JP2019006685A - Novel compound having triptycene skeleton and method for producing the same - Google Patents

Abstract

To provide a novel compound that can be used as a polymerization component of resin.SOLUTION: The present invention provides a compound represented by formula (1) (Rand Rindependently represent a substituent, Reach independently represent a hydroxyl group, a group [-OR] or a halogen atom; Ris a hydrocarbon group; m1 each independently represent an integer of 0-4; m2 is an integer of 0-2; n is an integer of 1 or greater).SELECTED DRAWING: None

Description

  The present invention relates to a novel compound having a triptycene skeleton (9,10-dihydro-9,10-o-benzenoanthracene skeleton), a method for producing the same, a novel polyester resin using the compound, and a molded article containing the resin About.

  Resins that are transparent and excellent in mechanical properties are widely used as optical materials (optical members or transparent members) such as compact disks, lenses, and automotive lamps. As such a transparent resin, for example, polymethyl methacrylate, alicyclic polyolefin, polycarbonate and the like are widely used. Of these, polymethyl methacrylate and alicyclic polyolefin are suitable for optical lenses and the like in view of high transparency, low birefringence, and low chromatic aberration, but tend to have low refractive index and heat resistance. Moreover, although polycarbonate is excellent in transparency and heat resistance, it has a drawback of high birefringence. Therefore, these transparent resins cannot satisfy high heat resistance, high refractive index, and low birefringence, and use as an optical member is limited. Therefore, development of resin materials capable of satisfying the above characteristics at a high level is advanced. ing.

As such a resin material, typically, a copolyester resin mainly composed of a bisphenylfluorene compound as a diol component has been proposed. For example, JP-A-7-198901 (Patent Document 1) discloses an aromatic dicarboxylic acid component, a predetermined proportion of 9,9-bis (4-hydroxyC _2-4 alkoxyphenyl) fluorenes and C _2-4. A linear polyester polymer having a diol component composed of an aliphatic glycol as a polymerization component is disclosed. It is described that this polyester resin has a high refractive index of 1.60 or more, excellent transparency and heat resistance, and small optical anisotropy. In the examples of this document, terephthalic acid and / or isophthalic acid components, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and ethylene glycol are polymerized at a predetermined ratio to copolymerize. A polyester resin is prepared.

  Although this copolyester resin can achieve high heat resistance, high refractive index, and low birefringence to some extent, there is a limit in reducing birefringence because a dicarboxylic acid component such as a terephthalic acid component is included in the polymerization component.

Japanese Patent No. 3331121 (Patent Document 2) discloses a dicarboxylic acid component containing an alicyclic dicarboxylic acid component and a diol component containing 9,9-bis (4-hydroxyC _2-4 alkoxyphenyl) fluorenes. A polyester polymer having a polymerization component as a polymerization component is disclosed.

  In the examples of this document, a dicarboxylic acid component containing dimethyl 2,6-decalin dicarboxylate and a diol component consisting of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and ethylene glycol are polymerized. A polyester resin is prepared.

  However, although both high heat resistance and low birefringence can be achieved by the alicyclic dicarboxylic acid component, the refractive index is not sufficient.

  Therefore, it is extremely difficult to satisfy high heat resistance, high refractive index, and low birefringence, and development of a novel polymerization component (monomer) that can improve these characteristics in a well-balanced manner is expected.

JP-A-7-198901 (Claims, Examples, [0035]) Japanese Patent No. 3331121 (Claims, Examples)

  Accordingly, an object of the present invention is to provide a novel compound that can be used as a polymerization component of a resin (polyester resin or the like), a method for producing the same, a polyester resin using the compound, and a molded body containing the polyester resin. is there.

  Another object of the present invention is to provide a novel compound capable of forming a resin satisfying high heat resistance, a high refractive index and a low birefringence, a method for producing the same, a polyester resin using the compound, and a molded article containing the polyester resin. Is to provide.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a novel compound having a triptycene skeleton can be used as a polymerization component of a resin, and thus completed the present invention.

  That is, the novel compound of the present invention is represented by the following formula (1).

(Wherein R ¹ and R ² are each independently a substituent, R ³ is each independently a hydroxyl group, a group [—OR ⁴ ] (wherein R ⁴ represents a hydrocarbon group) or a halogen atom, m1 is independently an integer of 0 to 4, m2 is an integer of 0 to 2, and n is an integer of 1 or more.

In the formula (1), R ¹ and R ² are each independently a group [—R ⁵ ], a group [—OR ⁵ ], a group [—SR ⁵ ], a group [— (C═O) —R ⁵ ]. , Group [— (C═O) —OR ⁵ ] (wherein R ⁵ represents a hydrocarbon group), a halogen atom, a nitro group, a cyano group or a substituted amino group, m1 is independently 0 to 2 An integer of about, m2 may be 0 or 1, and n may be an integer of about 1-6.

  In the present invention, a compound represented by the formula (1) is produced by reacting a compound represented by the following formula (2) with a compound represented by the following formula (3) in the presence of a base. To include a method.

(In the formula, X represents a halogen atom, and R ¹ , R ² , R ³ , m1, m2 and n are the same as those in the formula (1)).

  The present invention also provides a polyester resin formed of a dicarboxylic acid unit (A) and a diol unit (B), wherein the dicarboxylic acid unit (A) is a first dicarboxylic acid represented by the following formula (A1). A polyester resin containing at least the acid unit (A1) is also included.

(Wherein R ¹ , R ² , m1, m2 and n are the same as those in the formula (1)).

In the formula (A1), R ¹ and R ² are each independently a group [—R ⁵ ], a group [—OR ⁵ ], a group [—SR ⁵ ], a group [— (C═O) —R ⁵ ]. , Group [— (C═O) —OR ⁵ ], wherein R ⁵ represents a hydrocarbon group, a halogen atom, a nitro group, a cyano group, or a substituted amino group, m1 is independently 0 to 0. An integer of about 2, m2 may be 0 or 1, and n may be an integer of about 1-6.

  The diol unit (B) may contain a first diol unit (B1) represented by the following formula (B1).

Wherein Z is independently an arene ring, R ⁶ and R ⁷ are each independently a substituent, A ¹ is each independently a linear or branched alkylene group, and p is each independently 0 -4, q are each independently an integer of 0 or more, and r are each independently an integer of 0 or more).

In the formula (B1), Z is each independently a C _6-14 arene ring, R ⁶ is each independently a hydrocarbon group, a cyano group or a halogen atom, and R ⁷ is each independently a group [—R ⁸ ]. , Group [—OR ⁸ ], group [—SR ⁸ ], group [— (C═O) —R ⁸ ] (wherein R ⁸ represents a hydrocarbon group, respectively), halogen atom, nitro group, cyano group Or a substituted amino group, A ¹ is each independently a linear or branched C _2-6 alkylene group, p is each independently an integer of about 0 to 2, and q is each independently about 0 to 2. The integer and r may each independently be an integer of about 0 to 10.

  The diol unit (B) may further include a second diol unit (B2) represented by the following formula (B2). Further, the ratio between the first diol unit (B1) and the second diol unit (B2) may be, for example, the former / the latter (molar ratio) = 50/50 to 99/1.

(In the formula, A ² represents a linear or branched alkylene group, and s represents an integer of 1 or more).

  The present invention also includes a molded body (for example, an optical film or an optical lens) molded from the polyester resin.

  In the present specification and claims, “dicarboxylic acid unit” or “structural unit derived from dicarboxylic acid component” is a unit obtained by removing OH (hydroxyl group) from two carboxyl groups of the corresponding dicarboxylic acid ( Or a “dicarboxylic acid component” (including compounds exemplified as the dicarboxylic acid component) may be used synonymously with the corresponding “dicarboxylic acid unit”. Similarly, the “diol unit” or “structural unit derived from the diol component” means a unit (or a divalent group) obtained by removing a hydrogen atom from two hydroxyl groups of the corresponding diol component, “Component” (including compounds exemplified as the diol component) may be used synonymously with the corresponding “diol unit”.

In addition, in the present specification and claims, the “dicarboxylic acid component” means, in addition to dicarboxylic acid, an ester-forming derivative thereof [for example, dicarboxylic acid ester (methyl ester, ethyl ester, t-butyl ester, etc. C _1-4 alkyl ester, preferably C _1-2 alkyl ester), dicarboxylic acid halide (dicarboxylic acid chloride, etc.), dicarboxylic acid anhydride, etc.]. The “ester-forming derivative” may be a monoester (half ester) or a diester.

  The novel compound having a triptycene skeleton of the present invention can be used as a polymerization component of a resin (for example, a polyester resin). The resin containing the compound as a polymerization component can satisfy high heat resistance, high refractive index and low birefringence at a high level.

[Compound represented by Formula (1)]
The novel compound having the triptycene skeleton (9,10-dihydro-9,10-o-benzenoanthracene skeleton) of the present invention is represented by the following formula (1).

(Wherein R ¹ and R ² are each independently a substituent, R ³ is each independently a hydroxyl group, a group [—OR ⁴ ] (wherein R ⁴ represents a hydrocarbon group) or a halogen atom, m1 independently represents an integer of 0 to 4, m2 represents an integer of 0 to 2, n represents an integer of 1 or more. On the right side, “Organic Chemistry / Biochemical Nomenclature Revised 2nd Edition” : Kenzo Hirayama, Kazuo Hirayama, Issuer: Nanoedo Co., Ltd.)).

In the formula (1), examples of the substituent represented by R ¹ and R ² include a group [—R ⁵ ] (wherein R represents a hydrocarbon group, the same shall apply hereinafter), a group [—OR ⁵ ], Group [—SR ⁵ ], group [— (C═O) —R ⁵ ], group [— (C═O) —OR ⁵ ], halogen atom, nitro group, cyano group or substituted amino group. It is done.

Examples of the hydrocarbon group represented by R ⁵ (or group [—R ⁵ ]) include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s- Linear or branched C _1-12 alkyl group such as butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, preferably linear or branched A chain C _1-8 alkyl group); a cycloalkyl group (eg, a C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group); an aryl group (eg, a phenyl group, biphenylyl) A C _6-14 aryl group such as a naphthyl group, preferably a C _6-10 aryl group, etc .; an alkenyl group (eg, ethenyl group (vinyl group), 1-propenyl group, 2- A C _2-12 alkenyl group such as a propenyl group and a 1-butenyl group, preferably a C _2-8 alkenyl group; a cycloalkenyl group (eg, a C _5-10 cycloalkenyl group such as a cyclohexenyl group, preferably C _{5 -8} cycloalkenyl groups); alkynyl groups (for example, C _2-12 alkynyl groups such as ethynyl group, 1-propynyl group, 2-propynyl group (propargyl group), 1-octynyl group, preferably C _2-8 alkynyl) And a combination thereof [for example, mono to penta C _1-4 alkyl-C _6-10 aryl such as alkylphenyl group (for example, methylphenyl group (tolyl group), dimethylphenyl group (xylyl group), etc.) An aralkyl group (for example, a C _6-10 aryl-C such as a benzyl group or a phenethyl group). _1-4 alkyl group, etc.)] and the like.

Examples of the group [—OR ⁵ ] include an alkoxy group (for example, a linear or branched chain such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, and a t-butoxy group). Jo such _{C 1-12} alkoxy group); a cycloalkyl group (e.g., a _{C 5-10} cycloalkyl group such as cyclohexyl group); an aryloxy group (e.g., _{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) and the like.

Examples of the group [—SR ⁵ ] include an alkylthio group (for example, a C _1-10 alkylthio group such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, and a t-butylthio group); a cycloalkylthio group (for example, A C _5-10 cycloalkylthio group such as a cyclohexylthio group; an arylthio group (such as a C _6-10 arylthio group such as a thiophenoxy group); an aralkylthio group (such as a C _6-10 aryl such as a benzylthio group). _-C1-4 alkylthio group, etc.).

Examples of the group [— (C═O) —R ⁵ ] include an acyl group (eg, a C _1-8 acyl group such as an acetyl group or a benzoyl group).

As the group [— (C═O) —OR ⁵ ], for example, an alkoxycarbonyl group (for example, C _1-12 alkoxy- such as methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, etc.) A cycloalkyloxyoxycarbonyl group (eg, a C _5-10 cycloalkyloxy-carbonyl group such as a cyclohexyloxycarbonyl group); an aryloxycarbonyl group (eg, a C _6-10 aryl such as a phenoxycarbonyl group). Oxy-carbonyl group, etc.).

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of heat resistance, a fluorine atom or the like is preferable.

Examples of the substituted amino group include a mono-substituted amino group [for example, an alkylamino group (for example, a C _1-4 alkylamino group such as a methylamino group); an alkylcarbonylamino group (for example, a C ₁ such as an acetylamino group). _-4 alkyl-carbonylamino group etc.]; di-substituted amino group [eg dialkylamino group (eg _diC1-4 alkylamino group such as dimethylamino group); bis (alkylcarbonyl) amino group (eg Bis ( _C1-4 alkyl-carbonyl) amino group such as diacetylamino group, etc.]], preferably disubstituted amino groups such as dialkylamino group.

Among these groups R ¹ , a group [—R ⁵ ] (for example, a linear or branched C _1-4 alkyl group such as a methyl group, a C _6-10 alkyl group such as a phenyl group, etc.), a halogen atom (For example, a chlorine atom, a bromine atom, an iodine atom, etc.) are preferable.

Among these groups R ² , a group [—R ⁵ ] (for example, a linear or branched C _1-4 alkyl group such as a methyl group), a group [—OR ⁵ ] (for example, a methoxy group, etc.) A linear or branched C _1-4 alkoxy group, etc.) and a halogen atom (eg, a chlorine atom) are preferred.

The substitution number m1 of the group R ¹ is, for example, an integer of about 0 to 3, preferably an integer of about 0 to 2, more preferably 0 or 1, especially 0. In two different benzene rings constituting the triptycene skeleton, the number of substitutions m1 may be the same or different from each other. The types of the groups R ¹ substituted on the different benzene rings may be different from each other and are usually the same in many cases. When m1 is 2 or more, the types of two or more groups R ¹ substituted on the same benzene ring may be the same or different from each other. The substitution position of the group R ¹ is not particularly limited, and may be any of the 5-position to 8-position and the 13-position to 16-position of the triptycene skeleton. For example, the 5-position, 8 It may be in the -position, 13-position, 16-position and the like.

The substitution number m2 of the group R ² may be, for example, 0 or 1, and is preferably 0. When m2 is 2, the types of the ^two groups R ² may be the same or different from each other. Further, the substitution position of the group R ² is the 2-position and / or the 3-position of the triptycene skeleton.

In the group [—OR ⁴ ] represented by R ³ , the hydrocarbon group represented by R ⁴ is the same as the hydrocarbon group represented by R ⁵ exemplified in the above R ¹ and R ² terms. The representative group [—OR ⁴ ] is the same as the group [—OR ⁵ ] exemplified in the above R ¹ and R ² terms. Among the groups [—OR ⁴ ] represented by R ³ , an alkoxy group (for example, a linear or branched C ₁ -1 such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, a t-butoxy group, etc.) ₈ alkoxy groups, etc.) are preferable, and in particular, linear or branched C _1-6 alkoxy groups (particularly, linear or branched C _1-4 alkoxy groups such as methoxy group) are more preferable.

The two groups R ³ may be different from each other but are usually the same. Of the groups R ³ , the group is usually a hydroxyl group or a group [—OR ⁴ ] (particularly, a group [—OR ⁴ ]) because it is easy to prepare.

  The repeating number n of the methylene group may be selected from, for example, an integer of about 1 to 12 (for example, 1 to 10), for example, an integer of about 1 to 8 (for example, 1 to 6), preferably 1 to 1. It may be an integer of about 4 (for example, 1 to 3), more preferably 1 or 2 (particularly 1). If n is too large, the heat resistance of the resulting resin may be reduced when used as a polymerization component. The two n's may be different from each other but are usually the same.

As the compound represented by the formula (1), typically, a compound in which the group R ³ is a group [—OR ⁴ ], for example, 1,4-bis (methoxycarbonylmethoxy) triptycene, 1,4-bis 1,4-bis (C _1-4 alkoxycarbonylC _1-4 alkoxy) triptycene, such as (ethoxycarbonylmethoxy) triptycene, 1,4-bis [2- (methoxycarbonyl) ethoxy] triptycene, etc .; the group R ³ is hydroxyl A group of compounds such as 1,4-bis (carboxy C _1-4 alkoxy) triptycene such as 1,4-bis (carboxymethoxy) triptycene, 1,4-bis (2-carboxyethoxy) triptycene; ³ is a halogen atom compounds, such as 1,4-bis (chlorocarbonyl methoxy) triptycene, 1 4- bis (bromo carbonyl methoxyphenyl) triptycene, such as 1,4-bis [2- (chlorocarbonyl) ethoxy] triptycene such as 1,4-bis (halo carbonyl _{C 1-4} alkoxy) triptycene the like.

(Method for producing compound represented by formula (1))
The novel compound having a triptycene skeleton represented by the formula (1) can be prepared, for example, according to the following reaction formula.

(In the formula, X represents a halogen atom, and R ¹ , R ² , R ³ , m1, m2 and n are the same as those in formula (1), including preferred embodiments).

Reaction 1 (first reaction)
In the first reaction, an anthracene represented by the formula (5) and a p-benzoquinone represented by the formula (6) are reacted to synthesize a compound represented by the formula (4). Examples of the anthracene represented by the formula (5) include anthracene which is unsubstituted at least in the 9,10-position, for example, anthracene, mono to tetraalkylanthracene (for example, 2-t-butylanthracene, 2,3- And mono- to di-C _1-4 alkylanthracene such as dimethylanthracene). The p-benzoquinones represented by the formula (6) include p-benzoquinones which are unsubstituted at least in the 5,6-position, such as p-benzoquinone, alkyl-p-benzoquinone (for example, methyl-p-benzoquinone). C _1-4 alkyl-p-benzoquinone, etc.), alkoxy-p-benzoquinone (eg, C _1-4 alkoxy-p-benzoquinone, such as methoxy-p-benzoquinone) and the like. Commercially available products can be used for the anthracene represented by the formula (5) and the p-benzoquinones represented by the formula (6).

  The ratio of the anthracene represented by the formula (5) and the p-benzoquinone represented by the formula (6) is, for example, the former / the latter (molar ratio) = 1 / 0.9 to 1 / 1.5. (For example, 1 / 0.95 to 1 / 1.3), preferably 1 / 0.98 to 1 / 1.2 (for example, 1/1 to 1 / 1.1), more preferably 1/1 to It may be about 1 / 1.05.

  In many cases, the reaction is usually carried out in the presence of a solvent. Examples of the solvent include hydrocarbons (eg, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene), and halogenated hydrocarbons ( For example, halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, halogenated aromatic hydrocarbons such as chlorobenzene and o-dichlorobenzene, etc .; ethers (for example, chain forms such as diisopropyl ether) Ethers, cycloaliphatic ethers such as cyclopentylmethyl ether, cyclic ethers such as tetrahydrofuran and 1,4-dioxane); sulfoxides (such as dimethyl sulfoxide); amides (eg, N, N-dimethylformamide (DMF)) N, N-dimethylacetamide (D A), N-methyl-2-pyrrolidone, etc.) and the like. These solvents can be used alone or in combination of two or more. Of these solvents, aromatic hydrocarbons such as toluene and xylene, and halogenated aromatic hydrocarbons such as chlorobenzene and orthodichlorobenzene (particularly halogenated aromatic hydrocarbons) are preferable.

  The ratio of the solvent is not particularly limited as long as it dissolves the anthracenes and p-benzoquinones so that the reaction can proceed efficiently. Therefore, the ratio of the solvent is, for example, about 100 to 1000 parts by weight with respect to 100 parts by weight of the total amount of anthracenes represented by formula (5) and p-benzoquinones represented by formula (6). Also good.

  The reaction may be performed in the presence of a Lewis acid or in the absence. Examples of the Lewis acid include metal halides (for example, zinc halide, iron halide, cobalt halide, copper halide, titanium halide, etc.). These Lewis acids can be used alone or in combination of two or more. The ratio of the Lewis acid may be, for example, about 0.01 to 0.1 mol, preferably about 0.01 to 0.05 mol with respect to 1 mol of the anthracene represented by the formula (5).

  The reaction temperature can be selected from a range of, for example, about 40 to 200 ° C, and may be, for example, 100 to 180 ° C, preferably 110 to 150 ° C, and more preferably about 120 to 140 ° C. The reaction may be performed under reflux of the solvent. The reaction time may be, for example, 1 to 12 hours, preferably about 3 to 6 hours. After completion of the reaction, the reaction product is separated and purified by conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, or a combination of these. May be.

Reaction 2 (second reaction)
In the second reaction, the compound represented by the formula (4) obtained in the first reaction is isomerized in the presence of an acid catalyst to synthesize the compound represented by the formula (2).

  The acid catalyst may be a strong acid, and examples thereof include inorganic acids such as hydrogen halide, sulfuric acid and phosphoric acid, and organic acids such as methanesulfonic acid. These acid catalysts can be used alone or in combination of two or more. Of these acid catalysts, hydrogen halides are preferable, and hydrogen chloride, hydrogen bromide (particularly hydrogen bromide), and the like are preferable. The acid may be used in the form of an aqueous solution (for example, hydrochloric acid (hydrochloric acid), hydrobromic acid, etc.). The ratio of the acid catalyst may be, for example, about 0.01 to 0.2 mol, preferably about 0.1 to 0.2 mol, relative to 1 mol of the compound represented by formula (4).

  The reaction may be performed in the presence of a solvent. As the solvent, for example, carboxylic acids such as acetic acid and propionic acid can be used. These solvents can be used alone or in combination of two or more. Of these solvents, acetic acid is preferred.

  The ratio of the solvent is not particularly limited, and may be, for example, about 100 to 1000 parts by weight with respect to 100 parts by weight of the compound represented by Formula (4).

  The reaction temperature can be selected from the range of, for example, about 40 to 200 ° C. (for example, 60 to 180 ° C.), and may be, for example, about 80 to 150 ° C., preferably about 100 to 120 ° C. The reaction may be performed under reflux of the solvent. The reaction time may be, for example, about 0.25 to 3 hours, preferably about 0.5 to 1 hour. After completion of the reaction, the reaction product is separated and purified by conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, or a combination of these. May be.

Reaction 3 (Third reaction)
In the third reaction, the compound represented by the formula (2) obtained in the second reaction and the compound represented by the formula (3) are combined in the presence of a base (capturing agent or acid scavenger). By reacting, a compound represented by the formula (1) is synthesized.

In the formula (3), examples of the halogen atom represented by X include a chlorine atom and a bromine atom, and a bromine atom is particularly preferable. Further, the group R ³ is usually a group [—OR ⁴ ] (such as an alkoxy group such as a methoxy group (C _1-4 alkoxy group etc.)). Typically, the compound represented by the formula (3) is a haloalkanoic acid alkyl ester, for example, a halo C _2-7 alkanoic acid C _1-6 alkyl such as methyl bromoacetate, ethyl bromoacetate, methyl 3-bromopropionate, etc. Examples include esters. A commercial item etc. can be used for the compound represented by Formula (3).

  The ratio of the compound represented by the formula (2) and the compound represented by the formula (3) is, for example, the former / the latter (molar ratio) = 1 / 1.5 to 1/5, preferably 1/1. It may be about 8 to 1/3, more preferably about 1/2 to 1 / 2.5.

  The base may be an organic base such as amines (for example, a trialkylamine such as triethylamine), but usually an inorganic base is often used. Examples of the inorganic base include metal carbonate, metal bicarbonate (or metal bicarbonate), metal hydride and the like. These bases can be used alone or in combination of two or more. Among these bases, inorganic bases, among them, metal carbonates (for example, sodium carbonate, potassium carbonate, etc.), metal bicarbonates (for example, sodium bicarbonate, potassium bicarbonate, etc.) are preferable, and particularly potassium carbonate, etc. The metal carbonate is preferred.

  The ratio of the base is, for example, about 1.5 to 5 mol, preferably 1.8 to 3 mol, and more preferably about 2 to 2.5 mol with respect to 1 mol of the compound represented by the formula (2). May be.

  The reaction is usually carried out in the presence of a solvent. Examples of the solvent include the same solvents as those exemplified in the first reaction. These solvents can be used alone or in combination of two or more. Of these solvents, ethers (tetrahydrofuran, cyclopentyl methyl ether, etc.), sulfoxides (dimethylsulfoxide, etc.), amides (DMF, DMA, etc.) are preferred, and amides such as DMF are generally used.

  The ratio of the solvent is not particularly limited as long as the compounds represented by formula (2) and formula (3) can be dissolved. Therefore, the ratio of the solvent may be, for example, about 100 to 1000 parts by weight with respect to 100 parts by weight of the total amount of the compound represented by Formula (2) and the compound represented by Formula (3).

  The reaction temperature can be selected from the range of, for example, about 40 to 200 ° C. (for example, 50 to 150 ° C.), for example, 60 to 120 ° C. (for example, 65 to 100 ° C.), preferably about 70 to 90 ° C. Also good. The reaction time may be, for example, 1 to 12 hours, preferably about 4 to 6 hours. After completion of the reaction, the reaction product is separated and purified by conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, or a combination of these. May be.

  The compound represented by the formula (1) thus obtained can be effectively used for various applications, for example, as a polymerization component of a resin (polyester resin, polyamide resin, etc.).

[Polyester resin]
The compound represented by the formula (1) can be used as a polymerization component (monomer or monomer) of a resin, for example, a polymerization component of a polyester resin (for example, a dicarboxylic acid component for forming a dicarboxylic acid unit). .

(Dicarboxylic acid unit (A))
First dicarboxylic acid unit (A1)
The polyester resin of the present invention is a polyester resin formed of a dicarboxylic acid unit (A) and a diol unit (B), wherein the dicarboxylic acid unit (A) is represented by the following formula (A1). The dicarboxylic acid unit (A1) may be included at least.

(Wherein R ¹ , R ² , m1, m2 and n are the same as those in formula (1) including preferred embodiments).

In the formula (A1), the groups R ¹ and R ² are usually a group [—R ⁵ ], a group [—OR ⁵ ], a group [—SR ⁵ ], a group [— (C═O) —R ^5. ], Group [— (C═O) —OR ⁵ ], halogen atom, nitro group, cyano group or substituted amino group (for example, group [—R ⁵ ], group [—OR ⁵ ], group [—SR ⁵ ]). , A group [— (C═O) —R ⁵ ], a halogen atom, a nitro group, a cyano group, or a substituted amino group).

  Examples of the representative first dicarboxylic acid unit (A1) include dicarboxylic acid units corresponding to the first dicarboxylic acid component (A1) such as the representative compounds exemplified in the section of the formula (1). . These 1st dicarboxylic acid units (A1) can also be used individually or in combination of 2 or more types.

  By including such a first dicarboxylic acid unit (A1), it is possible to effectively reduce birefringence while improving (or reducing) the refractive index and heat resistance. Usually, when an aromatic skeleton is introduced into a resin, the refractive index and heat resistance can be improved, but birefringence also tends to increase. However, in the present invention, despite including the first dicarboxylic acid unit (A1) containing as many as three benzene ring skeletons, the birefringence can be surprisingly effectively reduced, so that high heat resistance, high refractive index and low Birefringence can be satisfied in a balanced manner.

  The ratio of the first dicarboxylic acid unit (A1) can be selected from a range of, for example, about 1 to 100 mol% (for example, 10 to 100 mol%) with respect to the entire dicarboxylic acid unit (A). Mol% or more (for example, 30 to 99 mol%), preferably 40 mol% or more (for example, 50 to 97 mol%), more preferably 60 mol% or more (for example, 70 to 95 mol%), particularly 80 mol%. The above may be sufficient (for example, 90 mol% or more), and may be substantially about 100 mol%. If the proportion of the first dicarboxylic acid unit (A1) is too small, the heat resistance and refractive index may be lowered, or birefringence may not be reduced.

Second dicarboxylic acid unit (A2)
In addition, as long as the dicarboxylic acid unit (A) is within a range that does not impair the effects of the present invention, the other dicarboxylic acid unit (second dicarboxylic acid unit (A2) not belonging to the range of the first dicarboxylic acid unit). May be included. The second dicarboxylic acid component (A2) for forming the second dicarboxylic acid unit (A2) typically includes, for example, an aliphatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, and an aromatic dicarboxylic acid. Components (excluding the first dicarboxylic acid component) and the like.

Examples of the aliphatic dicarboxylic acid component include saturated aliphatic dicarboxylic acid [oxalic acid, alkane dicarboxylic acid (for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decane). C _1-18 alkane-dicarboxylic acid such as dicarboxylic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid, etc., preferably C _1-12 alkane-dicarboxylic acid etc.]]; unsaturated aliphatic dicarboxylic acid (eg, maleic acid, fumaric acid, etc.) C _2-10 alkene-dicarboxylic acid such as acid and itaconic acid); and ester-forming derivatives thereof.

Examples of the alicyclic dicarboxylic acid component include saturated alicyclic dicarboxylic acids [for example, cycloalkane dicarboxylic acids (for example, C _5-10 cycloalkane-dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid), crosslinked cyclic Cycloalkane dicarboxylic acids (eg, dicalins such as decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.)]; unsaturated alicyclic dicarboxylic acid components [eg, cyclo alkene dicarboxylic acids (e.g., C _5-10 cycloalkenes such as cyclohexene dicarboxylic acid - dicarboxylic acid); crosslinked cyclic cyclo alkene dicarboxylic acids (e.g., di- or tri-cyclo alkene dicarboxylic acid, such as norbornene dicarboxylic acid), etc.]; Beauty such ester-forming derivatives.

  Aromatic dicarboxylic acids (excluding the first dicarboxylic acid component) can be broadly classified into, for example, arene dicarboxylic acids, dicarboxylic acids having a diaryl skeleton, dicarboxylic acids having a fluorene skeleton, and the like.

Examples of the arene dicarboxylic acid include benzene dicarboxylic acids [for example, benzene dicarboxylic acid (for example, phthalic acid, isophthalic acid, terephthalic acid); alkylbenzene dicarboxylic acid (for example, methyl terephthalic acid, 4-methylisophthalic acid, 5-methylisophthalic acid). C _1-4 alkyl-benzenedicarboxylic acids such as acids, etc.]]; polycyclic arene dicarboxylic acids {eg, condensed polycyclic arene dicarboxylic acids [eg, naphthalenedicarboxylic acid (eg, 1,2-naphthalenedicarboxylic acid, It has two carboxyl groups in different rings such as 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, etc. Naphthalene dicarboxylic Acid; naphthalenedicarboxylic acid having two carboxyl groups in the same ring such as 1,2-naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid), condensed polycyclic C _10- such as anthracene dicarboxylic acid and phenanthrenedicarboxylic acid ₁₈ arene-dicarboxylic acids, preferably fused polycyclic C _10-14 arene-dicarboxylic acids and the like]; ring assembled arene dicarboxylic acids (eg, 2,2′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 4 , 4′-biphenyldicarboxylic acid and the like bi-C _6-10 arene-dicarboxylic acid and the like) and the like, and ester-forming derivatives thereof.

Examples of the dicarboxylic acid having a diaryl skeleton include diarylalkane dicarboxylic acids (for example, diC _6-10 aryl C _1-6 alkane-dicarboxylic acids such as 4,4′-diphenylmethanedicarboxylic acid); diaryl ketone dicarboxylic acids [ For example, di (C _6-10 aryl) ketone-dicarboxylic acid and the like such as 4.4′-diphenyl ketone dicarboxylic acid]; and ester-forming derivatives thereof.

Examples of the dicarboxylic acid having a fluorene skeleton include 9,9-bis (carboxyalkyl) fluorene [for example, 9,9-bis (2-carboxyethyl) fluorene, 9,9-bis (2-carboxypropyl) fluorene, etc. 9,9-bis (carboxyC _2-6 alkyl) fluorene etc.]; 9- (dicarboxyalkyl) fluorene [eg 9- (1,2-dicarboxyethyl) fluorene, 9- (2,3-diene) 9- (dicarboxy C _2-8 alkyl) fluorene and the like such as carboxypropyl) fluorene]; 9,9-bis (carboxyaryl) fluorene [eg, 9,9 such as 9,9-bis (4-carboxyphenyl) fluorene and the like. 9- bis (carboxy _{C 6-10} aryl) fluorene]; dicarboxylate fluorene (example If, 2,7-carboxymethyl fluorene); 9,9-dialkyl - dicarboxylate fluorene (e.g., 2,7-dicarboxy-9,9-dimethyl fluorene such as _{9,9-di-C 1-10} alkyl - Dicarboxyfluorene and the like); and ester-forming derivatives thereof.

  These second dicarboxylic acid units (A2) may be used alone or in combination of two or more. By using these second dicarboxylic acid units (A2), characteristics such as heat resistance, refractive index, and birefringence can be adjusted according to applications. Among these second dicarboxylic acid units (A2), in applications where low birefringence is important, alicyclic dicarboxylic acid units, dicarboxylic acid units having a fluorene skeleton [for example, 9,9-bis (carboxyalkyl) fluorene , Units derived from 9,9-bis (carboxyaryl) fluorene, etc.] are preferred, and aromatic dicarboxylic acid units are preferred in applications where high refractive index and heat resistance are important. The dicarboxylic acid unit (A) may not contain an aliphatic dicarboxylic acid unit.

  The ratio of the second dicarboxylic acid unit (A2) may be, for example, 50 mol% or less (for example, 0.1 to 50 mol%), preferably 30 with respect to the entire dicarboxylic acid unit (A). It may be about mol% or less, more preferably about 10 mol% or less (for example, 5 mol% or less).

(Diol unit (B))
First diol unit (B1)
The diol unit (B) may include, for example, a first diol unit (B1) represented by the following formula (B1).

Wherein Z is independently an arene ring, R ⁶ and R ⁷ are each independently a substituent, A ¹ is each independently a linear or branched alkylene group, and p is each independently 0 -4, q are each independently an integer of 0 or more, and r are each independently an integer of 0 or more).

  In the formula (B1), examples of the arene ring (aromatic hydrocarbon ring) represented by the ring Z include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, and the like. The arene ring includes a condensed polycyclic arene ring (condensed polycyclic aromatic hydrocarbon ring), a ring assembly arene ring (ring assembly aromatic hydrocarbon ring) and the like.

Examples of the condensed polycyclic arene ring include a condensed bicyclic arene ring (for example, a condensed bicyclic C _10-16 arene ring such as a naphthalene ring and an indene ring), and a condensed tricyclic arene ring (for example, an anthracene ring). And condensed bi- to tetra-cyclic arene rings and the like. Preferred ring-fused polycyclic arene rings include condensed polycyclic C _10-16 arene rings such as naphthalene rings and anthracene rings (preferably fused polycyclic C _10-14 arene rings), and in particular naphthalene rings Is preferred.

Examples of the ring assembly arene ring include a bearene ring (for example, a bi-C _6-12 arene ring such as a biphenyl ring, a binaphthyl ring, a phenylnaphthalene ring (a 1-phenylnaphthalene ring, a 2-phenylnaphthalene ring, etc.), a tellarene ring ( For example, a tel C _6-12 arene ring such as a terphenylene ring) can be exemplified. A preferable ring assembly arene ring includes a bi-C _6-10 arene ring, and a biphenyl ring is particularly preferable.

The types of the two rings Z may be the same or different from each other, and are usually often the same. Among the rings Z, C _6-12 arene rings such as a benzene ring, naphthalene ring and biphenyl ring are preferable, and among them, a C _6-10 arene ring such as a benzene ring and a naphthalene ring (particularly a benzene ring) is preferable.

  In addition, the substitution position of the ring Z couple | bonded with 9-position of a fluorene ring is not specifically limited. For example, when ring Z is a benzene ring, it may be in any position, and when ring Z is a naphthalene ring, it may be in either the 1-position or 2-position, and ring Z is a biphenyl ring. In this case, the position may be any one of 2-position, 3-position and 4-position.

Examples of the substituent represented by R ⁶ include a hydrocarbon group [for example, an alkyl group (for example, a linear or branched group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, etc. Chain C _1-6 alkyl group etc.), aryl group (eg C _6-10 aryl group such as phenyl group etc.)], cyano group, halogen atom (eg fluorine atom, chlorine atom, bromine atom etc.) etc. Is mentioned. Of these groups R ¹ , an alkyl group (for example, a linear or branched C _1-4 alkyl group), a cyano group, and a halogen atom are preferable, and an alkyl group (particularly, a C _1-4 such as a methyl group). An alkyl group) is preferred.

The substitution number p of the group R ⁶ is, for example, an integer of about 0 to 3, preferably an integer of about 0 to 2, more preferably 0 or 1, especially 0. In the two different benzene rings constituting the fluorene ring, the number of substitutions p may be the same or different from each other. The types of the groups R ⁶ substituted on the different benzene rings may be different from each other and are usually the same in many cases. When p is 2 or more, the types of two or more groups R ⁶ substituted on the same benzene ring may be the same or different from each other. The substitution position of the group R ⁶ is not particularly limited, and may be, for example, the 2-position to the 7-position (2-position, 3-position, 7-position, etc.) of the fluorene ring.

Examples of the substituent represented by R ⁷ include a group [—R ⁸ ], a group [—OR ⁸ ], a group [—SR ⁸ ], a group [— (C═O) —R ⁸ ], a group [— (C═O) —OR ⁸ ] (wherein R ⁸ represents a hydrocarbon group), a halogen atom, a nitro group, a cyano group, a substituted amino group, and the like. Examples of the hydrocarbon group represented by R ⁸ include the same groups as the hydrocarbon groups exemplified as R ^{5 in} the section of the formula (1). The group represented by R ⁷ [—R ⁸ ], group [—OR ⁸ ], group [—SR ⁸ ], group [— (C═O) —R ⁸ ], group [— (C═O) —OR. ⁸ ], a halogen atom, and a substituted amino group include, for example, the group [—R ⁵ ] and the group [—OR ⁵ ] exemplified as the substituents represented by R ¹ and R ² in the section of the formula (1). Group [—SR ⁵ ], group [— (C═O) —R ⁵ ], group [— (C═O) —OR ⁸ ], a halogen atom, a group similar to the substituted amino group, and the like.

Of these groups R ⁷ , typically, a halogen atom, a hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group), alkoxy group, acyl group, nitro group, cyano group, substituted amino group, etc. Is mentioned. Preferred groups R ⁷ include an alkyl group (such as a linear or branched C _1-6 alkyl group such as a methyl group), an aryl group (such as a C _6-12 aryl group such as a phenyl group), an alkoxy group (methoxy A linear or branched C _1-4 alkoxy group such as a group), in particular, an alkyl group (particularly a linear or branched C _1-4 alkyl group such as a methyl group), an aryl group (phenyl group) C _6-10 aryl groups such as

The number of substitutions q of the group R ⁷ can be appropriately selected according to the kind of the ring Z, and may be an integer of about 0 to 8, for example, preferably an integer of about 0 to 4 (for example, 0 to 3), More preferably, it may be an integer of about 0 to 2 (for example, 0 or 1), particularly 0. In two different rings Z, the type of the group R ⁷ and the number of substitutions q may be the same or different from each other. When the number of substitutions q is 2 or more, the types of the two or more groups R ⁷ substituted on the same ring Z may be the same or different from each other. The substitution position of the group R ⁷ is not particularly limited as long as it is substituted at a position other than the bonding position between the ring Z and the 9-position of the group [—O— (A ¹ O) _r —] and the fluorene ring. Good.

The linear or branched alkylene group represented by A ^1, for example, ethylene group, propylene group (1,2-propanediyl), trimethylene, 1,2-butanediyl group, a tetramethylene group Linear or branched C _2-6 alkylene group, preferably linear or branched C _2-4 alkylene group, more preferably linear or branched C _2-3 alkylene group (especially ethylene Group).

The repeating number (added mole number) r of the oxyalkylene group (OA ¹ ) may be an integer of 0 or more, and is, for example, an integer of about 0 to 15 (for example, 1 to 10), preferably 0 to 8 (for example, , An integer of about 1 to 6), more preferably an integer of about 0 to 4 (e.g., 1 to 2), particularly 0 or 1, and is preferably 1 from the viewpoint of polymerization reactivity. In the present specification and claims, the “repetition number (addition mole number) r” may be an average value (arithmetic average value, arithmetic average value) or an average addition mole number, and a preferred embodiment is as follows. May be the same as the preferred integer range. If the repetition number r is too large, the refractive index and heat resistance may be reduced. The two repeating numbers r may be the same or different, and when r is 2 or more, the types of the two or more oxyalkylene groups (OA ¹ ) may be different from each other, and are usually the same or In many cases, it is the same level. The types of oxyalkylene groups (OA ¹ ) bonded to different rings Z via an ether bond (—O—) may be the same or different from each other, but are usually the same.

The substitution position of the group [—O— (A ¹ O) _r —] is not particularly limited as long as it is a position other than the bonding position between the ring Z and the fluorene ring. For example, when the ring Z is a benzene ring, What is necessary is just to be in any position of the 2-6-position of the phenyl group bonded to the 9-position of the fluorene ring. When ring Z is a naphthalene ring, it is usually substituted at the 5- to 8-position of the naphthyl group bonded at the 1-position or 2-position with respect to the 9-position of the fluorene ring The 1-position or 2-position of the naphthalene ring is substituted with respect to the 9-position of the fluorene ring (substitution in terms of 1-naphthyl or 2-naphthyl). Substitution is preferably made in the 5-position, 2,6-position (particularly the 2,6-position) and the like. When ring Z is a biphenyl ring, it may be substituted at any of positions 2-6 and 2 ′ to 6′-position of the biphenyl ring. For example, 3-position or 4-position of biphenyl ring The position may be bonded to the 9-position of the fluorene, and when the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene, the substitution position of the carbonyl group is, for example, the 2-position of the biphenyl ring, 4- Position, 5-position, 6-position, 2′-position, 3′-position, 4′-position, preferably any position of 6-position, 4′-position ( In particular, it may be substituted at the 6-position). When the 4-position of the biphenyl ring is bonded to the 9-position of fluorene, the substitution position of the carbonyl group is the 2-position, 3-position, 2′-position, 3′-position, 4′- of the biphenyl ring. Any position of the position may be sufficient, and it may be preferably substituted at any position of 2-position and 4′-position (particularly 2-position).

  The first diol unit (B1) is a structural unit derived from (or corresponding to) the first diol component (B1). As a representative first diol component (B1), for example, the formula (B1) ), 9,9-bis [hydroxy (poly) alkoxyaryl] fluorenes corresponding to units in which r is 1 or more (for example, 1 to 10, preferably 1 to 6, more preferably about 1 to 3), etc. Is mentioned. In the present specification and claims, unless otherwise specified, “(poly) alkoxy” is used to mean including both an alkoxy group and a polyalkoxy group.

Examples of 9,9-bis [hydroxy (poly) alkoxyaryl] fluorenes include (B1-1) 9,9-bis [hydroxy (poly) alkoxyphenyl] fluorene {for example, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [4- (2- (2-hydroxyethoxy) ethoxy) phenyl] fluorene including 9,9-bis [hydroxy (mono- to _{deca) C 2-4} alkoxy - phenyl] fluorene}; (B1-2) 9,9-bis [hydroxy (poly) alkoxy - alkyl phenyl] fluorene {e.g., 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydro Shietokishi) -3,5-dimethylphenyl] fluorene such as 9,9-bis [hydroxy (mono- to _{deca) C 2-4} alkoxy - (mono or _{di) C 1-4} alkyl - phenyl] fluorene}; (B1 -3) 9,9-bis [hydroxy (poly) alkoxy-arylphenyl] fluorene {for example, 9,9-bis such as 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene [Hydroxy (mono-deca) C _2-4alkoxy- C _6-10aryl- phenyl] fluorene and the like}; (B1-4) 9,9-bis [hydroxy (poly) alkoxynaphthyl] fluorene {eg, 9,9 -Bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphth Le] fluorene such as 9,9-bis [hydroxy (mono- to _{deca) C 2-4} alkoxy - naphthyl] fluorene}, and the like.

These 1st diol units (B1) can also be used individually or in combination of 2 or more types. Of these first diol units (B1), (B1-1) 9,9-bis [hydroxy (poly) alkoxyphenyl] fluorene, (B1-4) 9,9-bis [hydroxy (poly) alkoxynaphthyl Fluorene and the like are preferred; among them, 9,9-bis [hydroxy (mono to hexa) C _2-4 alkoxyphenyl] fluorene such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9 9,9-bis [hydroxy (mono-hexa) C _2-4alkoxy- naphthyl] fluorene (especially 9,9-bis), such as 1,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene. [4- (2-hydroxyethoxy) phenyl] 9,9-bis fluorene [hydroxy (mono- to _{tri) C 2-3} alkoxyphenyl] Units derived from fluorene, etc.) are preferable.

  The diol unit (B) may not necessarily contain such a first diol unit (B1), but the refractive index and heat resistance can be improved without greatly increasing the birefringence of the polyester resin. Therefore, it is preferable that the first diol unit (B1) is included. The ratio of the 1st diol unit (B1) can be selected from the range of about 10-100 mol% (for example, 30-99 mol%) with respect to the whole diol unit (B), for example, 40-95, for example. The mol% (for example, 50 to 90 mol%), preferably 55 to 85 mol% (for example, 60 to 80 mol%), more preferably about 65 to 75 mol% may be used. If the proportion of the first diol unit (B1) is too small, the refractive index and heat resistance may be lowered.

  The polyester resin of the present invention has a high level of mutually conflicting properties such as high heat resistance and high refractive index and low birefringence by appropriately combining the dicarboxylic acid unit (A1) and the diol unit (B1). It can be satisfied. Therefore, the ratio of the 1st diol unit (B1) is the range of about 0.1-10 mol (for example, 0.2-5 mol) with respect to 1 mol of 1st dicarboxylic acid units (A1), for example. For example, 0.3-3 mol (e.g. 0.4-2 mol), preferably 0.5-1 mol (e.g. 0.55-0.9 mol), more preferably 0.6 About -0.8 mol (for example, 0.65-0.75 mol) may be sufficient.

  The polyester resin of the present invention may be formed by only the dicarboxylic acid unit (A1) and the diol unit (B1). However, from the viewpoint of improving (or improving) the polymerization reactivity and mechanical properties in a balanced manner, A structural unit (or polymerization component) may be included.

Second diol unit (B2)
The diol unit (B) may contain a second diol unit (B2) represented by the following formula (B2) in addition to the first diol unit (B1).

(In the formula, A ² represents a linear or branched alkylene group, and s represents an integer of 1 or more).

In the formula (B2), the alkylene group A ² may be the same as the group A ¹ described in the first diol unit (B1), including preferred embodiments.

The repeating number s of the oxyalkylene group (OA ² ) may be, for example, an integer of about 1 to 10, for example, an integer of about 1 to 5 (1 to 3), preferably 1 or 2, and more preferably. 1 may be sufficient. If the repetition number s is too large, the refractive index and heat resistance may be reduced.

As the second diol unit (B2), specifically, for example, alkanediol (for example, ethylene glycol, propylene glycol, trimethylene glycol (1,3-propanediol), 1,2-butanediol, 1,3 -Butanediol, tetramethylene glycol (1,4-butanediol), 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol, 1,6-hexanediol, 1, Linear or branched C _2-12 alkanediols such as 8-octanediol and 1,10-decanediol); polyalkylene glycols (or polyalkanediols) [for example, polyethylene glycol, polypropylene glycol, polytetramethylene Polyether such as ether glycol And a structural unit derived from the second diol component (B2) such as di- to tetra-C _2-4 alkane diol such as di-C _2-6 alkane diol, preferably diethylene glycol, triethylene glycol, dipropylene glycol, etc. It is done.

These 2nd diol units (B2) can also be utilized individually or in combination of 2 or more types. Of these second diol units (B2), preferably a linear or branched C _2-6 alkanediol (eg, ethylene glycol, propylene glycol, 1,4-butanediol, etc.), more preferably straight chain or branched-chain C _2-4 alkane diols, particularly, ethylene glycol, a linear or branched C _2-3 alkane diols, such as propylene glycol (especially, ethylene glycol) units derived from the preferred.

  By including such a second diol unit (B2), it is possible to improve the polymerization reactivity and improve properties such as mechanical properties (for example, flexibility) and moldability of the polyester resin.

  The ratio of the total amount of the first diol unit (B1) and the second diol unit (B2) is, for example, 10 mol% or more (for example, about 30 to 100 mol%) with respect to the entire diol unit (B). For example, 50 mol% or more (for example, about 60 to 99.9 mol%), preferably 70 mol% or more (for example, about 80 to 99 mol%), more preferably 90 mol% or more (for example, , About 90 to 95 mol%), or substantially 100 mol% [only the first diol unit (B1) and / or the second diol unit (B2)].

  When the diol unit (B) includes both the first diol unit (B1) and the second diol unit (B2), the ratio is, for example, the former / the latter (molar ratio) = 10/90 to 99.9. /0.1 (for example, 20/80 to 99/1) or so, for example, 30/70 to 97/3 (for example, 40/60 to 95/5), preferably 50/50 to It may be about 90/10 (for example, 55/45 to 85/15), more preferably about 60/40 to 80/20 (for example, 65/35 to 75/25).

(Third diol unit (B3))
In addition, if the diol unit (B) is a range that does not impair the effects of the present invention, it is further a diol unit (a third diol unit (B3) that does not belong to the range of the first and second diol units). May be included. Examples of the third diol unit (B3) include alicyclic diol [eg, cycloalkanediol (eg, C _5-10 cycloalkanediol such as cyclohexanediol); bis (hydroxyalkyl) cycloalkane (eg, Bis (hydroxyC _1-4 alkyl) C _5-10 cycloalkane etc. such as cyclohexanedimethanol; Hydrogenated aromatic diol described below (for example, hydrogenated bisphenol A etc.)]; Aromatic diol ( Except for the first diol component) [e.g., dihydroxyarenes (e.g., hydroquinone, resorcinol, etc.); araliphatic diols (e.g., benzenedimethanol); bisphenols (e.g., bisphenol A, bisphenol F, bisphenol AD) , Bisuf Nord C, bisphenol G, bisphenol S, etc.); biphenols (e.g., p, p'-biphenol, etc.), etc.]; and _{C 2-4} alkylene oxide (or alkylene carbonate, halo alkanol) adducts of these diol components [ For example, a unit derived from the third diol component (B3) such as an adduct in which about 2 to 10 mol of ethylene oxide is added to 1 mol of bisphenol A can be used.

  These 3rd diol units (B3) can also be used individually or in combination of 2 or more types. The proportion of the third diol unit (B3) may be, for example, 50 mol% or less (for example, 0.1 to 50 mol%), preferably 30 mol%, based on the entire diol unit (B). Hereinafter, it may be more preferably about 10 mol% or less (for example, 5 mol% or less).

[Production method and characteristics of polyester resin]
The production method of the polyester resin of the present invention may be a conventional method, for example, ester, by reacting the dicarboxylic acid component (A) containing at least the first dicarboxylic acid component (A1) with the diol component (B). It can be prepared by an exchange method, a melt polymerization method such as a direct polymerization method, a solution polymerization method or an interfacial polymerization method, and a melt polymerization method is preferred. The reaction may be performed in the presence or absence of a solvent depending on the polymerization method.

  The use ratio (or charge ratio) of the dicarboxylic acid component (A) and the diol component (B) is usually the former / the latter (molar ratio) = for example, 1 / 1.2 to 1 / 0.8, preferably 1. /1.1 to 1 / 0.9). In addition, in reaction, the usage-amount (use ratio) of each dicarboxylic acid component (A) and diol component (B) may be the same including the ratio and preferable aspect of each said dicarboxylic acid unit and diol unit, If necessary, each component or the like may be used in excess. For example, the second diol component (B2) such as ethylene glycol that can be distilled from the reaction system may be used in excess of the ratio (or introduction ratio) introduced into the polyester resin.

  The reaction may be performed in the presence of a catalyst. As the catalyst, a conventional esterification catalyst such as a metal catalyst can be used. Examples of metal catalysts include alkali metals (sodium, etc.); alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (manganese, zinc, cadmium, lead, cobalt, titanium, etc.); periodic table group 13 metals (Aluminum etc.); Metal compounds containing Periodic Table Group 14 metals (Germanium etc.); Periodic Table Group 15 metals (antimony etc.) are used. The metal compound may be, for example, an alkoxide, an organic acid salt (acetate, propionate, etc.), an inorganic acid salt (borate, carbonate, etc.), a metal oxide, etc., and these hydrates. It may be. Typical metal compounds include, for example, germanium compounds (eg, germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, germanium-n-butoxide, etc.); antimony compounds (eg, antimony trioxide, antimony acetate) Titanium compounds (eg, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, titanium oxalate, potassium potassium oxalate); manganese compounds (manganese acetate, 4 water) Examples thereof include calcium compounds (calcium acetate monohydrate, etc.).

These catalysts can be used alone or in combination of two or more. When using a plurality of catalysts, each catalyst can be added according to the progress of the reaction. Of these catalysts, manganese acetate tetrahydrate, calcium acetate monohydrate, germanium dioxide and the like are preferable. The amount of the catalyst used is, for example, 0.01 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol, preferably 0.1 × 10 ⁻⁴ to 40 × 10 ^{−4 with} respect to 1 mol of the dicarboxylic acid component (A). It may be about a mole.

In addition, the reaction may be stabilized with a heat stabilizer (for example, a phosphorus compound such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, phosphorous acid, trimethyl phosphite, triethyl phosphite) or an antioxidant as necessary. You may carry out in presence of an agent. The amount of the heat stabilizer used is, for example, 0.01 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol, preferably 0.1 × 10 ⁻⁴ to 40 × 10, with respect to 1 mol of the dicarboxylic acid component (A). ^{About -4} mol may be sufficient.

The reaction may be performed in air, or may be generally performed in an inert gas atmosphere (for example, nitrogen; a rare gas such as helium or argon). The reaction can also be performed under reduced pressure (for example, about 1 × 10 ² to 1 × 10 ⁴ Pa). The reaction temperature can be selected according to the polymerization method. For example, the reaction temperature in the melt polymerization method may be about 150 to 300 ° C, preferably about 180 to 290 ° C, and more preferably about 200 to 280 ° C.

  Since the polyester resin of the present invention contains the first dicarboxylic acid unit (A1) having a triptycene skeleton, the polyester resin has high heat resistance and a high refractive index, and surprisingly has little optical anisotropy. (Or orientation treatment) shows low birefringence. Therefore, the mutually conflicting characteristics of high heat resistance, high refractive index, and low birefringence can be improved in a balanced manner.

  The glass transition temperature Tg of the polyester resin can be selected from the range of, for example, about 100 to 250 ° C. (for example, 120 to 230 ° C.), for example, 130 to 200 ° C. (for example, about 135 to 190 ° C.), preferably 140 to It may be about 180 ° C. (for example, 145 to 175 ° C.), more preferably about 150 to 170 ° C. (for example, 155 to 165 ° C.). If the glass transition temperature Tg is too low, the resin may be deformed or discolored (or colored) during use. If the Tg is too high, the surface of the molded product (for example, an optical lens) can be formed smoothly. There is a risk of disappearing.

  The weight average molecular weight Mw of the polyester resin can be selected from the range of, for example, about 10,000 to 200,000 in terms of polystyrene, for example, 15000 to 100,000, preferably 20000 to 80000, more preferably 25000 to 60000 (for example, 30000 to 40000). It may be about 35000 to 50000 (for example, 40000 to 45000). The number average molecular weight Mn of the polyester resin can be selected from a range of, for example, about 5000 to 500000 (for example, 7000 to 300000) in terms of polystyrene, for example, 8000 to 200000 (for example, 10000 to 100000), preferably 15000. -80000 (for example, 18000-50000), more preferably about 20000-30000. The molecular weight distribution Mw / Mn of the polyester resin is, for example, 1 to 5 (for example, 1.1 to 4), preferably 1.2 to 3 (for example, 1.3 to 2.8), and more preferably 1.5. About 2.5 (for example, 1.7 to 2.3) may be sufficient. In addition, the weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution Mw / Mn can be measured in terms of polystyrene by gel permeation chromatography (GPC).

  The refractive index of the polyester resin is, for example, 1.55 to 1.8 (for example, 1.57 to 1.7), preferably 1.59 to 1.68 (for example, 1.5) at a temperature of 20 ° C. and a wavelength of 589 nm. 6 to 1.66), more preferably about 1.61 to 1.65 (for example, 1.62 to 1.64).

  The Abbe number of the polyester resin is, for example, 30 or less (for example, 17 to 28), preferably 27 or less (for example, 20 to 26), more preferably 25 or less (for example, 22 to 25) at a temperature of 20 ° C. There may be.

The birefringence of the polyester resin may be evaluated by the birefringence (3-fold birefringence) of a stretched film obtained by uniaxially stretching a film formed of polyester alone at a stretch ratio of 3 times. Birefringence (3-fold birefringence) is expressed by the absolute value of the difference between the refractive index in the stretching direction and the refractive index in the direction perpendicular to this direction in the film plane. Therefore, the triple birefringence of the stretched film prepared under stretching conditions (glass transition temperature Tg + 10) ° C. and stretching conditions of 25 mm / min is, for example, 100 × 10 ⁻⁴ or less at a measurement temperature of 20 ° C. and a wavelength of 600 nm. (e.g., 0.001 × ¹⁰ -4 ~50 × ¹⁰ about ^-4) can be selected from the range of, for example, 30 × ^{10 -4} or less (e.g., 1 × ¹⁰ -4 ~25 × ¹⁰ about ^-4), preferably Is 20 × 10 ⁻⁴ or less (for example, about 5 × 10 ⁻⁴ to 18 × 10 ⁻⁴ ), more preferably 15 × 10 ⁻⁴ or less (for example, about 10 × 10 ^{−4 to} 14 × 10 ⁻⁴ ). There may be.

  In the present specification and claims, glass transition temperature Tg, weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution Mw / Mn, refractive index, Abbe number, and triple birefringence are described in the examples described later. It can be measured by the method described.

[Molded body]
Since the molded article of the present invention contains the polyester resin and has excellent heat resistance and optical properties (high refractive index, low birefringence, etc.), such as an optical film (or optical sheet), an optical lens, etc. It can be used as an optical member. The shape of the molded body is not particularly limited. For example, a one-dimensional structure (for example, a linear shape, a fiber shape, etc.), a two-dimensional structure (for example, a film shape, a sheet shape, a plate shape, etc.), a three-dimensional structure. (For example, a concave or convex lens shape, a rod shape, a hollow shape (tubular shape, etc.)) and the like.

  The molded article of the present invention has various additives [for example, fillers or reinforcing agents, colorants (for example, dyes and pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (for example, antioxidants, ultraviolet rays). Absorbents, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents (eg silicone oil, silicone rubber, various types) Plastic powders, various engineering plastic powders, etc.), heat resistance improvers (eg, sulfur compounds, polysilanes, etc.), carbon materials, etc.]. These additives may be used alone or in combination of two or more.

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

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

  The thickness (average thickness) of such a 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.

  Such a film (optical film) can be produced by forming (or molding) the polyester resin using a conventional film forming method, casting method (solvent casting method), melt extrusion method, calendar method, or the like. .

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

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

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

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

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

[Evaluation method]
(NMR)
The NMR spectrum was measured using “AVANCE III HD (300 MHz)” manufactured by Bruker Biospin.

(Glass transition temperature Tg)
Using a differential scanning calorimeter ("EXSTAR6000 DSC6220 ASD-2" manufactured by SII Nano Technology Co., Ltd.), the measurement was performed in a nitrogen atmosphere at a heating rate of 10 ° C / min in the range of 20 to 220 ° C.

(Molecular weight)
Using gel permeation chromatography (manufactured by Tosoh Corporation, “HLC-8320GPC”), the sample was dissolved in chloroform, and the weight average molecular weight Mw and molecular weight distribution Mw / Mn were measured in terms of polystyrene.

(Refractive index nD)
The sample was press-molded at 200 to 240 ° C. to form a film having a thickness of 200 to 300 μm. This film was cut into a strip of 20 to 30 mm × 10 mm to obtain a test piece. About the obtained test piece, using a multi-wavelength Abbe refractometer ("DR-M4 (Circulation type constant temperature water bath 60-C3)" manufactured by Atago Co., Ltd.), a measurement temperature of 20 ° C and a measurement wavelength of 589 nm (d line) Measured under conditions.

(Abbe number)
About the test piece used for the measurement of the refractive index, using a multi-wavelength Abbe refractometer ("DR-M4 (Circulation type constant temperature water bath 60-C3)" manufactured by Atago Co., Ltd.), the measurement temperature is 20 ° C and the contact liquid is used. Using diiodomethane, the refractive indices nF, nD, and nC at the measurement wavelengths of 486 nm (F line), 589 nm (D line), and 656 nm (C line) were measured and calculated according to the following equations.

    Abbe number = (nD-1) / (nF-nC).

(Birefringence (or triple birefringence))
The sample was press-molded at 200 to 240 ° C. to form a film having a thickness of 200 to 600 μm. This film was cut into a strip of 10 mm × 50 mm, and uniaxially stretched at 25 mm / min and a stretching ratio of 3 times under a temperature condition of Tg + 10 ° C. to obtain a test piece. The stretched test piece was measured for retardation using a parallel Nicol rotation method under the conditions of a measurement temperature of 20 ° C. and a measurement wavelength of 600 nm using “RETS-100” manufactured by Otsuka Electronics Co., Ltd. Calculated by dividing by thickness.

[Synthesis Example 1] Synthesis of 1,4-dihydroxytriptycene Anthracene (89.1 g, 50.0 mmol) and p-benzoquinone (54.6 g, 50.5 mmol) were heated in chlorobenzene (400 mL) and refluxed. And stirred. After refluxing for 4 hours, the mixture was cooled to room temperature, the solid was filtered off, and washed with 500 mL of warm water. This solid was dried under vacuum (80 ° C., 4 hours), and hydrobromic acid (20 drops) was added under reflux in acetic acid (710 g). After cooling, the solid was filtered off and dried in vacuo to give a white solid (116 g, 39 mmol, yield 78%).

[Example 1] Synthesis of 1,4-bis (methoxycarbonylmethoxy) triptycene To a solution of 1,4-dihydroxytriptycene (28.6 g, 100 mmol) in N, N-dimethylformamide (DMF, 250 mL) at 55 ° C. Added potassium carbonate (30.45 g, 220 mmol) and stirred for 30 minutes. Thereafter, methyl bromoacetate (33.7 g, 220 mmol) was added dropwise at 80 ° C., and the mixture was heated and stirred for 5 hours. After cooling, the reaction product was filtered and added to water (1500 mL). The resulting precipitate was filtered off and recrystallized with toluene (30.6 g, yield 71%).

¹ H NMR (300 MHz, DMSO-d ₆ ) δ (ppm) = 3.68 (s, 6H), 4.81 (s, 4H), 5.94 (s, 2H), 6.57 (s, 2H ), 7.00 (dd, J = 3.2, 5.3 Hz, 4H), 7.45 (dd, J = 3.2, 5.3 Hz, 4H).

[Example 2] Synthesis of polyester resin In a reactor, 19.38 g of 1,4-bis (methoxycarbonylmethoxy) triptycene obtained in Example 1, 9,9-bis [4- (2-hydroxyethoxy) phenyl] 13.8 g of fluorene (BPEF), 6.42 g of ethylene glycol (EG), and 7.4 mg of manganese acetate tetrahydrate were added, and the mixture was gradually heated to 240 ° C. and stirred to conduct a transesterification reaction. After removing the methanol produced by the transesterification reaction, add 15.8 mg of trimethyl phosphate and 14.1 mg of germanium oxide, gradually increase the temperature to 270 ° C. and 120 Pa, depressurize, and perform polycondensation until a predetermined stirring torque is reached. went.

When the obtained pellet was analyzed by ¹ H-NMR, 100 mol% of the dicarboxylic acid unit introduced into the polyester resin was derived from 1,4-bis (methoxycarbonylmethoxy) triptycene, 70 mol% was derived from BPEF and 30 mol% was derived from EG.

The obtained polyester resin has an Mw of 42900 (Mw / Mn = 1.9), a Tg of 160.2 ° C., an nD (20 ° C.) of 1.6327, an Abbe number of 25, and a birefringence of 13 when stretched by 13 times. × 10 ^-4 .

[Comparative Example 1]
Polycondensation was performed in the same manner as in Example 2 except that an equimolar amount of dimethyl terephthalate (DMT) was used instead of 1,4-bis (methoxycarbonylmethoxy) triptycene.

The obtained pellet was analyzed by ¹ H-NMR. As a result, 100 mol% of the dicarboxylic acid units introduced into the polyester resin were derived from DMT, 70 mol% of the introduced diol units were derived from BPEF, and 30 mol%. Was derived from EG.

Mw of the obtained polyester resin is 36000 (Mw / Mn = 2.1), Tg is 143.9 ° C., nD (20 ° C.) is 1.6332, Abbe number is 23, and birefringence at 3 times stretching is 45. × 10 ^-4 .

  The novel compound having a triptycene skeleton of the present invention is useful as a polymerization component (monomer or monomer) of a resin (for example, polyester resin, polyamide resin, etc.).

  The polyester resin containing the compound as a polymerization component has not only excellent optical properties such as high refractive index, low birefringence, and high transparency, but also high heat resistance. Therefore, the polyester resin (or resin composition thereof) of the present invention includes, for example, paints, inks, adhesives, pressure-sensitive adhesives, resin fillers, antistatic agents, protective films (such as protective films for electronic devices), Electronic materials (charging trays, conductive sheets, carrier transport agents, light emitters, organic photoreceptors, thermal recording materials, hologram recording materials, etc.), electrical / electronic components or equipment (inkjet printers, digital paper, organic semiconductor lasers, dye sensitization) Resin for type solar cell, photochromic material, organic EL element, etc., resin for mechanical parts or equipment (automobile, aerospace material, sensor, sliding member, etc.), optical member (optical film (or optical sheet)), It can be suitably used for optical lenses, optical fibers, optical discs, and the like. In particular, since the polyester resin of the present invention is excellent in optical characteristics, it is useful for constituting (or forming) a molded article (optical member such as an optical film or an optical lens) for optical use.

  Examples of the optical film include a protective film (liquid crystal protective film, etc.), a polarizing film (and a polarizing element and a polarizing plate protective film constituting the protective film), a retardation film, an alignment film (alignment film), and a viewing angle expansion (compensation). Film, diffusion 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 film (ACF), electromagnetic wave shielding (EMI) film, film for electrode substrate, film for color filter substrate, barrier film, color filter layer, black matrix layer, adhesive layer or separation between optical films Mold layers, etc., especially device displays (liquid crystal, organic L is useful as an optical film for use in, etc.). Specific examples of the display member (or display) provided with such an optical film include, for example, personal computer monitors, televisions, information terminals (for example, mobile phones such as smartphones, tablet terminals, etc.), and game machines. FPD devices (for example, LCD, PDP, etc.) such as car navigation systems and touch panels.

  Examples of the optical lens include a spectacle lens, a contact lens, a camera lens, a VTR zoom lens, a pickup lens, a Fresnel lens, a solar condenser lens, an objective lens, a rod lens array, and the like. A lens having a low Abbe number [for example, a lens mounted on a small device having a camera function (or a mobile device such as a mobile phone or a digital camera). In particular, since the polyester resin of the present invention has high heat resistance, it can be suitably used even for applications that are assumed to be used in a high-temperature environment (for example, in-vehicle lenses).

Claims (10)

A compound represented by the following formula (1).

[Wherein R ¹ and R ² are each independently a substituent, R ³ is each independently a hydroxyl group, a group [—OR ⁴ ] (wherein R ⁴ represents a hydrocarbon group) or a halogen atom, m1 is each independently an integer of 0 to 4, m2 is an integer of 0 to 2, and n is an integer of 1 or more. ] In Formula (1), R ¹ and R ² are each independently a group [—R ⁵ ], a group [—OR ⁵ ], a group [—SR ⁵ ], a group [— (C═O) —R ⁵ ], A group [— (C═O) —OR ⁵ ] (wherein R ⁵ represents a hydrocarbon group), a halogen atom, a nitro group, a cyano group or a substituted amino group, and m1 each independently represents 0 to 2 The compound according to claim 1, which is an integer, m2 is 0 or 1, and n is an integer of 1 to 6. The method of manufacturing the compound of Claim 1 or 2 by making the compound represented by following formula (2), and the compound represented by following formula (3) react in presence of a base.

(In the formula, X represents a halogen atom, and R ¹ , R ² , R ³ , m1, m2 and n are the same as in formula (1) in claim 1). A polyester resin formed of a dicarboxylic acid unit (A) and a diol unit (B), wherein the dicarboxylic acid unit (A) is a first dicarboxylic acid unit (A1) represented by the following formula (A1). Polyester resin containing at least.

(Wherein R ¹ , R ² , m1, m2 and n are the same as in formula (1) according to claim 1). In the formula (A1), R ¹ and R ² are each independently a group [—R ⁵ ], a group [—OR ⁵ ], a group [—SR ⁵ ], a group [— (C═O) —R ⁵ ], A group [— (C═O) —OR ⁵ ] (wherein R ⁵ represents a hydrocarbon group), a halogen atom, a nitro group, a cyano group or a substituted amino group, and m1 each independently represents 0 to 2 The polyester resin according to claim 4, wherein m2 is an integer, 0 or 1, and n is an integer of 1 to 6. The polyester resin according to claim 4 or 5, wherein the diol unit (B) includes a first diol unit (B1) represented by the following formula (B1).

Wherein Z is independently an arene ring, R ⁶ and R ⁷ are each independently a substituent, A ¹ is each independently a linear or branched alkylene group, and p is each independently 0 -4, q are each independently an integer of 0 or more, and r are each independently an integer of 0 or more.) In the formula (B1), Z is each independently a C _6-14 arene ring, R ⁶ is each independently a hydrocarbon group, a cyano group or a halogen atom, R ⁷ is each independently a group [—R ⁸ ], Group [—OR ⁸ ], group [—SR ⁸ ], group [— (C═O) —R ⁸ ] (wherein R ⁸ represents a hydrocarbon group), a halogen atom, a nitro group, a cyano group or A substituted amino group, A ¹ is each independently a linear or branched C _2-6 alkylene group, p is each independently an integer of 0-2, q is each independently an integer of 0-2, r Are each independently an integer of 0 to 10. The polyester resin according to any one of claims 4 to 6. The diol unit (B) further includes a second diol unit (B2) represented by the following formula (B2), and the ratio between the first diol unit (B1) and the second diol unit (B2) is: The former / the latter (molar ratio) = 50/50 to 99/1. The polyester resin according to claim 6 or 7.

(In the formula, A ² represents a linear or branched alkylene group, and s represents an integer of 1 or more.)   The molded object shape | molded with the polyester resin in any one of Claims 4-8.   The molded article according to claim 9, which is an optical film or an optical lens.