6-naphthyl) fluorene, 9,9-bis [ 1- (2-Hydroxyethoxy) -5-naphthyl)] 9,9-bis (hydroxy C _2-6 alkoxynaphthyl) fluorene such as fluorene} and the like are included.

(A3) 9,9-Bis (Hydroxypolyalkoxyaryl) Fluolenes Further, the 9,9-bis (hydroxypolyalkoxyaryl) fluorenes include 9,9 corresponding to the compounds of (a1) and (a2). -Bis [Hydroxypoly C _2-6 alkoxy C _6-10aryl ] Fluorenes, such as 9,9-bis [4- (2- (2-hydroxyethoxy) ethoxy) phenyl] fluorene, 9,9-bis [Hydroxydi or tri-C _2-6 alkoxyphenyl] fluorene, etc .; 9,9-bis [4- (2- (2-hydroxyethoxy) ethoxy) -2-methylphenyl] fluorene, 9,9-bis [4- 9 such as (2- (2-hydroxyethoxy) ethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (2-hydroxyethoxy) ethoxy) -3,5-dimethylphenyl] fluorene, etc. , 9-bis [mono or di C _1-4 alkylhydroxydi or tri C _2-6 alkoxyphenyl] fluorene, etc .; 9,9-bis [4- (2- (2-hydroxyethoxy) ethoxy) -3-phenyl 9,9-bis [C _6-10 arylhydroxydi or tri-C _2-6 alkoxyphenyl] fluorene such as phenyl] fluorene; 9,9-bis [2- (2- (2-hydroxyethoxy) ethoxy)- _{9,9-bis [hydroxydi or tri C 2-6} alkoxynaphthyl] fluorene such as 6-naphthyl] fluorene 9,9-bis [hydroxydi or tri C _2-6 alkoxy C _6-10aryl ) fluorenes Etc. are included.

(B) Compound in which at least one of ^{ring Ar 1} and ring Ar ² is a naphthalene ring In a typical compound represented by the above formula (1a), (b1) one ring Ar ¹ is a benzene ring. Benzenefluorenes in which the other ring Ar ² is a naphthalene ring, (b2) dibenzofluorenes in which the rings Ar ¹ and Ar ² are naphthalene rings, and the like are included.

(B1) Benzofluorene Examples of benzofluorene include 11,11-bis (hydroxy C _2-6 alkoxy C _6-10 aryl) benzo [a] fluorene, 11,11-bis (hydroxy C _2-6). Alkoxy C _6-10 aryl) benzo [b] fluorenes, 7,7-bis (hydroxy C _2-6 alkoxy C _6-10 aryl) benzo [c] fluorenes are included.

Specifically, in the above formula (1a), ^{benzofluorenes in which rings Z 1} and Z ² are benzene rings and m1 and m2 are 1, for example, 11,11-bis (4- (2-hydroxyethoxy) ) Phenyl) benzo [a] fluorenes, 11,11-bis (4- (2-hydroxyethoxy) phenyl) benzo [b] fluorenes, 7,7-bis (4- (2-hydroxyethoxy) phenyl) benzo [C] ^{Fluorenes; benzofluorenes in which Z 1} and Z ² are naphthalene rings and m1 and m2 are 1, for example, 11,11-bis (2- (2-hydroxyethoxy) -6-naphthyl) benzo. [A] Fluorenes, 11,11-bis (2- (2-hydroxyethoxy) -6-naphthyl) benzo [b] Fluorenes, 7,7-bis (2- (2-hydroxyethoxy) -6-naphthyl) ) Benzo [c] fluorenes; benzofluorenes in which Z ¹ and Z ² are benzene rings and m1 and m2 are 2 or more, for example, 11,11-bis [2- (2- (2-hydroxyethoxy)). Ethoxy) -6-naphthyl] benzo [a] fluorenes, 11,11-bis [2- (2- (2-hydroxyethoxy) ethoxy) -6-naphthyl] benzo [b] fluorenes and the like are included.

(B2) Dibenzofluorenes Typical dibenzofluorenes include 12,12-bis (hydroxy (poly) alkoxyaryl) dibenzo [b, h] fluorenes.

Specifically, in the above formula (1) ^{, dibenzofluorenes in which Z 1} and Z ² are benzene rings and m1 and m2 are 1, for example, 12,12-bis (4- (2-hydroxyethoxy)). phenyl) dibenzo [b, h] fluorene compound; ^{Z 1} and ^{Z 2} is a naphthalene ring, dibenzo fluorenes m1 and m2 is 1, for example, 12,12-bis (2- (2-hydroxyethoxy) - 6-naphthyl) dibenzo [b, h] fluorenes; ^{dibenzofluorenes in which Z 1} and Z ² are benzene rings and m1 and m2 are 2 or more, for example, 12,12-bis (4- (2- (2- (2- (2- (2-) 2-Hydroxyethoxy) ethoxy) phenyl) dibenzo [b, h] fluorenes and the like are included.

The diol component represented by the formula (1a) can be used alone or in combination of two or more, and the diol unit represented by the formula (1) can be introduced into the polyester resin by using such a diol component.

The diol component (A) corresponding to the diol unit may contain at least a diol component (first diol component) (A1) having a 9,9-bisarylfluorene skeleton, and the diol component (A) is the first. The diol component (A1) of 1 may contain a second diol component (A2).

The second diol component (A2) may be at least one selected from an aliphatic diol component, an alicyclic diol component, and an aromatic diol component.

Examples of the aliphatic diol component include alkanediols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol. C _2-10 alcan diol, preferably C _2-6 alcan diol, more preferably C _2-4 alcan diol; polyalkane diol (eg, di or tri C _{2- such as diethylene glycol, dipropylene glycol, triethylene glycol). 4} Alcandiol and the like can be exemplified.

Examples of the alicyclic diol component include cycloalkanediol (for example, C _5-8 cycloalkanediol such as cyclohexanediol); di (hydroxyalkyl) cycloalkane (for example, di (hydroxy C _{1-) such as cyclohexanedimethanol). 4 alkyl) C 5-8,} etc. cycloalkane); isosorbide, 1,4: 3,6-dianhydro-mannitol, 1,4: 3,6-dianhydro Idi Torr, 1,4-anhydroerythromycin erythritol; norbornane diol , Bi or tricycloalkanediols such as adamantandiol; di, such as 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane. (Hydroxy C _1-10 alkyl) tetraoxaspiroalkane) and the like oxaspirocyclic diols can be exemplified.

The aromatic diol component includes, for example, dihydroxyarene (for example, hydroquinone, resorcinol, etc.); dihydroxyalkylarene (for example, 1,3-benzenedimethanol, 1,4-benzenedimethanol, etc., di (hydroxy C _1-4). Alkyl) C _6-10 arenes, etc.); Bisphenols (eg, bis (hydroxyphenyl) C, such as biphenol, bisphenol A _{, 1-10} alkane, bis (hydroxyphenyl) C, such as 1,1-bis (hydroxyphenyl) cyclohexane). _4-10 cycloalkanes, etc.); alkylene oxide adducts of bisphenols (biphenol, bisphenol A, F, S, etc.) (for example, C _2-3 alkylene oxide adducts such as ethylene oxide adducts, etc.) can be exemplified.

These second diol components (A2) can be used alone or in combination of two or more.

In order to improve the flexibility of the polyester resin and reduce double refraction, an aliphatic diol component such as C _2-6 alkanediol such as ethylene glycol is useful as the second diol component (A2). In order to reduce the double refraction without reducing the mechanical properties of the polyester resin, an alicyclic diol component, for example, C _5-8 cycloalkanediol such as cyclohexanediol, di (hydroxy) such as cyclohexanedimethanol, etc. C _1-4 alkyl) C _5-8 cycloalkane and the like are useful. In order to improve the heat resistance, mechanical properties, and refractive index of the polyester resin, aromatic diol components such as benzenedimethanol and alkylene oxide adducts of bisphenols are useful.

The ratio of the first diol component (A1) is 10 to 100 mol% (for example, 20 to 98 mol%), preferably 30 to 100 mol%, based on the total diol component ((A1) + (A2)). % (For example, 40 to 95 mol%), more preferably about 50 to 100 mol% (for example, 60 to 90 mol%). Further, in order to effectively improve the heat resistance, mechanical strength, and solubility in an organic solvent by the first diol component (A1), 70 to 100 mol% (for example, 75 to 100 mol%), particularly 90 to 90 to 100 mol%. It may be about 100 mol% (for example, 93 to 100 mol%). In the present invention, the unit corresponding to the first diol component (A1) can be introduced into the polyester resin in a relatively large proportion, and the unit corresponding to the first diol component (A1) can be introduced into the first diol component (A1) in the polyester resin (the entire unit forming the resin). The proportion of the corresponding unit is 5-50 mol% (eg 10-50 mol%), preferably 20-50 mol% (eg 25-45 mol%), more preferably 30-50 mol% (eg 30-50 mol%). It may be about 35 to 45 mol%) or about 45 to 50 mol% (for example, 46 to 50 mol%).

Although isosorbide may be used as the second diol component (A2), in the present invention, the heat resistance and mechanical properties of the polyester resin are improved even if the second diol component (A2) does not contain isosorbide. it can. Therefore, the amount of isosorbide unit introduced into the polyester resin (total amount of diol unit and dicarboxylic acid unit) may be 0 to 5 mol% (preferably 0 to 3 mol%), and isosorbide may not be introduced. Good.

[Dicarboxylic acid unit (or component)]
The dicarboxylic acid component (B) corresponding to the dicarboxylic acid unit may contain the 2,5-furandicarboxylic acid component (B1) corresponding to the 2,5-furandicarboxylic acid unit, and the 2,5-furandicarboxylic acid may be contained. The component (B1) may be a free 2,5-furandicarboxylic acid, a reactive derivative thereof, such as a lower alkyl ester (such as a C _1-4 alkyl ester such as a methyl ester or ethyl ester), an acid halide. It may be (such as acid chloride) or an acid anhydride. Industrially, as the 2,5-flangecarboxylic acid component, 2,5-flangecarboxylic acid and 2,5-flangecarboxylic acid _C1-2 alkyl ester are often used.

In addition, 2,5-frangylcarboxylic acid (FDCA) can be prepared from conventional methods such as cellulose, glucose and fructose via (5-hydroxymethyl) fructose, and can be used as a raw material for engineering plastics and super engineering plastics. It is one of the few biomass-derived aromatic dicarboxylic acids that can be produced.

The dicarboxylic acid component (B) corresponding to the dicarboxylic acid unit includes a 2,5-frangicarboxylic acid component (first dicarboxylic acid component) (B1), an aliphatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, and an aromatic acid. It may contain at least one second dicarboxylic acid component (B2) selected from the dicarboxylic acid component and the heterocyclic dicarboxylic acid component.

Examples of the aliphatic dicarboxylic acid component (B2) include alkandicarboxylic acids [eg, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, _{Linear or branched C 2-30} alkandicarboxylic acids (preferably C _6-12 alkandicarboxylic acids) such as dodecanedioic acid, plaricic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, maleic acid and the like. Examples thereof include arcendicarboxylic acids. The aliphatic dicarboxylic acid component may be used alone or in combination of two or more.

Examples of the alicyclic dicarboxylic acid component include cycloalcandicarboxylic acids (eg, C _5-10 cycloalkane-dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and hexahydrophthalic anhydride); cycloalkendicarboxylic acids (tetrahydroan anhydride). Phthalic acid, methylhexahydrohydride phthalic acid, methylcyclohexcentricarboxylic acid anhydride, etc.); bi or tricycloalkandicarboxylic acid or bridging ring cycloalkandicarboxylic acid (eg, hetic acid anhydride, hymicic acid anhydride, decalindicarboxylic acid, etc. Norbornandicarboxylic acid, adamantandicarboxylic acid, tricyclodecanedicarboxylic acid, etc.) and the like.

The aromatic dicarboxylic acid component is roughly classified into a monocyclic dicarboxylic acid component and a polycyclic dicarboxylic acid component, and examples of the monocyclic dicarboxylic acid component include terephthalic acid, isophthalic acid, and alkylisophthalic acid (for example, 4). _{-C 1-4} alkyl terephthalic acid such as methyl isophthalic acid _{), C 6-10} arenedicarboxylic acid such as phthalic anhydride and phthalic acid can be exemplified. Examples of the polycyclic dicarboxylic acid component include condensed polycyclic dicarboxylic acids [for example, naphthalenedicarboxylic acids (eg, 1,6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, etc.). _{), Condensed polycyclic C 10-16} allene-dicarboxylic acid such as anthracendicarboxylic acid, more preferably condensed polycyclic C _10-14 allene-dicarboxylic acid]; biphenyldicarboxylic acid (2,2'-biphenyldicarboxylic acid, _{C 6-10aryl} C _6-10 allene dicarboxylic acid such as 4,4'-biphenyldicarboxylic acid]; diarylalcandicarboxylic acid [eg, diphenylalcandicarboxylic acid (eg, 4,4'-diphenylmethanedicarboxylic acid, 2) _{Diphenyl C 1-4} alcan-dicarboxylic acid such as 2-bis (4-carboxyphenyl) propane _{) DiC} 6-10aryl C _1-6 alcan-dicarboxylic acid]; Diarylketone dicarboxylic acid [eg, diphenyl _{DiC 6-10} arylketone-dicarboxylic acid such as ketone dicarboxylic acid (4,4'-diphenylketonedicarboxylic acid, etc.)] and the like can be exemplified. The polycyclic dicarboxylic acid component is 9,9-bis (carboxyC _6-10 aryl) fluorene such as 9,9-bis (4-carboxyphenyl) fluorene, which is represented by the following formula (2a) or (2b). Fluorene carboxylic acid component is also included.

(In the formula, X ^1a , X ^1b and X ² represent divalent hydrocarbon groups that may have the same or different substituents, p represents an integer of 0-4, respectively, and R ^3a , R ^3b , k1 and k2 are the same as above).

In the formulas (2a) and (2b), the groups R ^3a and R ^3b are the same as described above, and the preferred substituents R ^3a and R ^3b are C such as a halogen atom, a cyano group or an alkyl group (particularly a methyl group). _In many cases, it is a 1-4 alkyl group). The preferred substitution numbers k1 and k2 are, for example, 0-2, preferably 0 or 1, especially 0.

In the formulas (2a) and (2b), the ^{hydrocarbon group represented by X 1a} , X ^1b and X ² includes a linear or branched alkylene group, for example, a methylene group, an ethylene group or a trimethylene group. _{Examples thereof include a linear or branched C 1-8} alkylene group such as a propylene group, a 1,2-butandyl group and a 2-methylpropane-1,3-diyl group. Preferred alkylene groups are linear or branched C _1-6 alkylene groups (eg, linear or branched such as methylene group, ethylene group, trimethylene group, propylene group, 2-methylpropane-1,3-diyl group). Chain C _1-4 alkylene group).

Examples of the substituent of the hydrocarbon group include an aryl group (phenyl group and the like), a cycloalkyl group (cyclohexyl group and the like) and the like.

Group X ^1a and X ^1b is linear or branched C _2-4 alkylene group (e.g., an ethylene group, a linear or branched C _2-3 alkylene group such as propylene) in many cases is , X ² are often linear or branched C _1-3 alkylene groups (for example, methylene group, ethylene group, etc.). The hydrocarbon groups X ^1a and X ^1b having a substituent may be, for example, a 1-phenylethylene group, a 1-phenylpropane-1,2-diyl group, or the like.

In the above formula (2b), the number of repetitions p of the methylene group may be, for example, an integer of about 0 to 3, preferably an integer of about 0 to 2, and more preferably 0 or 1.

Specific examples of the dicarboxylic acid component represented by the formula (2a) include compounds in which X ^1a and X ^1b are linear or branched C _2-6 alkylene groups, 9,9-bis (). _{Examples thereof include 9,9-bis (carboxyC 2-6} alkyl) fluorene such as 2-carboxyethyl) fluorene and 9,9-bis (2-carboxypropyl) fluorene.

Specific examples of the dicarboxylic acid component represented by the formula (2b) include a compound in which p = 0 and X ² is a linear or branched C _1-6 alkylene group, for example. 9- (1-carboxy-2-carboxyethyl) fluorene; ^{compounds in which p = 1 and X 2} is a linear or branched C _1-6 alkylene group, such as 9- (2,3-) _Examples thereof include 9- (dicarboxy C 2-8 alkyl) fluorene such as dicarboxypropyl) fluorene.

The fluorene carboxylic acid component represented by the formula (2a) or (2b) may be used alone or in combination of two or more. Of these fluorene carboxylic acid components, the dicarboxylic acid component represented by the formula (2a) is useful for imparting negative wavelength dispersion characteristics to the polyester resin. Examples of the dicarboxylic acid component [9,9-bis (carboxyalkyl) fluorenes] represented by the above formula (2a) include 9,9-bis (2-carboxyethyl) fluorene, 9,9-. _{9,9-bis (carboxy C 2-6} alkyl) fluorene such as bis (2-carboxypropyl) fluorene, preferably 9,9-bis (carboxy C _2-4 alkyl) fluorene, more preferably 9,9-bis. (Carboxy C _2-3 alkyl) Fluorene and the like can be exemplified.

The aromatic dicarboxylic acid component may be a heterocyclic dicarboxylic acid component, for example, 2,5-thiophenedicarboxylic acid.

In the aromatic dicarboxylic acid component, the monocyclic aromatic dicarboxylic acid component and the polycyclic aromatic dicarboxylic acid component may be used alone or in combination of two or more. Further, the monocyclic aromatic dicarboxylic acid component and the polycyclic aromatic dicarboxylic acid component may be combined.

These second dicarboxylic acid components (B2) can be used alone or in combination of two or more.

Of these second dicarboxylic acid components (B2), the aliphatic dicarboxylic acid component (for example, arcandicarboxylic acid) is useful for improving the flexibility of the polyester resin and reducing double refraction, and is a fat. A cyclic dicarboxylic acid component (eg, cycloalcandicarboxylic acid, bi or tricycloalkandicarboxylic acid, etc. is useful for reducing double refraction without reducing the mechanical properties of the polyester resin, and is an aromatic dicarboxylic acid. Ingredients (for example, monocyclic allenedicarboxylic acid components such as terephthalic acid and isophthalic acid, polycyclic allenedicarboxylic acid components such as naphthalenedicarboxylic acid, etc.) are used to improve the heat resistance, mechanical properties, and refractive index of polyester resins. In order to reduce the crystallinity of the polyester resin, it is preferable that the carboxyl group or its reactive derivative group is substituted at an asymmetric position in the molecule of the aromatic dicarboxylic acid component.

The dicarboxylic acid unit (or component) may contain at least 2,5-furandicarboxylic acid unit (or component), for example, 2,5-frangylcarboxylic acid unit (or first dicarboxylic acid component) (B1). ) Is 10 to 100 mol% (for example, 20 to 98 mol%), preferably 25 to 100 mol% (for example,) with respect to the entire dicarboxylic acid unit (or component) ((B1) + (B2)). , 30 to 95 mol%), more preferably about 40 to 100 mol% (for example, 50 to 90 mol%), and more preferably about 60 to 100 mol% (for example, 75 to 100 mol%). May be good. In the present invention, 2,5-furandicarboxylic acid units can be introduced into the polyester resin in a relatively large proportion, and the proportion of 2,5-furandicarboxylic acid units in the polyester resin is 5 to 50 mol% (eg, 10). It may be about 50 to 50 mol%), preferably about 20 to 50 mol% (for example, 25 to 45 mol%), and more preferably about 30 to 50 mol% (for example, 35 to 45 mol%).

Further, the diol component (A) and the dicarboxylic acid component (B) may contain a hydroxycarboxylic acid component and / or a lactone, if necessary. _{Examples of the hydroxycarboxylic acid component include hydroxy C 3-11} alcan-carboxylic acid components such as glycolic acid, lactic acid, butyric acid, and hydroxyvaleric acid, and hydroxy C _{3-10 cycloalcan} -carboxylic acid components such as 4-hydroxycyclohexanecarboxylic acid. Examples thereof include hydroxy C _6-10 arene-carboxylic acids such as hydroxybenzoic acid. _{Examples of the lactone include C 3-15} lactones such as γ-butyrolactone, γ-dimethylbutyrolactone, δ-valerolactone, and ε-caprolactone. These hydroxycarboxylic acid components and / or lactones can be used alone or in combination of two or more. The amount of these hydroxycarboxylic acid components and / or lactones used is about 0 to 25 mol% (for example, 3 to 10 mol%) with respect to the total of the diol component (A) and the dicarboxylic acid component (B). You may.

If necessary, the diol component (A) may be used in combination with a polyol such as an alkane polyol such as glycerin, trimethylolethane, trimethylolpropane, or pentaerythritol. Further, the dicarboxylic acid component (B) may be used in combination with a tricarboxylic acid anhydride, a methylcyclohexcentricarboxylic acid or an acid anhydride thereof, a polycarboxylic acid component such as pyromellitic acid, or the like. By using such a component in combination, a branched structure or the like may be introduced into the polyester resin.

The polyester resin of the present invention has a repeating unit containing a diol unit having a 9,9-bisarylfluorene skeleton and a 2,5-furandicarboxylic acid unit, for example, a repeating unit represented by the following formula (3). May be.

(In the formula, rings Z ¹ , Z ² , Ar ¹ and Ar ² , R ^1a and R ^1b , m 1 and m ² , R ^{2a, R 2b} , R ^3a and R ^3b , n1, n2, k1 and k2 are the same as described above. ).

The ratio (molar ratio) of the diol unit having a 9,9-bisarylfluorene skeleton to the 2,5-furandicarboxylic acid unit can be selected from a wide range of the former / latter = 5/95 to 95/5, for example. It may be about 10/90 to 90/10 (for example, 20/80 to 80/20), preferably about 30/70 to 70/30 (for example, 40/60 to 60/40). The ratio of the diol unit to the 2,5-furandicarboxylic acid unit may correspond to the molar ratio charged into the reaction system.

The weight average molecular weight of the polyester resin of the present invention can be selected from the range of about ^{0.1 × 10 4} to 50 × 10 ^{4 in terms of polystyrene when measured by gel permeation chromatography (GPC), for example, 1 × 10. It} may be about 4 to 30 × 10 ⁴ , preferably 1.5 × 10 ^{4 to} 20 × 10 ⁴ , and more preferably 2 × 10 ⁴ to 10 × 10 ^4. The number average molecular weight by the end group quantification method can be selected from the range of, for example, about ^{0.3 × 10 4} to 30 × 10 ^{4 , and is, for example, 0.5 × 10 4 to} 20 × 10 ⁴ , preferably 0. It may be about 7 × 10 ⁴ to 15 × 10 ⁴ , more preferably 0.8 × 10 ⁴ to 10 × 10 ^4. In the terminal group quantification method, it can be measured by comparing the integrated value of the proton derived from the molecular chain terminal group by ^{1 H-NMR with the integrated value of the proton derived from the repeating unit.}

The polyester resin of the present invention has low crystallinity, probably because of the cardo structure of the first diol component (A1), and when measured using a powder X-ray diffractometer, a halo indicating that it is amorphous is found. Often observed.

The polyester resin has high heat resistance. For example, when measured with a thermogravimetric analyzer (TGA) in a nitrogen atmosphere, the 5% weight loss temperature (Td5) of the polyester resin is 300 to 450 ° C. (for example, 330 to 420). ° C.), preferably about 350 to 400 ° C. (for example, 370 to 390 ° C.). The glass transition temperature (Tg) of a polyester resin is, for example, 50 to 120 ° C. (for example, 55 to 100 ° C.), preferably 60 to 80 ° C. (for example, 60 to 60 to 100 ° C.) when measured with a differential scanning calorimeter (DSC). It may be about 70 ° C.), and when measured with a micromelting point measuring device, the softening temperature Ts may be, for example, 150 to 230 ° C. (for example, 160 to 200 ° C.), preferably about 170 to 190 ° C. Good.

Further, the polyester resin of the present invention has higher transparency than the polyester resin using dimethyl terephthalate instead of the first dicarboxylic acid component (B1), and has a thickness of 480 nm or more in a film having a thickness of 30 μm. It exhibits a high transmittance of about 80% or more (for example, 80 to 100%), preferably 83 to 98% (for example, 85 to 95%) in terms of wavelength.

The polyester resin of the present invention often has a relatively high refractive index. Therefore, it can be used alone or in combination with other resins as an optical resin. The refractive index of the polyester resin is 1.56 or more (for example, 1.56 to 1.75), more preferably 1.57 or more (for example, 1.57 to 1.7) at 20 ° C. and a wavelength of 589 nm. It may be preferably about 1.58 or more (for example, 1.58 to 1.67). The polyester resin may have low birefringence (the absolute value of birefringence is small) or negative birefringence.

Polyester resin also has high mechanical properties. When a tensile test is performed on a film having a thickness of 100 μm, a yield elongation of about 0.5 to 5% (for example, 1 to 4%, preferably 1.5 to 3%) and a yield stress of 3 to 12 MPa (for example, 5) are performed. It may be about 10 MPa, preferably about 6 to 8 MPa). Further, the polyester resin shows some ductility even if it is an aromatic polyester, and the elongation at break is 1 to 10% (for example, 2 to 8%, preferably 3 to 7%) in a film having a thickness of 100 μm. The breaking strength may be about 3 to 15 MPa (for example, 5 to 12 MPa, preferably 6 to 10 MPa). Further, in a film having a thickness of 100 μm, the tensile elastic modulus (calculated from the initial gradient) may be about 250 to 500 MPa (for example, 270 to 400 MPa, preferably 300 to 350 MPa). In the dynamic viscoelasticity measurement, the storage elastic modulus (E') of the film having a thickness of 100 μm does not seem to change significantly from low temperature to around room temperature.

Further, even if the polyester resin has an aromatic ring, it has high solubility in an organic solvent probably because of the cardo structure of the 9,9-bisarylfluorene skeleton. For example, when the solubility at room temperature (about 15 to 25 ° C.) at a concentration of 1% by weight is examined, halogenated hydrocarbons (chloroform, dichloromethane, trichloromethane, tetrachloroethane, etc.) and amides (dimethylformamide, dimethylacetamide, etc.) are examined. Etc.), ethers (such as tetrahydrofuran), and sulfoxides (such as dimethyl sulfoxide). A soluble organic solvent can also be selected depending on the type of copolymerization component and the copolymerization ratio.

Therefore, the organic solvent in which the polyester resin is soluble may be, if necessary, a hydrocarbon (for example, an aromatic hydrocarbon such as toluene or xylene, an alicyclic hydrocarbon such as cyclohexane, or an aliphatic hydrocarbon such as hexane). Ketones (alkyl ketones such as methyl ethyl ketone and methyl isobutyl ketone, cycloalkanones such as cyclohexanone), esters (ethyl acetate, butyl acetate, etc.), ethers (chain ethers such as diethyl ether and diisopropyl ether), and these. May be used in combination with a mixed solvent of. The ethers include alkylene glycol monoalkyl ethers (cellosolves, alkylene glycol monoC _1-4 alkyl ethers such as propylene glycol monomethyl ether), these acetates (cellosolve acetates, etc.), and dialkylene glycol monoalkyl. Ethers (carbitols, dialkylene glycol mono C _1-4 alkyl ethers such as dipropylene glycol monomethyl ether) and acetates thereof (carbitol acetates, etc.) are also included.

[Manufacturing method of polyester resin]
The polyester resin has a diol component (A) containing a diol component (A1) having at least a 9,9-bisarylfluorene skeleton and a dicarboxylic acid component (B) containing at least a 2,5-furandicarboxylic acid component (B1). It can be produced by reacting with.

The polyester resin can be prepared by using a conventional esterification method, for example, a melt polymerization method, a solution polymerization method, an interfacial polymerization method, etc., and esterification is carried out while removing water or acid halide produced by the reaction from the reaction system. Either the method or the transesterification method in which a dicarboxylic acid ester is used as the dicarboxylic acid component and the reaction is carried out while removing the alcohol produced by the reaction may be used. An industrially preferred method is a melt polymerization method (eg, transesterification method).

In the reaction, one component of the dicarboxylic acid component and the diol component may be used in excess of the other component. For example, a reaction component that volatilizes or sublimates in the reaction system (alkanediol such as ethylene glycol, 2,5-furandicarboxylic acid component, etc.) may be excessively used.

The reaction involves metal catalysts such as alkali metals (sodium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (manganese, zinc, cadmium, lead, cobalt, etc.), periodic table Group 13 metals (group 13 metals). It may be carried out in the presence of a compound containing (such as aluminum), a metal of Group 14 of the periodic table (such as germanium), and a metal of Group 15 of the periodic table (such as antimony). Examples of the metal compound include alkoxides, organic acid salts (acetates and the like), inorganic acid salts (borates, carbonates and the like), metal oxides 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, 0.01 × 10 ^{-4 to} 1000 × 10 ^-4 mol, preferably 0.1 × 10 ^{-4 to} 500 × 10 ^-4 , more preferably 0.1 × 10 -4 to 500 × 10 -4 per mol of the dicarboxylic acid component. May be about 0.5 × 10 ^{-4 to 300 × 10 -4} (for example, 0.7 × 10 ^-4 to 200 × 10 ^-4 ). As the amount of the catalyst used increases, a high molecular weight polyester resin may be easily produced.

The reaction may be carried out in the presence of additives such as stabilizers (antioxidants, heat stabilizers, etc.), if necessary. The reaction can usually be carried out in an atmosphere of an inert gas (nitrogen, helium, etc.). The reaction can also be carried out under reduced pressure (for example, about 1 × 10 ² to 1 × 10 ^{4 Pa).} The reaction temperature can be selected according to the polymerization method, and the reaction temperature in the melt polymerization method is, for example, 150 to 350 ° C. (for example, 180 to 300 ° C.), preferably 200 to 280 ° C., and more preferably 220 to 250 ° C. It may be about.

In the melt polymerization method, in order to suppress volatilization or sublimation of the 2,5-furandicarboxylic acid component, etc., the temperature is equal to or higher than the melting point of the dicarboxylic acid component and the diol component, and the temperature at which the esterification or transesterification reaction occurs ( For example, the reaction (precondensation reaction) is carried out at 100 to 200 ° C., preferably 130 to 180 ° C., more preferably about 150 to 170 ° C., and then the temperature is raised to react to produce a low molecular weight oligomer (step). 1 or oligomer production step), the temperature may be raised and further polymerized under reduced pressure to produce a polyester resin (step 2 or high molecular weight step).

Step 1 can be carried out at a temperature of about 170 to 250 ° C. (for example, 180 to 230 ° C., preferably 190 to 210 ° C.), and the reaction time is, for example, 1 to 10 hours (for example, 2.5 to 8 hours). , Preferably about 3 to 7 hours). In this step 1, in order to increase the molecular weight of the polyester resin, it is advantageous to lengthen the reaction time, and it may be, for example, about 3 to 10 hours (for example, 4 to 7 hours).

Further, in step 2, finally, at about 250 to 330 ° C. (for example, 260 to 310 ° C., preferably 270 to 300 ° C.) for 1 to 10 hours (for example, 2.5 to 8 hours, preferably 3 to 3 to 300 ° C.). The water or alcohol produced may be removed while reacting for about 7 hours). If necessary, the temperature between step 1 and step 2 is set to a temperature higher than the temperature of step 1 and lower than the temperature of step 2, for example, about 200 to 270 ° C (for example, 210 to 250 ° C) under reduced pressure. A transition step may be provided in which the temperature is raised and the water or alcohol produced in the first step (oligomer formation step) is distilled off in a short time (for example, 10 minutes to 2 hours, preferably 15 minutes to 1 hour). ..

The polyester resin thus produced may be purified by a conventional separation method, for example, a reprecipitation method in which the polyester resin is dissolved in an organic solvent and then put into a poor solvent.

[Use]
As described above, the polyester resin of the present invention has high solubility in organic solvents. Therefore, the polyester resin of the present invention can be used as a composition containing an organic solvent, for example, a coating agent, a paint, an ink, or the like. Further, the polyester resin of the present invention is excellent in moldability (melt moldability, etc.) even if it has high heat resistance, and if necessary, forms a resin composition (or resin molded product) together with an additive to form a molded product. Can be formed. Therefore, the present invention also includes a molded product formed of the polyester resin or a composition thereof.

The additives include various additives such as fillers or reinforcing agents, colorants (dye pigments), plasticizers, lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), and release agents. Examples thereof include molds, antistatic agents, conductive agents, flame retardants, dispersants, flow modifiers, leveling agents, surface modifiers, defoamers, low stress agents, and heat resistance improvers. These additives may be used alone or in combination of two or more.

The shape of the molded product is not particularly limited and can be selected according to the application. For example, a two-dimensional structure (film shape, sheet shape, plate shape, etc.) and a three-dimensional structure (tubular, tubular, rod-shaped, hollow) Shape, housing shape, casing shape, etc.).

Since the polyester resin or resin composition of the present invention has excellent optical properties, an optical material or an optical molded body (particularly, an optical component such as an optical film or an optical lens) may be formed. The thickness of the film can be selected from the range of about 1 to 1000 μm depending on the application, and may be, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably about 10 to 120 μm. The film (optical film) can be produced by forming a film (or molding) using a conventional film forming method, a casting method or a casting method (solvent casting method), a melt extrusion method, a calendar method, or the like. The film may be a non-stretched film or may be either a uniaxial or biaxially stretched film. The draw ratio may be about 1.1 to 10 times (preferably 1.2 to 8 times, more preferably 1.5 to 6 times) in each of the uniaxial or biaxial directions, and 1.1 to 1.1 to It may be about 2.5 times.

The molded body can be manufactured by 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, or the like.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The characteristics and evaluation of the obtained polyester resin were measured as follows.

(1) Infrared spectroscopy (FT-IR)
In the wave number range of uses infrared spectrophotometer (JASCO Corp. "FT / IR-400") from 4000cm ^-1 to 500cm ^-1 was measured by the KBr tablet method.

(2) Differential scanning calorimetry (DSC)
Using a differential scanning calorimeter (“DSC-8000” manufactured by PerkinElmer Co., Ltd.), the temperature is raised from 50 ° C to 100 ° C at a heating rate of 2 ° C / min in a nitrogen atmosphere, and after the temperature is raised, the temperature is raised from 100 ° C to 50. The temperature was lowered to ° C. at a temperature lowering rate of 2 ° C./min, and then from 50 ° C. to 100 ° C. at a heating rate of 2 ° C./min. The glass transition point (Tg) in the first temperature raising process was evaluated.

(3) Thermogravimetric analysis (TGA)
Using a thermogravimetric analyzer (“TGA-7” manufactured by PerkinElmer Co., Ltd.), the temperature was raised from 50 ° C. to 700 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere, and the 5% weight loss temperature was measured.

(4) Wide-angle X-ray diffraction measurement (WAXS)
A sample plate is filled with about 0.1 g of a sample so that the measurement surface is flat, and a diffraction angle 2θ is detected from 5 ° to 50 ° using a powder X-ray diffractometer (“Gaiger Flex” manufactured by RIGAKU). The measurement was performed at a speed of 1 ° / min. An intensity profile was obtained using CuKα rays obtained by monochromating X-rays generated at 35 kV and 15 mA with a graphite monochromator.

(5) Nuclear Magnetic Resonance Spectroscopy (NMR)
Nuclear magnetic resonance spectroscopy (JEOL Ltd. "AL300 ^{SC-NMR", 1} H resonance frequency 300MHz) was measured in.

(6) Solubility test The solubility of the sample was evaluated at a concentration of 1% by weight and 25 ° C.

(7) Softening point measurement A sample was sandwiched between cover glasses and observed under cross Nicol using a trace melting point measuring device (“MP-500D type” manufactured by Yanaco Kikikai Development Laboratory Co., Ltd.).

(8) Tensile strength test A film having a thickness of 100 μm was prepared by a solution casting method. This film was fixed to a universal material tester (“5583 type” manufactured by Instron) and measured at a load of 500 N and a tensile speed of 0.5 mm / min. The breaking strength, breaking stress, and tensile elastic modulus were obtained from the average value of the three measured values.

(9) Dynamic viscoelasticity test A film having a thickness of 100 μm was prepared by a solution casting method. This film was fixed to a dynamic viscoelasticity measuring device (“DMS6100” manufactured by SII Nanotechnology Co., Ltd.), and the temperature rise rate was 3 ° C./min, the static tension was 5 gf, the measurement frequency was 10 Hz, and the measurement temperature range was −150 ° C. It was measured under the condition of ~ 150 ° C.

(10) Measurement of Solution Viscosity The reduced viscosity (hsp / c), which is an index of molecular weight, was measured at 25 ° C. in a 0.5 g / dL chloroform solution using an Ostwald viscometer.

(11) Visible / ultraviolet spectroscopic measurement (UV-Vis)
A film having a thickness of 30 μm was prepared by the solution casting method. These films were fixed to a visible ultraviolet spectrophotometer (“V-700 type” manufactured by JASCO Corporation) and measured in a wave number range ^{from 300 cm -1} to 600 cm ^-1.

[Example 1]
Equal molar amounts of dimethyl 2,5-furandicarboxylate (DMFC) (1.00 g; 5.43 x ^10-3 mol) and 9,9-bis [4- (2-hydroxyethoxy) phenyl) in a two-necked flask. ] Fluolene (BPEF) (2.38 g; 5.43 × 10 ^-3 mol) and isopropyl titanate (TTIP) (0.0154 g; 1.0 mol% with respect to DMFC) were charged into a polymerization tube and stirred. After heating at 160 ° C. for 1 hour, the temperature was raised to 200 ° C. and heated for 5 hours (step 1). Then, the reaction system was depressurized (0.1 to 0.5 mmHg), heated at 230 ° C. for 30 minutes, further heated to 280 ° C., and polymerized for 2 hours and 30 minutes (step 2). The obtained polymer was dissolved in chloroform and then purified by a reprecipitation method in which it was put into methanol.

[Example 2 and Example 3]
The reduced viscosity is the same as in Example 1 except that the amount of isopropyl titanate (TTIP) used is 0.5 mol% (Example 2) and 1.5 mol% (Example 3) with respect to the DMFC. A 0.20 dL / g polyester resin (Example 2) and a polyester resin having a reduced viscosity of 0.15 dL / g (Example 3) were obtained.

[Example 4 and Example 5]
A polyester resin having a reducing viscosity of 0.23 dL / g (implementation) in the same manner as in Example 1 except that the reaction time in step 2 is 1 hour (Example 4) and the reaction temperature in step 2 is 300 ° C. (Example 5). Example 4) and a polyester resin having a reduced viscosity of 0.15 dL / g (Example 5) were obtained.

[Reference example 1]
The reaction was carried out in the same manner as in Example 1 except that the amount of isopropyl titanate (TTIP) used was 0.1 mol% with respect to the DMFC and the reaction time in step 1 was 2 hours. However, the DMFC was sublimated, the reduced viscosity of the product was 0.03 dL / g, and a high molecular weight polyester resin could not be obtained.

[Reference example 2]
The reaction was carried out in the same manner as in Example 1 except that the amount of isopropyl titanate (TTIP) used was 0.1 mol% with respect to the DMFC and the reaction time in step 1 was 5 hours. However, the reduced viscosity of the product was 0.06 dL / g, and a high molecular weight polyester resin could not be obtained.

The characteristics of the polyester resin obtained in Example 1 are shown below.

FT-IR (KBr) (ν / cm -1); 2800-3160cm -1 ( aromatic C-H stretching), 1721 cm ^-1 (ester C = O stretching), 1245cm ^-1 (ether C-O-C stretch ), 1220 cm ^-1 (Fran ring COC expansion and contraction)
^{1 1} H-NMR (DMSO-d ₆ , δ / ppm); 7.83 (s, Ar, 2H), 7.18-7.35 (s, Ar, 2H, d, Ar, 2H, d, Ar, 2H, d, Ar, 2H), 6.94 (d, Ar, 2H), 6.88 (d, Ar, 2H), 4.53 (s, Ar, 4H), 4.18 (s, Ar, 4H), 3.87 (s, Ar, 2H), 3.80 (s, Ar, 3H), 3.65 (s, Ar, 2H)

The powder X-ray diffraction spectrum of the polyester resin obtained in Example 1 is shown in FIG. As is clear from the halo of FIG. 1, the polyester resin was amorphous.

The polyester resin has a 5% weight loss temperature (Td5) of 380 ° C., a glass transition temperature (Tg) of 65 ° C., and a softening temperature Ts of 180 ° C., and has high heat resistance.

Further, the polyester resin showed a transmittance of 80% or more at a wavelength of 480 nm or more in a film having a thickness of 30 μm.

The polyester resin obtained in Example 1 exhibited a yield elongation of 2.3% and a yield stress of 7.3 MPa in a film having a thickness of 100 μm. Further, it showed some ductility, and in a film having a thickness of 100 μm, the elongation at break was 4.6%, the strength at break was 7.0 MPa, and the tensile elastic modulus (calculated from the initial gradient) was 330 MPa. In the dynamic viscoelasticity measurement, the storage elastic modulus (E') of the film having a thickness of 100 μm did not change significantly from low temperature to around room temperature.

Further, the polyester resin obtained in Example 1 is soluble in chloroform, tetrachloroethane, dimethylformamide, dimethylacetamide, tetrahydrofuran and dimethyl sulfoxide at a temperature of 25 ° C., and is soluble in acetone, n-hexane, toluene and acetonitrile. It was insoluble.

The polyester resin of the present invention is, for example, a coating agent, a paint, an ink, an adhesive, an adhesive, an electric / electronic material, an electric / electronic component or device, a mechanical component or device (for example, an automobile, an aviation / space material, a sensor, etc.). ) Etc. In particular, the resin composition can be easily molded by extrusion molding, injection molding, etc., and various molded bodies or molding members (for example, molded bodies such as casings and housings), containers (food, daily necessities, electricity, electronic devices, parts, etc.) Can be suitably used for packaging materials such as films and sheets.

Claims (8)

A polyester resin having a repeating unit of a diol unit (excluding isosorbide) and a dicarboxylic acid unit (excluding aromatic dicarboxylic acid having a sulfonic acid base), wherein the diol unit is at least the following formula (1). ) , The dicarboxylic acid unit contains at least 2,5-furandicarboxylic acid units, and the diol unit has the 9,9-bisarylfluorene skeleton. A polyester resin in which the ratio of the amount to the 2,5-furandicarboxylic acid unit is 30/70 to 70/30 (molar ratio).

(In the formula, rings Z ¹ , Z ² , Ar ¹ and Ar ² indicate the same or different arene rings, ^{respectively, R 1a} and R ^{1 b} are the same or different, respectively, and alkylene groups, m 1 and m 2 are the same or different, respectively. Integers greater than or equal to 0 or 1, R ^2a and R ^2b represent the same or different C _1-4 alkyl groups, R ^3a and R ^3b are the same or different substituents, n1, n2, k1 and k2 are the same or different, respectively. Differently indicates an integer of 0 or 1 to 4) The polyester resin according to claim 1, wherein the diol unit contains the diol unit represented by the formula (1) in a proportion of 10 to 100 mol%. In formula (1), rings Z ¹ and Z ² are the same or different, benzene ring or naphthalene ring; rings Ar ¹ and Ar ² are the same or different, benzene ring or naphthalene ring; R ^1a. The polyester resin according to claim 1 or 2, wherein R ^1b is the same or different C _2-4 alkylene group; and m 1 and m 2 are the same or different integers of 0 or 1-10. In formula (1), rings Z ¹ and Z ² are benzene or naphthalene rings; rings Ar ¹ and Ar ² are benzene rings ; n 1 and n 2 are integers 0-2; k1 and k2 are The polyester resin according to any one of claims 1 to 3, which is 0. The polyester resin according to any one of claims 1 to 4, wherein the dicarboxylic acid unit contains 2,5-furandicarboxylic acid units in a proportion of 10 to 100 mol%. The polyester resin according to any one of claims 1 to 5, wherein the dicarboxylic acid unit contains 2,5-furandicarboxylic acid units in a proportion of 25 to 100 mol%. A method for producing a polyester resin by reacting a diol component (excluding isosorbide) with a dicarboxylic acid component (excluding aromatic dicarboxylic acid having a sulfonic acid base), wherein the diol component is at least claimed. Item 1 Contains a diol component corresponding to a diol unit having a 9,9-bisarylfluorene skeleton represented by the formula (1), and the dicarboxylic acid component contains at least a 2,5-furandicarboxylic acid component. A method for producing a polyester resin, in which a diol component having a 9,9-bisarylfluorene skeleton and the 2,5-frangicarboxylic acid component are used in a ratio of the former / the latter = 30/70 to 70/30 (molar ratio). A molded product formed of the polyester resin according to any one of claims 1 to 6.

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