KR102341901B1 - Polycondensation resin and optical film comprising same - Google Patents

Abstract

An object of the present invention is to provide a resin having excellent balance in various properties such as optical properties, heat resistance, mechanical properties, and thermal stability, and an optical film and retardation film obtained using the same. The present invention relates to a polycondensed resin having a repeating structural unit containing an aromatic structure, wherein the content of the aromatic structure in the repeating structural unit satisfies the following formula (I) and has a structural unit. will be.
5 ≤ A ≤ -22.5 × B + 38.3 (I)
provided that 0.75 ≤ B ≤ 0.93
A: Content of aromatic structure in the repeating structural unit constituting the resin [mass %]
B: Ratio (R450/R550) of the retardation (R450) at 450 nm and the retardation (R550) at 550 nm of the stretched film produced from the resin

Description

Polycondensation-based resin and optical film comprising the same TECHNICAL FIELD

The present invention relates to a resin excellent in various properties such as optical properties, heat resistance, mechanical properties, and thermal stability, and an optical film obtained using the same.

The present invention also relates to a novel trifluorenediester, an oligofluorenediester composition comprising the same, and a resin composition containing a polymer having a repeating unit derived from the novel trifluorenediester, and elongation obtained using the same It relates to films, circular polarizers and image display devices.

The present invention also relates to a novel oligofluorene, an oligofluorene composition containing the same, and a resin composition obtained by using the oligofluorene.

The present invention also relates to an oligofluorenediester and a method for producing a resin composition using the same.

Recently, the demand for optical transparent resins used in optical systems such as optical lenses, optical films, and optical recording media is increasing. Among them, the spread of thin flat panel displays (FPDs) typified by liquid crystal displays and organic EL displays is particularly remarkable, and the purpose of improving display quality such as improvement of contrast and coloration, enlargement of viewing angle, and prevention of external light reflection Various optical films have been developed and used.

In the organic EL display, a quarter-wave plate for preventing reflection of external light is used. In order to suppress coloration and enable clean black display, the retardation film used for the quarter wave plate is required to have a broadband wavelength dispersion characteristic that can obtain ideal retardation characteristics at each wavelength in the visible region. .

As a thing corresponding to this, it is disclosed that, for example, a broadband retardation film is obtained by laminating|stacking two types of retardation films from which birefringent wavelength dispersion|distribution differs so that each slow axis may be orthogonal (patent document 1). Moreover, the method obtained by laminating|stacking a 1/2 wave plate and a 1/4 wave plate so that each slow axis may become a specific arrangement|positioning is also disclosed (patent document 2). In addition, a broadband retardation film made of cellulose acetate having a specific degree of acetylation (Patent Document 3), or a polycarbonate copolymer comprising a bisphenol structure having a fluorene ring in a side chain, and a reverse wavelength at which the retardation becomes smaller as the wavelength becomes shorter. A retardation film exhibiting dispersibility is disclosed (Patent Document 4).

In recent years, many resins which have the said fluorene ring in a side chain have been reported, and it is proposed as a material useful for an optical use, taking advantage of characteristics, such as the optical characteristic and heat resistance derived from a fluorene ring (patent document 5).

These resins often contain relatively easily available monomers, such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. used (Patent Documents 6 and 7).

Also, a resin having a new structure has been developed. The diamine compound which has a fluorene ring in a side chain is disclosed by patent document 8, Furthermore, the stretched film of the polyimide resin using the same is described. Patent Document 9 discloses a polycarbonate resin using a fluorene compound having no aromatic ring on the main chain. Patent Document 10 discloses a dihydroxy compound or a diester compound having two fluorene rings in the same molecule, and also describes a stretched film of a polyester resin using the same.

In Patent Documents 11 and 12, by controlling the content of the repeating unit having a fluorene ring in the polycarbonate resin to a specific range, the stretched film made of the polycarbonate resin exhibits reverse wavelength dispersion in which the retardation becomes smaller as the wavelength becomes shorter. Therefore, what has excellent performance as a retardation film is disclosed. The retardation film exhibiting so-called reverse wavelength dispersion, in which the retardation becomes smaller as the wavelength becomes shorter, can obtain ideal retardation characteristics at each wavelength in the visible region, and is useful as a circular polarizing plate to prevent external light reflection of an image display device, correct viewing angle, etc. .

Examples of the dihydroxy compound having a fluorene ring in the side chain include 9,9-bis[4-(2-hydroxyethoxy)phenyl)fluorene and 9,9-bis described in Patent Documents 11 and 12. (4-hydroxy-3-methylphenyl)fluorene is frequently used. Patent Document 13 discloses a diester compound having two fluorene rings in the same molecule, and also describes a polyester resin using the same. Patent Document 10 discloses a dihydroxy compound or a diester compound having two fluorene rings in the same molecule, and also describes a stretched film of a polyester resin using the same.

In particular, since polyester using a difluorene compound having two fluorene rings has a relatively high glass transition temperature and negative birefringence, it is known that it is useful for a reflective polarizing plate use (Patent Document 10). . Moreover, it is known to use together two types of difluorene compounds from which the functional group of the terminal differs as a resin raw material.

On the other hand, in the use of a protecting group of an amino group in peptide solid-phase synthesis, a difluorene compound having only one reactive functional group at the terminal is known (Patent Document 14, Non-Patent Document 1).

In Patent Documents 11 and 12, by controlling the content of the repeating unit having a fluorene ring in the polycarbonate resin to a specific range, the stretched film made of the polycarbonate resin exhibits reverse wavelength dispersion in which the retardation becomes smaller as the wavelength becomes shorter. Therefore, what has excellent performance as a retardation film is disclosed. The retardation film exhibiting so-called reverse wavelength dispersion, in which the retardation becomes smaller as the wavelength becomes shorter, can obtain ideal retardation characteristics at each wavelength in the visible region, and is useful as a circular polarizing plate to prevent external light reflection of an image display device, correct viewing angle, etc. .

Examples of the dihydroxy compound having a fluorene ring in the side chain include 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and 9,9-bis described in Patent Documents 11 and 12. (4-hydroxy-3-methylphenyl)fluorene is frequently used.

On the other hand, although it is not for reverse wavelength dispersion use, when a specific diester compound is used as a raw material for polyester carbonate, it is known that the content of chlorine contained in the compound is set to a predetermined amount or less from the viewpoint of light transmittance (patent literature 15).

Japanese Patent Laid-Open No. 5-27118 Japanese Patent Laid-Open No. 10-68816 Japanese Laid-Open Patent Publication No. 2000-137116 Japanese Patent Publication No. 3325560 Japanese Patent Laid-Open No. 10-101786 Japanese Patent Publication No. 5119250 Japanese Patent Publication No. 5204200 Japanese Laid-Open Patent Publication No. 2008-112124 Japanese Patent Laid-Open No. 2008-222965 Specification of US Patent Application Publication No. 2012/0170118 International Publication No. 2006/041190 International Publication No. 2011/149073 US Patent Publication No. 3324084 International Publication No. 1991/08190 Japanese Laid-Open Patent Publication No. 2-20518

Synthesis, 1992, 819.

The development of the FPD field is dazzling, and the retardation film is required to improve additional optical properties, quality, reliability, etc., or to make the film thinner. Moreover, there are also demands such as cost reduction of materials and improvement of productivity in each process such as film forming, stretching, and lamination. In connection with it, it came to be calculated|required for retardation film to have various characteristics. For example, as a material used for retardation film, it has various characteristics such as low photoelastic coefficient, high heat resistance, melt processability, mechanical strength, etc. while having the required wavelength dispersion, and also has large intrinsic birefringence, flexibility and It is excellent in stretchability and the material from which a high molecular orientation degree is obtained by extending|stretching is calculated|required.

However, in the method of laminating|stacking retardation film like patent document 1 or patent document 2, a polarizing plate will become thick. Moreover, each retardation film must be laminated|stacked so that a slow axis may become a specific arrangement|positioning, and there exists a problem that productivity and yield of a polarizing plate deteriorate. Although the retardation film of Patent Document 3 and Patent Document 4 has reverse wavelength dispersion and broadband retardation characteristics are obtained with one film, the cellulose acetate of Patent Document 3 has insufficient heat resistance and moisture absorption. There is a problem of generating image non-uniformity due to dimensional deformation by

It is known that the retardation film made of a polycarbonate resin having a fluorene ring of Patent Documents 4, 6, and 7 is useful as a retardation film showing reverse wavelength dispersion or a circular polarizing plate for preventing external light reflection of an image display device. However, as a result of investigations by the present inventors, the resin using 9,9-bis(4-hydroxy-3-methylphenyl)fluorene has a soft film, so it is difficult to draw a high degree of orientation, and 9,9-bis[ Although the resin using 4-(2-hydroxyethoxy)phenyl]fluorene was comparatively excellent in stretchability, it turned out that the photoelastic coefficient is slightly high, and it is inferior to the reliability under high temperature.

As a means for improving various characteristics, it is considered to change the copolymerization component or adjust the ratio. On the other hand, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene has very high heat resistance, whereas the resin It has the property of becoming brittle, and it has been difficult to improve the flexibility of the resin while maintaining moderate heat resistance. Moreover, in the case of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, in order to express a desired reverse wavelength dispersion, it is necessary to contain about 50-70 mass % of these monomer components, , the degree of freedom in molecular design by copolymerization was low, and it was difficult to achieve both properties such as heat resistance and mechanical strength and optical properties.

Moreover, polycarbonate resin using the diol containing the fluorene ring of patent document 9 is insufficient in characteristics, such as reverse wavelength dispersion property, a photoelastic coefficient, and heat resistance. As for the polyester of patent document 10, it is described that negative refractive index anisotropy, ie, the refractive index of an extending|stretching direction, is smaller than the refractive index of an extending|stretching right angle direction. However, as a retardation film, it is necessary to have positive refractive index anisotropy, and the above-mentioned polyester stretched film does not satisfy this requirement. Moreover, in patent document 10, there is also no description about the wavelength dependence of a phase difference.

As mentioned above, it is difficult for the conventional retardation film to obtain various characteristics, such as reverse wavelength dispersion property, an optical characteristic, heat resistance, and mechanical strength, in a balanced way. In order to radically improve the characteristics of the retardation film, it is required to use a new compound excellent in the balance of various characteristics as a raw material.

The first object of the present invention is to solve the above problems and provide a resin excellent in various properties such as optical properties, heat resistance, mechanical properties and thermal stability, and an optical film obtained using the same.

Moreover, it is known that the stretched film which consists of a polycarbonate resin which has a fluorene ring of patent document 11 or 12 is useful as a retardation film which shows reverse wavelength dispersion property, and a circularly polarizing plate for external light reflection prevention of an image display apparatus. However, as a result of the present inventors examining, in resin using 9,9-bis (4-hydroxy-3-methylphenyl) fluorene of patent document 11, although it has high heat resistance, desired reverse wavelength dispersion is expressed. In order to do this, it is necessary to increase the ratio of the repeating unit having a fluorene ring, so it is easy to form a brittle film, and there is a problem in flexibility. On the other hand, in the resin using 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene of Patent Document 12, although excellent in flexibility, in order to express a desired reverse wavelength dispersion, fluorene It was necessary to increase the ratio of the repeating unit having a ring, and it was difficult to achieve coexistence of various physical properties such as heat resistance and optical properties. For this reason, in order to further improve the optical properties of the resin, various physical properties such as heat resistance and flexibility, it is required to use a new compound excellent in the balance of optical properties and various physical properties such as mechanical strength as a raw material.

Although polyester obtained using a difluorene compound is disclosed by patent document 13 and 10, it originates in a difluorene structure, and heat resistance is not yet satisfactory. Moreover, in patent document 13, it is not used as a film, and an optical characteristic etc. are unclear, and in patent document 10, examination as a retardation film is not made|formed, and it is also unclear also about the wavelength dependence of retardation.

A second object of the present invention is to provide a novel fluorene compound that has sufficient heat resistance and exhibits excellent optical properties when a resin composition is prepared using a small amount of it and formed into a film, thereby increasing the degree of freedom in resin design. is in doing Moreover, it is providing the resin composition obtained using a novel fluorene compound.

Moreover, as described in patent document 10, as a method of providing specific physical properties to resin, the method of using together two types of oligofluorene compounds from which the reactive functional group of the terminal differs is mentioned. However, it is difficult to obtain an oligofluorene compound, and in order to produce a resin having desired physical properties, it is necessary to separately synthesize two types of oligofluorene compounds as raw materials. could not be said to be sufficient.

As a result of earnest examination by the present inventors, it discovered that it is useful to use the oligofluorene compound which has high practicality and which has different reactive functional groups at both terminals as a method of providing desired physical properties to resin. As a method for producing such an oligofluorene compound, a method of first preparing an oligofluorene compound having one reactive functional group as a raw material, and then introducing a reactive functional group different from the reactive functional group into the oligofluorene compound can be heard

As a method for producing an oligofluorene compound having one reactive functional group, for example, the method described in Non-Patent Document 1 is known, but in this method, it is difficult to selectively obtain an oligofluorene compound having one reactive functional group. , there was a problem that it is difficult to efficiently prepare an oligofluorene compound having different reactive functional groups at both terminals.

Therefore, a third object of the present invention is to provide an oligofluorene compound having a specific reactive functional group which selectively has a desired reactive functional group and can be suitably used as a monomer or monomer raw material for a resin composition for optical use.

In addition, as a result of the present inventors earnestly examining the resin composition for reverse wavelength dispersion, by using a specific oligofluorenediester compound as a raw material monomer, desired optical properties can be efficiently expressed even if the content ratio in the resin is low, , it was found that the degree of freedom in resin design can be increased.

Usually, in manufacturing a resin composition, in order to make a polymerization rate and the physical property of the resin composition obtained into predetermined|prescribed thing, it is necessary to strictly control the amount ratio of a raw material. The oligofluorenediester compound is usually a solid, and in using it as a raw material of a resin composition, in order to control the amount, it is preferable to melt and use it. As a result of earnest examination by the present inventors, depending on the amount of metal contained in the compound, coloration occurs in the compound when it is subjected to a melting process, and it is newly discovered that it is difficult to use as a monomer of a resin composition for optical use. became

On the other hand, although there are various methods for producing a polyester carbonate resin using a diester compound, as a general method, a melt polycondensation method in which diols, diaryl carbonates and diesters are polymerized in a molten state by transesterification is known. have. In this method, when a diaryl carbonate and a dialkyl ester are used as diesters, the reaction rate of the transesterification reaction and the polycarbonate polymerization are significantly different, so that the dialkyl ester is difficult to be incorporated into the polyester carbonate resin. Therefore, it is preferable to use a diaryl ester as diesters. In addition, as a method of producing an oligofluorenediaryl compound having aryl groups at both terminals, a method in which both terminals of the oligofluorenediester compound are replaced with aryl groups, included in the oligofluorenediester compound It was newly discovered that the amount of metals in the oligofluorenediaryl compound obtained increased depending on the quantity of the carboxylic acid used, and coloration generate|occur|produced when it passed through a melting process.

Therefore, the fourth object of the present invention is an oligofluorene diester that can be suitably used as a monomer of a resin composition for optical use and can increase the degree of freedom in resin design, and it is possible to suppress coloration that may occur when it undergoes a melting process. It is to provide a possible oligofluorenediester compound.

Moreover, an object of this invention is to provide the oligofluorenediester compound which can be used as a raw material for manufacturing the oligofluorenediaryl ester compound which can suppress coloring.

As a result of repeated intensive studies in view of the first object, the present inventors have the characteristics that the content of the aromatic structure in the repeating structural unit constituting the resin is within a specific range and the desired wavelength dispersibility is expressed. It was discovered that the resin used as exhibits the outstanding optical characteristic and mechanical property, and led to this invention. That is, this invention makes the following summary.

[1-1]

As a polycondensation-based resin having a repeating structural unit containing an aromatic structure,

The content of the aromatic structure in the repeating structural unit satisfies the following formula (I),

Resin having at least one structural unit selected from structural units represented by the following formulas (1) and (2).

5 ≤ A ≤ -22.5 × B + 38.3 (I)

provided that 0.75 ≤ B ≤ 0.93

A: Content of aromatic structure in the repeating structural unit constituting the resin [mass %]

B: Ratio (R450/R550) of the retardation (R450) at 450 nm and the retardation (R550) at 550 nm of the stretched film produced from the resin

[Formula 1]

(In formulas (1) and (2), R ¹ to R ³ are each independently a direct bond or an optionally substituted alkylene group having 1 to 4 carbon atoms.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.)

[1-2]

A polycondensation-based resin having a repeating structural unit containing an aromatic structure, wherein the content of the aromatic structure in the repeating structural unit satisfies the following formula (III), and the resin has a glass transition temperature of 110°C or higher and 160°C Resin characterized in that the following.

5 ≤ A ≤ -22.5 × B + 34.8 (III)

provided that 0.75 ≤ B ≤ 0.93

A: Content of aromatic structure in the repeating structural unit constituting the resin [mass %]

B: Ratio (R450/R550) of the retardation (R450) at 450 nm and the retardation (R550) at 550 nm of the stretched film produced from the resin

[1-3]

The resin according to [1-1] or [1-2], wherein the refractive index in a sodium d-line (589 nm) is 1.49 to 1.56.

[1-4]

The resin according to any one of [1-1] to [1-3], wherein the storage elastic modulus is 1 GPa or more and 2.7 GPa or less.

[1-5]

The resin according to any one of [1-1] to [1-4], wherein the melt viscosity at a measurement temperature of 240°C and a shear rate of 91.2 sec ^{-1 is 700 Pa·s or more and 5000 Pa·s or less.}

[1-6]

The resin according to any one of [1-1] to [1-5], wherein the resin is at least one resin selected from the group consisting of polycarbonate, polyester, and polyester carbonate.

[1-7]

The resin according to any one of [1-1] to [1-6], wherein the aromatic structure included in the repeating structural unit is only fluorene.

[1-8]

The resin according to any one of [1-1] to [1-7], comprising a structural unit represented by the following formula (3).

[Formula 2]

[1-9]

A transparent film containing the resin according to any one of [1-1] to [1-8].

[1-10]

A retardation film obtained by stretching the transparent film according to [1-9] in at least one direction.

[1-11]

The retardation film according to [1-10], which consists of a single layer and has a film thickness of 10 µm or more and 60 µm or less.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest examination in view of the said 2nd object, the specific trifluorenediester compound has sufficient heat resistance, and the optical characteristic excellent when using a small amount to manufacture a resin composition and film-molding. was found, and the present invention was reached.

That is, this invention makes the following summary.

[2-1]

including three fluorene units a which may have a substituent;

The carbon atoms at the 9th position of the fluorene unit a are directly bonded or linked in a chain form via an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent. Characterized in that, trifluorene diester.

[2-2]

It is represented by the following general formula (1), The trifluorenediester as described in [2-1] characterized by the above-mentioned.

[Formula 3]

(during the meal,

R ¹ and R ² are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ^3a and R ^3b are each independently an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 6 to 10 carbon atoms.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.)

R ¹⁰ is an organic substituent having 1 to 10 carbon atoms.)

[2-3]

The trifluorenediester according to [2-2], wherein ^{R 10} in the general formula (1) is an optionally substituted C4-C10 aryl group.

[2-4]

An oligofluorenediester composition comprising the trifluorenediester according to any one of [2-1] to [2-3] and a difluorenediester, comprising:

The said difluorene diester contains two fluorene units b which may have a substituent,

The carbon atoms at the 9th position of the fluorene unit b are bonded directly or in a chain form through an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent, Characterized in that there is, an oligofluorene diester composition.

[2-5]

The said difluorenediester is represented by the following general formula (2), The oligofluorenediester composition as described in [2-4] characterized by the above-mentioned.

[Formula 4]

(during the meal,

R ¹ to R ³ are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.)

R ¹⁰ is an organic substituent having 1 to 10 carbon atoms.)

[2-6]

The oligofluorenediaryl ester composition according to [2-4] or [2-5], wherein the content ratio of the trifluorenediester to the total mass of the composition is 1% by mass or more.

[2-7]

A resin composition comprising or containing a polymer having divalent trifluorene as a repeating unit,

Said divalent trifluorene contains three fluorene units a which may have a substituent, and carbon atoms at the 9th position of the fluorene unit a are a direct bond, or an alkylene group which may have a substituent; A resin composition characterized by bonding in a chain form via an arylene group which may have a substituent or an aralkylene group which may have a substituent.

[2-8]

The resin composition according to [2-7], wherein the divalent trifluorene is represented by the following general formula (11).

[Formula 5]

(during the meal,

R ¹ and R ² are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ^3a and R ^3b are each independently an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 6 to 10 carbon atoms.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.)

[2-9]

In addition, having divalent difluorene as a repeating unit,

The divalent difluorene includes two fluorene units b which may have a substituent, and the carbon atoms at the 9th position of the fluorene unit b are a direct bond or an alkylene group which may have a substituent; The resin composition according to [2-7] or [2-8], wherein the resin composition is bonded in a chain form via an arylene group which may have a substituent or an aralkylene group which may have a substituent.

[2-10]

Any one of [2-7] to [2-9], characterized in that the ratio of the phase difference (Re450) measured at a wavelength of 450 nm to the phase difference (Re550) measured at a wavelength of 550 nm satisfies the following formula (20) The resin composition described in.

Re450/Re550 ≤ 1.0 (20)

[2-11]

A molded article obtained by molding the resin composition according to any one of [2-7] to [2-10].

[2-12]

[2-7] An optical member comprising the resin composition according to any one of [2-10].

[2-13]

A film comprising the resin composition according to any one of [2-7] to [2-10].

[2-14]

A stretched film obtained by stretching the film according to [2-13] in at least one direction.

[2-15]

A 1/4λ plate comprising the stretched film according to [2-14].

[2-16]

A circular polarizing plate having the 1/4λ plate according to [2-15].

[2-17]

An image display device comprising the circularly polarizing plate according to [2-16].

As a result of repeated studies by the present inventors in view of the third object, a desired oligofluorene compound with high selectivity and efficiency can be obtained by replacing the hydrogen oligofluorene compound at both terminals with an olefin compound having a specific reactive functional group. Furthermore, it was discovered that this oligofluorene compound was suitable as a monomer or monomer raw material of the resin composition for optical use, and this invention was reached.

That is, this invention makes the following summary.

[3-1]

The carbon atoms at the 9th position of the two or more fluorene units a which may have a substituent are in a chain form via an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent. As an oligofluorene comprising a bonded oligofluorene structural unit (hereinafter referred to as "oligofluorene structural unit a"),

In the oligofluorene structural unit a, it has a reactive functional group represented by the following formula (A) at the carbon atom at the 9-position of the fluorene unit a at one terminal, and at the 9-position of the fluorene unit a at the other end of the oligofluorene structural unit a An oligofluorene having a hydrogen atom at a carbon atom.

[Formula 6]

(Wherein, R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted C 6 to 10 carbon atoms; an alkyl group, and X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group. * is a bond with the carbon atom at the 9th position of the fluorene unit a.)

[3-2]

The oligofluorene as described in [3-1] characterized by being represented by the following general formula (1).

[Formula 7]

(In the formula, R ³ is each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms.

X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group.

n represents an integer value of 1 to 5.)

[3-3]

The carbon atoms at the 9th position of the two or more fluorene units a which may have a substituent are in a chain form via an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent. An oligofluorene comprising a bonded oligofluorene structural unit a,

In the oligofluorene structural unit a, it has a reactive functional group represented by the following formula (A) at the carbon atom at the 9-position of the fluorene unit a at one terminal, and at the 9-position of the fluorene unit a at the other end of the oligofluorene structural unit a An oligofluorene having a reactive functional group different from the reactive functional group on a carbon atom.

[Formula 8]

(Wherein, R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted C 6 to 10 carbon atoms; an alkyl group, and X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group. * is a bond with the carbon atom at the 9th position of the fluorene unit.)

[3-4]

The oligofluorene according to [3-3], which is represented by the following general formula (2).

[Formula 9]

(In the formula, R ³ is each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is a direct bond, optionally substituted alkylene group having 1 to 10 carbon atoms, optionally substituted arylene group having 4 to 10 carbon atoms, or optionally substituted aralkylene group having 6 to 10 carbon atoms;

or two or more groups selected from the group consisting of an optionally substituted C1-C10 alkylene group, an optionally substituted C4-C10 arylene group, and optionally substituted C6-C10 aralkylene group, an oxygen atom; It is an optionally substituted sulfur atom, an optionally substituted nitrogen atom, or a group linked to a carbonyl group.

R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms,

X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group,

A is a hydroxyl group, an amino group, an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group.

n represents an integer value of 1 to 5.)

[3-5]

The oligofluorene according to any one of [3-1] to [3-4] (hereinafter referred to as "oligofluorene A") and the oligofluorene having a different chemical structure from the oligofluorene A (hereinafter referred to as "oligofluorene A") , referred to as "oligofluorene B".) As an oligofluorene composition comprising:

In the oligofluorene B, the carbon atoms at the 9th position of two or more fluorene units b which may have a substituent are an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aral which may have a substituent. and an oligofluorene structural unit (hereinafter referred to as "oligofluorene structural unit b") bonded in a chain form via a chelenium group;

An oligofluorene composition having the same reactive functional group represented by the following formula (B) at the carbon atom at position 9 of the fluorene unit b at both terminals in the oligofluorene structural unit b.

[Formula 10]

(Wherein, R ^d to R ^f are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted C 6 to 10 carbon atoms; an alkyl group, and X ¹ is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group. * is a bond with the carbon atom at the 9th position of the fluorene unit b.)

[3-6]

A resin comprising or comprising the polymer of the oligofluorene composition according to any one of [3-1] to [3-4] or the polymer of the oligofluorene composition according to [3-5] composition.

[3-7]

A film comprising the resin composition according to [3-6].

[3-8]

A stretched film obtained by stretching the film according to [3-7] in at least one direction.

[3-9]

An image display device having the stretched film according to [3-8].

[3-10]

An oligofluorene represented by the following formula (1) is obtained by reacting an oligofluorene represented by the following formula (3) with an olefin having an electron-withdrawing group represented by the following formula (4) in the presence of a base in the presence of a base A method for producing fluorene.

[Formula 11]

(In the formula, R ³ is each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms;

X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group.

n represents an integer value of 1 to 5.)

[3-11]

An oligofluorene represented by the following formula (2) is obtained by reacting an oligofluorene represented by the above formula (1) obtained by the method of [3-10] with a compound having electrophilicity A method for producing oligofluorene.

[Formula 12]

(during the meal,

R ³ is each independently a direct bond or a C1-C4 alkylene group which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is a direct bond, optionally substituted alkylene group having 1 to 10 carbon atoms, optionally substituted arylene group having 4 to 10 carbon atoms, or optionally substituted aralkylene group having 6 to 10 carbon atoms;

or two or more groups selected from the group consisting of an optionally substituted C1-C10 alkylene group, an optionally substituted C4-C10 arylene group, and optionally substituted C6-C10 aralkylene group, an oxygen atom; a group linked to an optionally substituted sulfur atom, an optionally substituted nitrogen atom, or a carbonyl group;

R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms,

X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group,

A is a hydroxyl group, an amino group, an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group.

n represents an integer value of 1 to 5.)

As a result of the present inventors repeating earnest examination in view of the said 4th objective, by making the content rate of the metal component contained in an oligofluorenediester compound into a specific range, stability in a molten state improves and coloration is suppressed found out what was possible.

In addition, as a raw material for producing an oligofluorenediaryl ester compound capable of suppressing coloration, an oligofluorene diester compound having a carboxylic acid content within a specific range is used in the diaryl ester compound obtained by using It discovered that it was possible to reduce the content rate of a metal component.

That is, this invention makes the following summary.

[4-1]

As an oligofluorene diester containing two or more fluorene units which may have a substituent,

The carbon atoms at the 9th position of the fluorene unit are bonded in a chain form through a direct bond or an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent, , Also,

An oligofluorenediester having a metal content of 500 mass ppm or less.

[4-2]

[4-1] wherein the metal is at least one metal selected from the group consisting of a long-period periodic table, Group 1, Group 2, Group 12, Group 14, and a transition metal, in [4-1] described oligofluorenediesters.

[4-3]

It is represented by the following general formula (1), The oligofluorenediester of [4-1] or [4-2] characterized by the above-mentioned.

[Formula 13]

(In the formula, R ¹ to R ³ are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is an organic substituent having 1 to 10 carbon atoms.

n represents an integer value of 1 to 5.)

[4-4]

^{The oligofluorenediester according to [4-3], wherein R 10} in the general formula (1) is an aryl group having 4 to 10 carbon atoms.

[4-5]

As an oligofluorene diester containing two or more fluorene units which may have a substituent,

The carbon atoms at the 9th position of the fluorene unit are directly bonded or linked in a chain form through an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent, , Also,

The content of carboxylic acid is 10 mass % or less, The oligofluorenediester characterized by the above-mentioned.

[4-6]

It is represented by the following general formula (1), The oligofluorenediester of [4-5] characterized by the above-mentioned.

[Formula 14]

(In the formula, R ¹ to R ³ are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is an organic substituent having 1 to 10 carbon atoms.

n represents an integer value of 1 to 5.)

[4-7]

A method for producing an oligofluorenediaryl ester, comprising using the oligofluorenediester according to [4-6] as a raw material and ^{substituting the R 10} group with an aryl group to obtain a diaryl ester.

[4-8]

A method for producing a resin composition, wherein the oligofluorenediester according to any one of [4-1] to [4-6] is used as a raw material.

The resin of the present invention has excellent balance of various properties such as optical properties, heat resistance, mechanical properties, and reliability. Therefore, the resin of the present invention can be suitably used for optical films such as retardation films.

In addition, the novel fluorene compound of the present invention has sufficient heat resistance and exhibits excellent optical properties when a resin composition is prepared using the fluorene compound and formed into a film, thereby increasing the degree of freedom in resin design.

Moreover, the oligofluorene compound which concerns on this invention selectively has a desired reactive functional group, and can be used suitably as a monomer or monomer raw material of the resin composition for optical use.

Moreover, the oligofluorenediester compound which concerns on this invention can be used suitably as a monomer of a resin composition for optical use, or a raw material of a monomer, When the freedom degree of resin design is improved, and also passed through a melting process, It is possible to suppress the coloration that may occur.

BRIEF DESCRIPTION OF THE DRAWINGS It is a graph which compared the metal content in Examples 4-1 to 4-4 and the oligofluorenediester of Comparative Example 4-1, and the absorbance difference before and behind heating.
2 is a graph showing the particle size distribution of the oligofluorenediester of Reference Example 4-1 and Reference Example 4-2.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is limited to the following content unless the gist thereof is exceeded doesn't happen

In addition, in this invention, "repeating structural unit" is a structural unit in which the same structure repeatedly appears in resin, and means the structural unit which comprises the said resin by connecting each. More specifically, if it is a polycarbonate resin, for example, a carbonyl group is included and it is called a repeating structural unit.

In addition, a "structural unit" refers to a specific partial structure included in the repeating structural unit as a partial structure constituting the resin. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin or a partial structure sandwiched between a polymerization reactive group present at an end portion of a polymer and a linking group adjacent to each other in the polymerizable reactive group, and more specifically, for example, For example, if it is a polycarbonate resin, a carbonyl group is a coupling group, and the partial structure sandwiched by the carbonyl group adjacent to each other is called a structural unit.

In the present invention, "weight" has the same meaning as "mass".

In this invention, "it may have a substituent" has the same meaning as "it may be substituted".

In the present invention, the "general formula" may be simply described as "formula".

≪Invention 1≫

Hereinafter, the resin and film of the present invention 1 will be described in detail.

In addition, (general) formulas (1) - (9) and (11) - (15) described below demonstrate each structure in this invention 1 .

A first aspect of the present invention is a polycondensation resin having a repeating structural unit containing an aromatic structure, wherein the content of the aromatic structure in the repeating structural unit satisfies the following formula (I), and the following formulas (1) and It is a resin which has at least 1 structural unit selected from the structural unit represented by (2).

5 ≤ A ≤ -22.5 × B + 38.3 (I)

provided that 0.75 ≤ B ≤ 0.93

A: Content of aromatic structure in the repeating structural unit constituting the resin [mass %]

B: Ratio (R450/R550) of the retardation (R450) at 450 nm and the retardation (R550) at 550 nm of the stretched film produced from the resin

[Formula 15]

(In formulas (1) and (2), R ¹ to R ³ are each independently a direct bond or an optionally substituted C1-C4 alkylene group.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.)

A second aspect of the present invention is a polycondensation resin having a repeating structural unit containing an aromatic structure, wherein the content of the aromatic structure in the repeating structural unit satisfies the following formula (III), and the glass transition of the resin It is a resin characterized by the temperature being 120 degreeC or more and 160 degrees C or less.

5 ≤ A ≤ -22.5 × B + 34.8 (III)

provided that 0.75 ≤ B ≤ 0.93

A: Content of aromatic structure in the repeating structural unit constituting the resin [mass %]

B: Ratio (R450/R550) of the retardation (R450) at 450 nm and the retardation (R550) at 550 nm of the stretched film produced from the resin

<Resin of the present invention>

The resin of the present invention is a polycondensation-based resin. Polycondensation-based resin refers to a resin obtained by polycondensation, which is defined in Glossary of basic terms in polymer science (IUPAC Recommendations 1996), and a resin obtained by polymerization in which the growth of a polymer chain proceeds by an intermolecular condensation reaction. say The polycondensation-based resin of the present invention is preferably a resin having at least one bond selected from a carbonate bond and an ester bond, and more specifically, it is preferably a resin of any one of polycarbonate, polyester, and polyester carbonate. do. These resins are excellent in heat resistance, mechanical properties, and melt processability, and by copolymerizing a plurality of monomers, various physical properties such as optical properties, heat resistance, and mechanical properties can be easily controlled within a desired range.

Although resin of this invention contains an aromatic structure, as an aromatic structure, any structure shall be included as long as it is a cyclic structure which has aromaticity. More specifically, a benzenoid aromatic ring, a bibenzenoid aromatic ring, a heteroaromatic ring, etc. are mentioned, Among these, a benzenoid aromatic ring or a heteroaromatic ring is preferable. In this invention, the calculation method of content of the aromatic structure in the repeating structural unit which comprises resin is given and demonstrated below with a specific example.

[Calculated molecular weight of various aromatic structures]

The molecular weight of the aromatic structure in the present invention includes a carbon atom, a hydrogen atom, and a hetero atom in the cyclic structure having aromaticity. A carbon atom or a hetero atom bonded to a cyclic structure having aromaticity is not included in the aromatic structure. In addition, when a vinyl group, an ethynyl group, or a carbonyl group is bonded to a cyclic structure having aromaticity, the conjugated system of the aromatic ring extends to those functional groups, but a substituent bonded to the cyclic structure having aromaticity is not included in the aromatic structure. does not

[Formula 16]

[Formula 17]

[Calculation Example 1]

[Formula 18]

Molecular weight of repeating structural unit: C ₁₀ H ₈ O ₄ = 192.17

Molecular weight of aromatic structure in repeating structural unit: C ₆ H ₄ = 76.10

Content of aromatic structure = 76.10/192.17 × 100 = 39.6 [mass%]

[Calculation Example 2]

[Formula 19]

A copolymer resin of the repeating structural unit A and the repeating structural unit B, wherein the molar ratio of the repeating structural unit A and the repeating structural unit B is m:n = 3:7.

Molecular weight of repeating structural unit A: C ₃₀ H ₂₄ O ₅ = 464.51

Molecular weight of aromatic structure in repeating structural unit A: C ₆ H ₄ × 4 = 304.38

Molecular weight of repeating structural unit B: C ₁₆ H ₁₄ O ₃ = 254.28

Molecular weight of aromatic structure in repeating structural unit B = C ₆ H ₄ × 2 = 152.19

Content of aromatic structure: (304.38 × 0.3 + 152.19 × 0.7) / (464.51 × 0.3 + 254.28 × 0.7) × 100 = 62.3 [mass%]

The resin of the present invention is characterized in that the content of the aromatic structure in the repeating structural unit constituting the resin calculated as described above satisfies the following formula (I). Moreover, it is preferable to satisfy|fill the following formula (II), and it is especially preferable to satisfy|fill formula (III).

5 ≤ A ≤ -22.5 × B + 38.3 (I)

7 ≤ A ≤ -22.5 × B + 37.5 (II)

8 ≤ A ≤ -22.5 × B + 34.8 (III)

However, 0.75 ≤ B ≤ 0.93.

A: Content of aromatic structure in the repeating structural unit constituting the resin [mass %]

B: Ratio (R450/R550) of the retardation (R450) at 450 nm and the retardation (R550) at 550 nm of the stretched film produced from the resin

When the value of R450/R550 in the formula (I) is less than 1, the phase difference has reverse wavelength dispersion, and when used as a quarter wave plate, the phase difference close to the ideal in a wide wavelength range It becomes possible to obtain properties. One of the methods for expressing this reverse wavelength dispersion property is to orient a component having a larger wavelength dispersion (wavelength dependence) of refractive index than the main chain component of the polymer chain in a direction perpendicular to the main chain. In general, the longer the aromatic conjugated system is, the greater the wavelength dispersion of the refractive index. Therefore, it is preferable that the resin having reverse wavelength dispersion contains an aromatic structure. On the other hand, when an aromatic is contained in a main chain component, since the aromatic component on a main chain expresses strong positive wavelength dispersion property, reverse wavelength dispersion property will be cancelled. Moreover, when many aromatics are generally contained, a photoelastic coefficient and refractive index will become large, and it is an unpreferable direction from an optical property. The said formula (I) introduce|transduces the aromatic structure with high expression efficiency of reverse wavelength dispersion|distribution, and means suppressing the other aromatic component to a necessary minimum. By carrying out such a molecular design, resin excellent in the balance of optical properties, such as a photoelastic coefficient and orientation, can be obtained, having reverse wavelength dispersion property. A specific preferred molecular structure will be described later.

As the value of B (R450/R550), a value of wavelength dispersion measured by evaluation using a stretched film obtained from an unstretched film produced from a resin by a hot press method is used.

<Oligofluorene structural unit>

It is preferable that the resin of this invention has 1 or more types of structural unit from the group which consists of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). Hereinafter, the structural unit may be referred to as an oligofluorene structural unit.

[Formula 20]

In the general formulas (1) and (2), R ¹ to R ³ each independently represent a direct bond or an optionally substituted C1-C4 alkylene group.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group.

In R<^1> and R<^2> , the following alkylene groups are employable as "the C1-C4 alkylene group which may have a substituent", for example. linear alkylene groups such as methylene group, ethylene group, n-propylene group and n-butylene group; methylmethylene group, dimethylmethylene group, ethylmethylene group, propylmethylene group, (1-methylethyl)methylene group, 1 -Methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1,1-dimethylethylene group, 2,2-dimethylpropylene group , an alkylene group having a branched chain, such as a 3-methylpropylene group. Here, ^{the positions of the branched chains in R 1} and R ² are indicated by numbers assigned so that the carbon on the fluorene ring side becomes the 1st position.

The selection of R ¹ and R ² has a particularly important influence on the expression of reverse wavelength dispersion. The resin exhibits the strongest reverse wavelength dispersion in a state in which the fluorene ring is oriented perpendicular to the main chain direction (stretching direction). In order to make the orientation state of a fluorene ring close to the said state and to express strong reverse wavelength dispersion, it is preferable to employ|adopt ^R<1> and R<^{2> of C2-C3 on the main chain of an alkylene group.} When carbon number is 1, reverse wavelength dispersion property may not be shown unexpectedly. As this factor, the orientation of a fluorene ring is fixed in a direction other than perpendicular|vertical with respect to the main chain direction, etc. by steric hindrance of the carbonate group or ester group which are the coupling groups of an oligofluorene structural unit. On the other hand, when there is too much carbon number, there exists a possibility that reverse wavelength dispersion property may become weak because fixation of the orientation of a fluorene ring becomes weak. Moreover, the heat resistance of resin also falls.

As shown in the above general formulas (1) and (2), R ¹ and R ² are either an oxygen atom or carbonyl carbon in which one end of the alkylene group is bonded to a fluorene ring and the other end is contained in the linking group. binding to From the viewpoint of thermal stability, heat resistance and reverse wavelength dispersion, it is preferable that the other end of the alkylene group is bonded to the carbonyl carbon. As will be described later, as a monomer having an oligofluorene structure, a structure of diol or diester (hereinafter, diester also includes dicarboxylic acid) is considered as a monomer having an oligofluorene structure, but polymerization is performed using diester as a raw material It is preferable to do

Moreover, from a viewpoint of facilitating manufacture, it is preferable to employ|adopt the same alkylene group for ^R<1> and R<^2>.

In R<^3> , the following alkylene groups are employable as "the C1-C4 alkylene group which may have a substituent", for example. linear alkylene groups such as methylene group, ethylene group, n-propylene group and n-butylene group; methylmethylene group, dimethylmethylene group, ethylmethylene group, propylmethylene group, (1-methylethyl)methylene group, 1 -Methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1,1-dimethylethylene group, 2,2-dimethylpropylene group , an alkylene group having a branched chain such as a 3-methylpropylene group.

It is preferable that C1-C2 on the main chain of an alkylene group is R<^{3>, and it is especially preferable that C1 is especially preferable. When R 3} having too many carbon atoms on the main chain is employed, ^{the immobilization of the fluorene ring becomes weak like R 1} and R ^{2 ,} and there is a risk of causing a decrease in reverse wavelength dispersion, an increase in the photoelastic coefficient, a decrease in heat resistance, etc. have. On the other hand, if the number of carbon atoms on the main chain is small, the optical properties and heat resistance are better, but when the 9-position of the two fluorene rings leads to a direct bond, the thermal stability is deteriorated.

In the R ¹ ~ R ^3, the substituent group is an alkylene which may have, although possible to employ a substituent exemplified below, may be adopted for a substituent other than the above. A halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; an acyl group having 1 to 10 carbon atoms such as an acetyl group and a benzoyl group; an acetamide group , an acylamide group having 1 to 10 carbon atoms, such as a benzoylamide group; a nitro group; a cyano group; 1 to 3 by the halogen atom, the alkoxy group, the acyl group, the acylamide group, the nitro group, the cyano group, etc. An aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group, which may be substituted with hydrogen atoms.

Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. When the number of substituents is too large, there exists a possibility that reaction may be inhibited or thermally decomposed during superposition|polymerization. Moreover, it is preferable that ^R<1> -R<^3> is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

In R ⁴ to R ⁹ , the “alkyl group having 1 to 10 carbon atoms which may have a substituent” is, for example, the following alkyl groups. Linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-decyl group; isopropyl group, 2-methylpropyl group, 2,2-dimethylpropyl group an alkyl group having a branched chain such as a group or a 2-ethylhexyl group; a cyclic alkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group.

It is preferable that it is 4 or less, and, as for carbon number of the said alkyl group, it is more preferable that it is 2 or less. If it is in this range, steric hindrance between fluorene rings does not generate|occur|produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired.

As a substituent which the said alkyl group may have, although the substituent illustrated below can be employ|adopted, you may employ|adopt substituents other than these. A halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; an acyl group having 1 to 10 carbon atoms such as an acetyl group and a benzoyl group; an acetamide group , an acylamide group having 1 to 10 carbon atoms, such as a benzoylamide group; a nitro group; a cyano group; 1 to 3 by the halogen atom, the alkoxy group, the acyl group, the acylamide group, the nitro group, the cyano group, etc. An aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group, which may be substituted with hydrogen atoms.

Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. When there are too many such substituents, there exists a possibility of inhibiting reaction or thermally decomposing during superposition|polymerization. Moreover, it is preferable that ^R<4> -R<^9> is unsubstituted from a viewpoint that it can manufacture at low industrial cost. Specific examples of the alkyl group include a trifluoromethyl group, a benzyl group, a 4-methoxybenzyl group, and a methoxymethyl group.

Moreover, in R<^4>-R<^9> , the following aryl groups are employable as "the C4-C10 aryl group which may have a substituent", for example. Aryl groups, such as a phenyl group, 1-naphthyl group, and 2-naphthyl group; Heteroaryl groups, such as a 2-pyridyl group, 2-thienyl group, and 2-furyl group.

It is preferable that it is 8 or less, and, as for carbon number of the said aryl group, it is more preferable that it is 7 or less. If it is in this range, steric hindrance between fluorene rings does not generate|occur|produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired.

As a substituent which the said aryl group may have in R<^4>-R<^9> , although the substituent illustrated below can be employ|adopted, you may employ|adopt substituents other than these. A halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, and an isopropyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; an acetyl group , an acyl group having 1 to 10 carbon atoms, such as a benzoyl group; an acylamide group having 1 to 10 carbon atoms, such as an acetamide group and a benzoylamide group; a nitro group; a cyano group. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that ^R<4> -R<^9> is unsubstituted from a viewpoint that it can manufacture at low industrial cost.

Specific examples of the aryl group include 2-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-benzoylphenyl group, 4-methoxyphenyl group, 4-nitrophenyl group, 4-cyanophenyl group, 3- trifluoromethylphenyl group, 3,4-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-methylfuryl group, etc. are mentioned.

Also, in the R ⁴ R ~ ^9, roneun "an acyl group having 1 to 10 carbon atoms which may have a substituent", for example, there may be employed a group of the following acyl. Aliphatic acyl groups such as formyl group, acetyl group, propionyl group, 2-methylpropionyl group, 2,2-dimethylpropionyl group, and 2-ethylhexanoyl group; benzoyl group, 1-naphthylcarbonyl group, 2-naphthyl group Aromatic acyl groups, such as a carbonyl group and 2-furyl carbonyl group.

It is preferable that it is 4 or less, and, as for carbon number of the said acyl group, it is more preferable that it is 2 or less. If it is in this range, steric hindrance between fluorene rings does not generate|occur|produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired.

As a substituent which the said acyl group may have, although the substituent illustrated below can be employ|adopted, you may employ|adopt substituents other than these. A halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an isopropyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; acetamide an acylamide group having 1 to 10 carbon atoms such as a group and a benzoylamide group; a nitro group; a cyano group; An aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group, in which 1 to 3 hydrogen atoms may be substituted by the nitro group, the cyano group, or the like.

Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that ^R<4> -R<^9> is unsubstituted from a viewpoint that it can manufacture at low industrial cost.

Specific examples of the acyl group include a chloroacetyl group, a trifluoroacetyl group, a methoxyacetyl group, a phenoxyacetyl group, a 4-methoxybenzoyl group, a 4-nitrobenzoyl group, a 4-cyanobenzoyl group, 4 -trifluoromethylbenzoyl group etc. are mentioned.

In addition, R ⁴ and roneun in R ^9, "acyloxy group having 1 to 10 carbon atoms which may have a substituent", for example, there may be employed an acyloxy or less. Aliphatic acyloxy groups, such as a formyl group, an acetyl group, a propanoyl group, a butanoyl group, acrylyl group, methacrylyl group; Aromatic acyloxy groups, such as a benzoyl group.

It is preferable that it is 4 or less, and, as for carbon number of the said acyl group, it is more preferable that it is 2 or less. If it is in this range, steric hindrance between fluorene rings does not generate|occur|produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired.

As a substituent which the said acyloxy group may have, although the substituent illustrated below can be employ|adopted, you may employ|adopt substituents other than these. A halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an isopropyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; acetamide an acylamino group having 1 to 10 carbon atoms such as a group and a benzoylamide group; a nitro group; a cyano group; An aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group, in which 1 to 3 hydrogen atoms may be substituted by a group, the cyano group, or the like.

Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that ^R<4> -R<^9> is unsubstituted from a viewpoint that it can manufacture at low industrial cost. Specific examples of the acyl group include a chloroacetyl group, a trifluoroacetyl group, a methoxyacetyl group, a phenoxyacetyl group, a 4-methoxybenzoyl group, a 4-nitrobenzoyl group, a 4-cyanobenzoyl group, 4 -trifluoromethylbenzoyl group etc. are mentioned.

Moreover, in R<^4>-R<^9> , the following alkoxy groups and aryloxy groups are employable as "the C1-C10 alkoxy group or aryloxy group which may have a substituent", for example. Alkoxy groups, such as a methoxy group, an ethoxy group, an isopropoxy group, a tert- butoxy group, and a trifluoromethoxy group; Aryloxy groups, such as a phenoxy group.

Among the said alkoxy group and the said aryloxy group, an alkoxy group is preferable, It is preferable that carbon number of an alkoxy group is 4 or less, It is more preferable that it is 2 or less. If it is in this range, steric hindrance between fluorene rings does not generate|occur|produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired.

Also, in the R ⁴ R ~ ^9, as a specific structure of "an amino group which may have a substituent", for the amino group the following can be employed, but one, it is also possible to employ an amino group other than the above. Amino group; N-methylamino group, N,N-dimethylamino group, N-ethylamino group, N,N-diethylamino group, N,N-methylethylamino group, N-propylamino group, N,N-dipropylamino group, N- Aliphatic amino groups such as isopropylamino group and N,N-diisopropylamino group; Aromatic amino groups such as N-phenylamino group and N,N-diphenylamino group; Formamide group, acetamide group, decanoylamide group, benzoylamide group , an acylamide group such as a chloroacetamide group; an alkoxycarbonylamino group such as a benzyloxycarbonylamino group or a tert-butyloxycarbonylamino group.

As the amino group, a N,N-dimethylamino group, N-ethylamino group, or N,N-diethylamino group, which does not have a high acidity proton, has a small molecular weight, and tends to increase the fluorene ratio, is employed. It is preferable to do this, and it is more preferable to employ a N,N-dimethylamino group.

In addition, in R ⁴ to R ⁹ , as "a vinyl group or ethynyl group having 1 to 10 carbon atoms which may have a substituent", for example, the following vinyl groups and ethynyl groups can be employed, but vinyl groups other than these It is also possible to employ etc. Vinyl group, 2-methylvinyl group, 2,2-dimethylvinyl group, 2-phenylvinyl group, 2-acetylvinyl group, ethynyl group, methylethynyl group, tert-butylethynyl group, phenylethynyl group, acetyl group an ethynyl group, a trimethylsilylethynyl group.

It is preferable that carbon number of the said vinyl group and the said ethynyl group is 4 or less. If it is in this range, steric hindrance between fluorene rings does not generate|occur|produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired. Moreover, when the conjugated system of a fluorene ring becomes long, it becomes easy to obtain stronger reverse wavelength dispersion.

In addition, ^{as the "sulfur atom having a substituent" for R 4} to R ⁹ , for example, the following sulfur-containing groups can be employed, but sulfur-containing groups other than these can also be employed. Sulfo group; Alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, and isopropylsulfonyl group; Arylsulfonyl groups such as phenylsulfonyl group and p-tolylsulfonyl group; Methylsulfinyl group, ethylsulfinyl group, propylsulfonyl group Alkylsulfinyl groups such as nyl group and isopropylsulfinyl group; Arylsulfinyl groups such as phenylsulfinyl group and p-tolylsulfinyl group; Alkylthio groups such as methylthio group and ethylthio group; phenylthio group, p-tolylthio group, etc. of arylthio group; alkoxysulfonyl group such as methoxysulfonyl group and ethoxysulfonyl group; Aryloxysulfonyl group such as phenoxysulfonyl group; aminosulfonyl group; N-methylaminosulfonyl group, N-ethylaminosulfonyl group, Alkylsulfonyl groups such as N-tert-butylaminosulfonyl group, N,N-dimethylaminosulfonyl group, N,N-diethylaminosulfonyl group; N-phenylaminosulfonyl group, N,N-diphenylaminosulfonyl group, etc. of an arylaminosulfonyl group. In addition, the sulfo group may form a salt with lithium, sodium, potassium, magnesium, ammonium, etc.

Among the sulfur-containing groups, it is preferable to employ a methylsulfinyl group, an ethylsulfinyl group, or a phenylsulfinyl group that does not have a high acidity proton, has a small molecular weight, and can increase the fluorene ratio, and a methylsulfinyl group is adopted. It is more preferable to

Also, in the R ⁴ R ~ ^9, roneun "silicon atom having a substituent", for example, there may be employed a group of the following silyl. Trialkylsilyl groups, such as a trimethylsilyl group and a triethylsilyl group; Trialkoxysilyl groups, such as a trimethoxysilyl group and a triethoxysilyl group. Among these, the trialkylsilyl group which can be handled stably is preferable.

Further, R ⁴ in R ~ ^9, roneun "halogen atom", there may be employed a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, it is preferable to employ a fluorine atom, a chlorine atom, or a bromine atom, which is relatively easy to introduce and has electron-withdrawing property and thus has a tendency to increase the reactivity of the fluorene 9-position. It is more preferable to employ

In addition, ^{two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring. Specific examples thereof include a substituted fluorene structure having a skeleton illustrated in the following group [A].

[A]

[Formula 21]

As described above, by making R ⁴ to R ^{9 a} specific atom or substituent as described above, there is little steric hindrance between the main chain and the fluorene ring or between the fluorene rings, and There is a tendency that optical properties can be obtained.

The fluorene ring contained in the oligofluorene structural unit has a structure in which ^{all of R 4} to R ⁹ are hydrogen atoms, or R ⁴ and/or R ⁹ is a halogen atom, an acyl group, a nitro group, a cyano group, and a sulfonyl group. It is preferably any one selected from the group consisting of an agar, and any one of the structures in which ^{R 5} to R ^{8 is a hydrogen atom is preferable.} When it has the former structure, the compound containing the said oligofluorene structural unit can be derived from industrially inexpensive fluorene. Further, in the case of the latter structure, since the reactivity at the 9-position of fluorene is improved, various induction reactions tend to be adaptable in the course of synthesizing the compound containing the oligofluorene structural unit. The fluorene ring is more preferably a structure in which ^{all of R 4} to R ⁹ are hydrogen atoms, or R ⁴ and/or R ⁹ is selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and a nitro group Any and any ^{of the structures in which R 5} to R ⁸ is a hydrogen atom is more preferable, and a structure in which all of R ⁴ to R ⁹ is a hydrogen atom is particularly preferable. By employing the above configuration, the fluorene ratio can be increased, and steric hindrance between the fluorene rings is less likely to occur, and there is a tendency that desired optical properties derived from the fluorene ring can be obtained.

Among the divalent oligofluorene structural units represented by the general formulas (1) and (2), a structure having a skeleton specifically exemplified in the following group [B] is exemplified as a preferable structure.

[B] military

[Formula 22]

The oligofluorene structural unit of the present invention is a structural unit derived from 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (the following structural formula (9)) or 9,9 which has been widely used in the past. Compared with the structural unit derived from -bis(4-hydroxy-3-methylphenyl)fluorene (the following structural formula (10)), it has the following characteristics.

- Since aromatic components, such as the phenyl ring which were conventionally inserted in the main chain of a polymer, are no longer inserted in the main chain of a polymer, a photoelastic coefficient can be reduced.

Since the aromatic component inserted into the main chain exhibits positive wavelength dispersion in which birefringence increases as the wavelength becomes shorter, conventionally, reverse wavelength dispersion derived from the fluorene ring of the side chain is canceled and the reverse wavelength of the resin as a whole The dispersibility was falling. On the other hand, reverse wavelength dispersibility can be expressed more strongly by preventing an aromatic component from being inserted in a principal chain.

- High heat resistance can be provided by introduce|transducing two fluorene rings in 1 molecule.

· Since the main chain is composed of a flexible alkylene chain, flexibility and melt processability can be imparted to the resin.

[Formula 23]

The resin of the present invention contains a resin including at least one bonding group among a carbonate bond and an ester bond, and the oligofluorene structural unit. Polycarbonate, polyester, and polyester carbonate, which are resins having the bonding group, are excellent in heat resistance, mechanical properties, and melt processability. Moreover, it has the advantage that the said oligofluorene structural unit can be introduce|transduced comparatively easily into resin by copolymerizing with another monomer, and it has the advantage that it is easy to control the ratio of the oligofluorene structural unit in resin to a desired range.

As a method of introduce|transducing the said oligofluorene structural unit into resin, the method of copolymerizing the diol or diester which has the said oligofluorene structural unit with another diol or diester is mentioned, for example. Specifically, polycarbonate can be obtained by superposing|polymerizing with the combination of diol and the diester carbonate represented by following General formula (11). Moreover, polyester can be obtained by superposing|polymerizing with the combination of diol and diester. Moreover, polyester carbonate can be obtained by superposing|polymerizing with the combination of diol, diester, and diester carbonate.

[Formula 24]

In the general formula (11), A ¹ and A ² each represent an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent or an aromatic hydrocarbon group which may have a substituent, and A ¹ and A ² may be the same or different. You can do it.

As a monomer which has the said oligofluorene structural unit, the specific diol represented by the following general formula (12), and the specific diester represented by the following general formula (13) are mentioned, for example.

[Formula 25]

In the general formulas (12) and (13), R ¹ to R ³ are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, a substituent a vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group.

A ³ and A ⁴ are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may each have a substituent, or an aromatic hydrocarbon group which may have a substituent, and A ³ and A ⁴ may be the same or different.

It is preferable to use the specific diester represented by the said General formula (13) as said monomer which has the said divalent oligofluorene structural unit. The said specific diester has comparatively better thermal stability than the specific diol represented by the said General formula (12), and the fluorene ring in a polymer orientates in a preferable direction, and there exists a tendency for stronger reverse wavelength dispersion property.

On the other hand, when polycarbonate and polyester are compared, the polycarbonate obtained by polymerization of a diol and a diester carbonate tends to have a better balance of heat resistance and mechanical properties. Therefore, as resin of this invention, the polyester carbonate which inserted the said specific diester which has an oligofluorene structural unit into the structure of a polycarbonate is especially preferable.

^{When A 3} and A ⁴ in the general formula (13) are a hydrogen atom or an aliphatic hydrocarbon group such as a methyl group or an ethyl group, the polymerization reaction of the polycarbonate usually used may not readily occur under polymerization conditions. Accordingly, A ³ and A ⁴ in the formula 13 is preferably an aromatic hydrocarbon group.

Moreover, when the polymerization reaction is also carried out using diester carbonate represented by the general formula (11), A ¹ , A ^{2 in} the general formula (11) and A ³ , A ⁴ in the general formula (13) are If they are all the same structure, the component which detach|desorbs during the polymerization reaction is the same, and it is easy to collect|recover and reuse. Further, in terms of usefulness in polymerization reactivity and reused, A ¹ ~ A ⁴ is particularly preferably a phenyl group. In the case where A ¹ ~ A ⁴ is a phenyl group, component desorbed during the polymerization reaction is phenol.

The resin of the present invention WHEREIN: In order to obtain the positive refractive index anisotropy mentioned later and sufficient reverse wavelength dispersion property, it is necessary to adjust the ratio of the said oligofluorene structural unit in the said resin to a specific range. As a method of adjusting the ratio of the oligofluorene structural unit in the resin, for example, a method of copolymerizing the monomer having the oligofluorene structural unit with another monomer, or a resin having the oligofluorene structural unit and The method of blending other resin is mentioned. The content of the oligofluorene structural unit can be precisely controlled, and high transparency is obtained, and uniform properties are obtained over the entire surface of the film. The method of copolymerization is preferable.

It is preferable that content of the said oligofluorene structural unit in the said resin is 1 mass % or more and 40 mass % or less with respect to the whole resin, It is more preferable that they are 10 mass % or more and 35 mass % or less, 15 mass % or more and 32 mass % The following is more preferable, and 20 mass % or more and 30 mass % or less are especially preferable. When there is too much content of an oligofluorene structural unit, there exists a possibility that a photoelastic coefficient and reliability may deteriorate, or high birefringence may not be obtained by extending|stretching. In addition, since the proportion of the oligofluorene structural unit in the resin increases, the molecular design becomes narrow, and improvement becomes difficult when the resin is required to be modified. On the other hand, even if the desired reverse wavelength dispersion is obtained with a very small amount of oligofluorene structural units, in this case, since the optical properties are sensitively changed according to small deviations in the content of oligofluorene, various properties are It becomes difficult to manufacture so that it may fall within a certain range.

It is preferable to obtain resin of this invention by copolymerizing the monomer which has the said oligofluorene structural unit, and another monomer. As another monomer to copolymerize, a dihydroxy compound and a diester compound are mentioned, for example.

It is preferable that resin of this invention contains the structural unit of the following general formula (3) as a copolymerization component from viewpoints, such as an optical characteristic, a mechanical characteristic, heat resistance.

[Formula 26]

As a dihydroxy compound into which the structural unit represented by the said General formula (3) can be introduce|transduced, isosorbide (ISB), isomannide, and isoidide which exist in a stereoisomer relationship are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, it is most preferable to use ISB from the viewpoint of availability and polymerization reactivity.

The structural unit represented by the general formula (3) is preferably contained in 5 mass% or more and 70 mass% or less in the resin, more preferably in 10 mass% or more and 65 mass% or less, and 20 mass% or more. % or more and 60 mass% or less are particularly preferably contained. When there is too little content of the structural unit represented by the said General formula (3), there exists a possibility that heat resistance may become inadequate. On the other hand, when there is too much content of the structural unit represented by the said General formula (3), heat resistance will become high excessively, and a mechanical characteristic and melt workability will deteriorate. Moreover, since the structural unit represented by the said General formula (3) has a structure with high hygroscopicity, when there is too much content, the water absorption of resin becomes high, and there exists a possibility that dimensional deformation|transformation may occur in a high-humidity environment.

Moreover, the resin of this invention may contain another structural unit in combination with the structural unit of the said General formula (3), or without using the structure of the said General formula (3). (Hereinafter, such structural units are sometimes referred to as "other structural units.")

As the above-described other structural units, those having structural units represented by the following general formulas (4) to (8) which do not contain an aromatic component are particularly preferable.

[Formula 27]

In the said General formula (4), R<^1>-10 represents the C2-C20 alkylene group which may have a substituent.

As a dihydroxy compound into which the structural unit of the said General formula (4) can be introduce|transduced, the following dihydroxy compounds are employable, for example. Ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1 and dihydroxy compounds of linear aliphatic hydrocarbons such as 9-nonanediol, 1,10-decanediol and 1,12-dodecanediol; dihydroxy compounds of branched aliphatic hydrocarbons such as neopentyl glycol and hexylene glycol.

[Formula 28]

In the general formula (5), R ^1-11 represents a cycloalkylene group having 4 to 20 carbon atoms which may have a substituent.

As a dihydroxy compound into which the structural unit of the said General formula (5) can be introduce|transduced, the following dihydroxy compounds are employable, for example. Examples include 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, etc. A dihydroxy compound that is a secondary alcohol and a tertiary alcohol of an alicyclic hydrocarbon.

[Formula 29]

In the general formula (6), R ^1-12 represents a cycloalkylene group having 4 to 20 carbon atoms which may have a substituent.

As a dihydroxy compound into which the structural unit of the said General formula (6) can be introduce|transduced, the following dihydroxy compounds are employable, for example. 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1, Derived from terpene compounds such as 5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantane dimethanol, and limonene The dihydroxy compound which is a primary alcohol of an alicyclic hydrocarbon illustrated by a dihydroxy compound etc.

[Formula 30]

In the said General formula (7), R ^1-13 represents the C2-C10 alkylene group which may have a substituent, and p is an integer of 1-40.

As a dihydroxy compound into which the structural unit of the said General formula (7) can be introduce|transduced, the following dihydroxy compounds are employable, for example. oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol.

[Formula 31]

In the said General formula (8), R ^1-14 represents the group which has a C2-C20 acetal ring which may have a substituent.

As the dihydroxy compound into which the structural unit of the general formula (8) can be introduced, for example, spiroglycol represented by the following structural formula (14), dioxane glycol represented by the following structural formula (15), or the like can be employed.

[Formula 32]

Moreover, you may use the dihydroxy compound containing the aromatic component illustrated below other than the dihydroxy compound mentioned above. 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl) Propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2,2-bis(4 -Hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) methane, 1, 1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyl Phenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl) Decane, bis(4-hydroxy-3-nitrophenyl)methane, 3,3-bis(4-hydroxyphenyl)pentane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl) Benzene, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydro Roxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl) aromatic bisphenol compounds such as sulfide, bis(4-hydroxyphenyl)disulfide, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether; 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane, 1,3-bis(2-hydroxyl dihydroxy compounds having an ether group bonded to an aromatic group, such as ethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, and bis(4-(2-hydroxyethoxy)phenyl)sulfone; 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl) ) fluorene, 9,9-bis (4- (2-hydroxypropoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene; 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl) Fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl ) Fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3- A dihydroxy compound having a fluorene ring, such as tert-butyl-6-methylphenyl)fluorene and 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene.

Moreover, as a diester compound which can be used for copolymerization with the monomer which has the said oligofluorene structural unit, the dicarboxylic acid etc. which are shown below are employable, for example. Terephthalic acid, phthalic acid, isophthalic acid, 4,4'-diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 4,4'-diphene Aromatic dicarboxylic acids such as oxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid; 1,2-cyclohexanedicarboxylic acid, 1 alicyclic dicarboxylic acids such as ,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid aliphatic dicarboxylic acids such as acids and sebacic acids. In addition, although these dicarboxylic acid components can be used as a raw material of the said polyester carbonate as dicarboxylic acid itself, dicarboxylic acid esters, such as a methyl ester form, a phenyl ester form, and dicarboxylic acid esters, depending on a manufacturing method, Dicarboxylic acid derivatives, such as an acid halide, can also be used as a raw material.

From the viewpoint of optical properties, it is preferable to use those that do not contain an aromatic component as the other structural units exemplified above. If the main chain of the polymer contains an aromatic component, since the reverse wavelength dispersion of the fluorene ring is canceled as described above, it is necessary to increase the content of the oligofluorene structural unit, and the photoelastic coefficient will also deteriorate. There are concerns. By employing the above-mentioned other structural unit not containing an aromatic component, it is possible to prevent the aromatic component from being inserted into the main chain derived from the structural unit.

On the other hand, it may be effective to insert an aromatic component in the main chain or side chain of a polymer in order to balance heat resistance, a mechanical characteristic, etc. while ensuring an optical characteristic. In this case, an aromatic component can be introduce|transduced into a polymer by the said other structural unit containing an aromatic component, for example.

From the viewpoint of balancing various characteristics, a structural unit containing an aromatic group in the resin (however, the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) are excluded). It is preferable that content of is 5 mass % or less.

As the monomer having other structural units exemplified above, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, spiroglycol, and 1,4-cyclohexanedicarboxylic acid (and derivatives thereof) are employed. Especially preferred. Resin containing the structural unit derived from these monomers is excellent in the balance of optical properties, heat resistance, mechanical properties, and the like.

In the case of the most preferable polyester carbonate in the present invention, since the polymerization reactivity of the diester compound is relatively low, from the viewpoint of increasing the reaction efficiency, a diester compound other than the diester compound having an oligofluorene structural unit is used It is preferable not to

You may use the dihydroxy compound and diester compound for introduce|transducing another structural unit individually or in combination of 2 or more type according to the required performance of resin obtained. 1 mass % or more and 60 mass % or less are preferable, as for content of the other structural unit in resin, 5 mass % or more and 55 mass % or less are more preferable, 10 mass % or more and 50 mass % or less are especially preferable. Since other structural units are particularly responsible for adjusting the heat resistance of the resin and imparting flexibility and toughness, when the content is too small, the mechanical properties and melt workability of the resin deteriorate, and when the content is too large, the heat resistance or toughness There is a possibility that an optical characteristic may deteriorate.

<The manufacturing method of the resin of this invention>

Polycarbonate, polyester, and polyester carbonate, which are suitably used with the resin of the present invention, can be produced by a polymerization method generally used. That is, the said resin can be manufactured using, for example, the solution polymerization method or the interfacial polymerization method using phosgene or a carboxylic acid halide, or the melt polymerization method which performs reaction without using a solvent. Among these manufacturing methods, it is preferable to manufacture by the melt polymerization method which can reduce an environmental load and is excellent also in productivity since a solvent or a highly toxic compound is not used.

Moreover, when using a solvent for polymerization, since the glass transition temperature of resin falls by the plasticizing effect by the residual solvent in resin, in the extending process mentioned later, it becomes difficult to control molecular orientation constant. Moreover, when a halogen-type organic solvent, such as methylene chloride, remains in resin, if a molded object using this resin is attached to an electronic device etc., it may become a cause of corrosion. Since the resin obtained by the melt polymerization method does not contain a solvent, it is advantageous also in a processing process and stabilization of product quality.

When the above resin is produced by melt polymerization, a monomer having an oligofluorene structural unit, a copolymer monomer of another diol or diester, and a polymerization catalyst are mixed, subjected to a transesterification reaction under melting, and the desorption component is removed. The reaction rate increases while removing it outside. At the end of polymerization, the reaction proceeds to the target molecular weight under conditions of high temperature and high vacuum. When the reaction is completed, resin in a molten state is extracted from the reactor to obtain a resin raw material used for molded articles such as retardation film.

In the present invention, the polycarbonate or polyester carbonate can be obtained by polycondensing a monomer containing at least an oligofluorene structural unit, one or more dihydroxy compounds and diester carbonate as raw materials, and polycondensing them.

As a diester carbonate used for a polycondensation reaction, what is normally represented by the general formula (11) mentioned above is mentioned. These diester carbonates may be used individually by 1 type, and may mix and use 2 or more types.

[Formula 33]

In the general formula (11), A ¹ and A ² each represent an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent or an aromatic hydrocarbon group which may have a substituent, and A ¹ and A ² may be the same or different. You can do it.

A ¹ and A ² are preferably a substituted or unsubstituted aromatic hydrocarbon group, and more preferably an unsubstituted aromatic hydrocarbon group. Moreover, as a substituent of an aliphatic hydrocarbon group, an ester group, an ether group, carboxylic acid, an amide group, and a halogen atom are mentioned, As a substituent of an aromatic hydrocarbon group, alkyl groups, such as a methyl group and an ethyl group, are mentioned.

Examples of the diester carbonate represented by the general formula (11) include substituted diphenyl carbonates such as diphenyl carbonate (DPC) and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate. Although illustrated, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, diester carbonate may contain impurities such as chloride ions and may inhibit polymerization reaction or deteriorate the color of the polycarbonate obtained. It is preferable to use

Polycondensation reaction can control reaction rate and molecular weight of resin obtained by adjusting strictly the molar ratio of all the dihydroxy compounds used for reaction, and a diester compound. In the case of polycarbonate, the molar ratio of diester carbonate to all dihydroxy compounds is preferably adjusted to 0.90 to 1.10, more preferably 0.96 to 1.05, particularly preferably 0.98 to 1.03. do. In the case of polyester, the molar ratio of all diester compounds to all dihydroxy compounds is preferably adjusted to 0.70 to 1.10, more preferably 0.80 to 1.05, and particularly to adjust to 0.85 to 1.00. desirable. In the case of polyester carbonate, the molar ratio of the total amount of diester carbonate and all diester compounds to all dihydroxy compounds is preferably adjusted to 0.90 to 1.10, more preferably 0.96 to 1.05, and 0.98 It is especially preferable to adjust to 1.03.

When the above molar ratios greatly deviate vertically, it becomes impossible to produce a resin having a desired molecular weight. Moreover, when said molar ratio becomes small too much, the hydroxyl group terminal of the manufactured resin increases, and the thermal stability of resin may deteriorate. In addition, when the molar ratio is too large, the rate of the transesterification reaction is lowered under the same conditions, or the residual amount of diester carbonate or diester compound in the produced resin increases, and the remaining low molecular weight component volatilizes during film forming or stretching. and may cause defects in the film.

The melt polymerization method is usually performed in a multistage process of two or more steps. The polycondensation reaction may be carried out in two or more steps using one polymerization reactor, changing sequential conditions, or using two or more reactors, changing each condition and performing in two or more steps, but production efficiency From the viewpoint of The polycondensation reaction may be carried out in a batch type, a continuous type, or a combination of a batch type and a continuous type, but the continuous type is preferable from the viewpoint of production efficiency and stability of quality.

In the polycondensation reaction, it is important to appropriately control the balance between the temperature and the pressure in the reaction system. When either one of temperature and pressure is changed too quickly, unreacted monomer flows out to the outside of the reaction system. As a result, the molar ratio of a dihydroxy compound and a diester compound changes, and resin of a desired molecular weight may not be obtained.

Moreover, the polymerization rate of a polycondensation reaction is controlled by the balance of a hydroxyl group terminal, an ester group terminal, or a carbonate group terminal. Therefore, especially in the case of continuous polymerization, if the balance of the terminal groups fluctuates due to the outflow of unreacted monomers, it becomes difficult to control the polymerization rate uniformly, and there is a risk that the molecular weight of the resin obtained will fluctuate greatly. have. Since the molecular weight of the resin is correlated with the melt viscosity, when the obtained resin is melt-formed, the melt viscosity fluctuates, and it becomes difficult to keep the quality such as the film thickness of the film constant, resulting in a decrease in the quality and productivity of the film. do.

In addition, when the unreacted monomer flows out, not only the balance of the terminal groups but also the copolymer composition of the resin deviate from the desired composition, and there is a fear that the optical quality of the retardation film is affected. In the retardation film of the present invention, since the wavelength dispersibility of the retardation described later is controlled by the ratio of the oligofluorene and the copolymerization component in the resin, if the ratio collapses during polymerization, the optical properties as designed are not obtained, or When obtaining a long film, an optical characteristic changes with the position of a film, and there exists a possibility that it may become impossible to manufacture a polarizing plate of constant quality.

Specifically, as the reaction conditions in the first stage reaction, the following conditions can be adopted. That is, the maximum temperature of the internal temperature of the polymerization reactor is usually 130°C or higher, preferably 150°C or higher, more preferably 170°C or higher, and usually 250°C or lower, preferably 240°C or lower. , More preferably, it is set in the range of 230 degrees C or less. Moreover, the pressure of a polymerization reactor is 70 kPa or less normally (hereafter, pressure shows absolute pressure), Preferably it is 50 kPa or less, More preferably, 30 kPa or less, Furthermore, it is 1 kPa or more normally, Preferably is set in the range of 3 kPa or more, more preferably 5 kPa or more. The reaction time is usually 0.1 hours or more, preferably 0.5 hours or more, and usually 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less. The reaction in the first stage is carried out while distilling off the generated monohydroxy compound derived from the diester compound to the outside of the reaction system. For example, when diphenyl carbonate is used as diester carbonate, the monohydroxy compound distilled out of the reaction system in the first stage reaction is phenol.

In the first stage reaction, the polymerization reaction can be accelerated as the reaction pressure is lowered, but on the other hand, the outflow of unreacted monomers increases. It is effective to use a reactor equipped with a reflux condenser in order to make both suppression of the outflow of an unreacted monomer and acceleration|stimulation of reaction by pressure reduction compatible. In particular, it is preferable to use a reflux condenser at the beginning of the reaction in which there are many unreacted monomers.

In the reaction after the second stage, the pressure of the reaction system is gradually lowered from the pressure of the first stage, the monohydroxy compound continuously generated is removed out of the reaction system, and finally the pressure of the reaction system is lowered to 5 kPa or less, preferably 3 It is kPa or less, More preferably, it is set as 1 kPa or less. Moreover, the maximum internal temperature is 210 degreeC or more normally, Preferably it is 220 degreeC or more, Furthermore, it is 270 degrees C or less normally, Preferably it sets in the range of 260 degrees C or less. The reaction time is usually 0.1 hours or more, preferably 0.5 hours or more, more preferably 1 hour or more, and usually 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less. set in the range. In order to suppress coloring and thermal deterioration and to obtain a resin having good color and thermal stability, the maximum internal temperature in the entire reaction step is preferably 270°C or less, preferably 260°C or less, and more preferably 250°C or less. do.

A transesterification catalyst (hereinafter, simply referred to as a catalyst or a polymerization catalyst) that can be used during polymerization can have a very large effect on the reaction rate, color tone and thermal stability of the resin obtained by polycondensation. The catalyst used is not limited as long as it can satisfy the transparency, color, heat resistance, thermal stability, and mechanical strength of the prepared resin, but is not limited to Group 1 or Group 2 (hereinafter simply referred to as “1” in the long-period periodic table). group" and "group 2."), basic compounds such as metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds. Preferably, at least one metal compound selected from the group consisting of metals of Group 2 of the long-period periodic table and lithium is used.

As said Group 1 metal compound, although the following compound is employable, for example, Group 1 metal compound other than these is also employable. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, acetic acid Lithium, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium tetraphenylborate, potassium tetraphenylborate, tetraphenylboric acid Lithium, cesium tetraphenylborate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, disodium hydrogen phosphate, disodium hydrogen phosphate, 2 cesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, phenyl dilithium phosphate, dicesium phenyl phosphate, sodium, potassium, lithium, alcoholates of cesium, phenolate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, dicesium salt, etc. are mentioned. Among these, it is preferable to use a lithium compound from a viewpoint of polymerization activity and the hue of the polycarbonate obtained.

As said Group 2 metal compound, although the following compounds are employable, for example, Group 2 metal compounds other than these are also employable. For example, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, acetate Magnesium, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc. are mentioned. Among these, it is preferable to use a magnesium compound, a calcium compound, and a barium compound, and from the viewpoint of polymerization activity and the color of the polycarbonate obtained, it is more preferable to use a magnesium compound and/or a calcium compound, and a calcium compound is used. it is most preferable

In addition, it is also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound in combination with the above Group 1 metal compound and/or Group 2 metal compound, but a long-period cycle It is particularly preferable to use at least one metal compound selected from the group consisting of metals of Table 2 and lithium.

As said basic phosphorus compound, although the following compounds are employable, for example, It is also possible to employ|adopt basic phosphorus compounds other than these. Examples include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, or quaternary phosphonium salt. have.

As said basic ammonium compound, although the following compounds are employable, for example, Basic ammonium compounds other than these are also employable. For example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, N,N,N-trimethylethanolamine (choline), trimethylethylammonium hydroxide , trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenyl Ammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, etc. are mentioned.

As said amine compound, although the following compounds are employable, for example, It is also possible to employ|adopt amine compounds other than these. For example 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, guanidine, etc. are mentioned.

The usage-amount of the said polymerization catalyst is 0.1 micromol - 300 micromol per 1 mol of all the dihydroxy compounds used for superposition|polymerization normally, Preferably they are 0.5 micromol - 100 micromol. As the polymerization catalyst, when at least one metal compound selected from the group consisting of metals of Group 2 of the long-period periodic table and lithium is used, particularly when a magnesium compound and/or a calcium compound is used, the amount of metal is , The polymerization catalyst is usually 0.1 μmol or more, preferably 0.3 μmol or more, particularly preferably 0.5 μmol or more, per 1 mol of the total dihydroxy compound. Moreover, 30 micromol or less is good, and, as for the usage-amount of the said polymerization catalyst, Preferably it is 20 micromol or less, Especially preferably, it is 10 micromol or less.

Moreover, when using a diester compound as a monomer to manufacture polyester or polyester carbonate, a titanium compound, a tin compound, a germanium compound, an antimony compound, a zirconium compound, together with or without the said basic compound, A transesterification catalyst, such as a lead compound, an osmium compound, a zinc compound, and a manganese compound, can also be used. The usage-amount of these transesterification catalyst is a metal amount with respect to 1 mol of all the dihydroxy compounds used for reaction, Usually, it uses within the range of 1 micromol - 1 mmol, Preferably it is 5 micromol - 800 It exists in the range of micromolar, Especially preferably, it is 10 micromoles - 500 micromoles.

When the catalyst amount is too small, the polymerization rate is slowed, and therefore, in order to obtain a resin having a desired molecular weight, the polymerization temperature must be increased by that much. Therefore, the possibility that the color of the obtained resin will deteriorate increases, and unreacted raw materials volatilize during polymerization, the molar ratio of the dihydroxy compound and the diester compound may collapse, and the desired molecular weight may not be reached. On the other hand, when there is too much usage-amount of a polymerization catalyst, an undesirable side reaction may occur and the color deterioration of the resin obtained or coloring of the resin at the time of a molding process may be caused.

Among the Group 1 metals, sodium, potassium, and cesium may adversely affect the color when contained in large amounts in the resin. Incidentally, these metals may be mixed not only from the catalyst to be used, but also from the raw material or the reaction apparatus. Regardless of the source, the total amount of these metal compounds in the resin is preferably 2 μmol or less, more preferably 1 μmol or less, more preferably, per 1 mol of the total dihydroxy compound as the amount of metal. 0.5 μmol or less.

In addition, as a monomer having an oligofluorene structural unit, when a polyester carbonate is produced using the diester compound represented by the general formula (13), the diester compound in which A ³ and A ⁴ are aromatic hydrocarbon groups is used. It is preferable to use the above diester compound in which ^{A 3} and A ^{4 are phenyl groups.} By using these diester compounds, polymerization reactivity is favorable, the quantity of the catalyst used can be reduced, the color tone and thermal stability of resin obtained can be improved, and the foreign material in resin can be reduced.

After the resin of the present invention is polymerized as described above, it is usually cooled and solidified, and can be pelletized with a rotary cutter or the like. The method of pelletization is not limited, but a method of withdrawing in a molten state from the polymerization reactor of the final stage, cooling and solidifying in the form of strands to pelletize, and a resin in a single-screw or twin-screw extruder in a molten state from the polymerization reactor of the final stage A method of supplying, melt-extruding, cooling and solidifying to pelletize, or extracting in a molten state from the polymerization reactor of the final stage, cooling and solidifying in the form of a strand, and once pelletizing, a single-screw or twin-screw extruder After supplying resin to and melt-extruding, the method of making it solidify by cooling and pelletizing, etc. are mentioned.

Thus, the molecular weight of the obtained resin can be expressed by reduced viscosity. If the reduced viscosity of the resin is too low. There is a possibility that the mechanical strength of the molded product becomes small. Therefore, a reduced viscosity is 0.20 dL/g or more normally, and it is preferable that it is 0.30 dL/g or more. On the other hand, when the reduced viscosity of the resin is too large, the fluidity at the time of molding decreases, and there is a tendency to decrease productivity and moldability. Therefore, the reduced viscosity is usually 1.20 dl/g or less, preferably 1.00 dl/g or less, and more preferably 0.80 dl/g or less. In addition, reduced viscosity is measured using methylene chloride as a solvent, polycarbonate density|concentration is precisely prepared to 0.6 g/dL, and using the Uberode viscometer at the temperature of 20.0 degreeC±0.1 degreeC.

Since the reduced viscosity is correlated with the melt viscosity of the resin, usually, the stirring power of the polymerization reactor, the discharge pressure of a gear pump that transports the molten resin, and the like can be used as an index of operation management. That is, when the indication value of the operating device reaches the target value, the polymerization reaction is stopped by returning the pressure of the reactor to normal pressure or withdrawing the resin from the reactor.

It is preferable that melt viscosity of resin of this invention is 700 Pa.s or more and 5000 Pa.s or less in the measurement conditions of a ^{temperature of 240 degreeC and a shear rate of 91.2 sec -1.} 800 Pa.s or more and 4500 Pa.s or less are more preferable, and further 900 Pa.s or more and 4000 Pa.s or less are preferable, and 1000 Pa.s or more and 3500 Pa.s or less are especially preferable. In addition, melt viscosity is measured using a capillary rheometer (made by Toyo Seiki Co., Ltd.).

It is preferable that they are 110 degreeC or more and 160 degrees C or less, and, as for the glass transition temperature of resin of this invention, it is more preferable that they are 120 degrees C or more and 155 degrees C or less. When the glass transition temperature is excessively low, heat resistance tends to deteriorate, dimensional changes may occur after film forming, or reliability of the quality under the conditions of use of the retardation film may deteriorate. On the other hand, when the glass transition temperature is excessively high, there may be cases in which non-uniformity in film thickness occurs at the time of film forming, the film becomes brittle, and the ductility deteriorates, and the transparency of the film may be impaired.

The resin has a storage modulus of preferably 1 GPa or more and 2.7 GPa or less, more preferably 1.1 GPa or more and 2.5 GPa or less, still more preferably 1.2 GPa or more and 2.3 GPa or less, and particularly preferably 1.3 GPa or more and 2.2 GPa or less. When the storage elastic modulus is in the above range, the handling properties and strength of the film are excellent. The measuring method of a storage elastic modulus is mentioned later in the term of an Example.

In order to obtain a polycarbonate resin film having a storage elastic modulus in a specific range specified in the present invention, a polycarbonate resin having a specific structure specified in the present invention is employed, and then the melt viscosity is appropriately adjusted, or a structural unit thereof. It can be achieved by appropriately selecting the film, adjusting the ratio of the structural unit, adding a plasticizer in the polycarbonate resin, and the like, or selecting appropriate film forming conditions and stretching conditions.

When a diester compound is used for the polycondensation reaction, a byproduct monohydroxy compound remains in the resin, volatilizes during film forming or stretching, and becomes odorous to deteriorate the working environment, or to contaminate the conveying roll, etc. There is a possibility of impairing the appearance of a film. When diphenyl carbonate (DPC), which is a particularly useful diester carbonate, is used, the by-product phenol has a relatively high boiling point, is not sufficiently removed even by reaction under reduced pressure, and tends to remain in the resin.

Therefore, it is preferable that the monohydroxy compound derived from diester carbonate contained in resin of this invention is 1500 mass ppm or less. Furthermore, 1000 mass ppm or less is preferable, and it is especially preferable that it is 700 mass ppm or less. In addition, in order to solve the above problem, the monohydroxy compound is better as the content is smaller, but in the melt polymerization method, it is difficult to zero the monohydroxy compound remaining in the polymer, and excessive effort is required for removal. . Usually, the said problem can fully be suppressed by reducing content of a monohydroxy compound to 1 mass ppm.

In order to reduce the low molecular weight components including the monohydroxy compound derived from diester carbonate remaining in the resin of the present invention, the resin is degassed with an extruder as described above, or the pressure at the end of polymerization is 3 kPa or less, preferably It is effective to set it as 2 kPa or less, More preferably, to set it as 1 kPa or less.

In the case of lowering the pressure at the end of polymerization, if the pressure of the reaction is too low, the molecular weight rises rapidly and the control of the reaction may become difficult. It is preferable to make it excessively, and to manufacture by biasing terminal group balance. Among them, from the viewpoint of thermal stability, the hydroxyl group terminal amount is preferably 50 mol/ton or less, particularly 40 mol/ton or less. The hydroxyl group terminal amount ^{can be quantified by 1} H-NMR or the like. The hydroxyl group terminal amount can be adjusted by the molar ratio of the total dihydroxy compound to the total diester compound.

In the resin of the present invention, if necessary, a thermal stabilizer may be blended in order to prevent a decrease in molecular weight or deterioration of color during molding or the like. As such a thermal stabilizer, a commonly known hindered phenol-based thermal stabilizer and/or a phosphorus-based thermal stabilizer may be mentioned.

As a hindered phenol type compound, the following compounds are employable, for example. 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6 -di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,5-di-tert-butylhydroquinone, n-octadecyl-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4 -Methylphenyl acrylate, 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis-(6-cyclohexyl-4-methylphenol), 2, 2'-ethylidene-bis-(2,4-di-tert-butylphenol), tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)prop cionate]-methane, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and the like. Among them, tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]-methane, n-octadecyl-3-(3',5 '-di-tert-butyl-4'-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxy benzyl)benzene is preferred.

As the phosphorus compound, for example, phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, esters thereof and the like shown below can be employed, but phosphorus compounds other than these compounds can also be employed. For example, triphenylphosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecyl Monophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis(2,6-di-tert) -Butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2, 4-di-tert-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl Phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), dimethyl benzene phosphonate, diethyl benzene phosphonate, benzene phosphonate phonsandipropyl, etc. are mentioned. These thermal stabilizers may be used individually by 1 type, and may use 2 or more types together.

Such a heat stabilizer may be added to the reaction liquid at the time of melt polymerization, or it may be added to resin using an extruder, and may be kneaded. When the film is formed by the melt extrusion method, the heat stabilizer or the like may be added to the extruder to form a film, or the heat stabilizer or the like may be added to the resin in advance using an extruder to form pellets or the like. .

The blending amount of these thermal stabilizers is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, still more preferably 0.001 parts by mass or more, and 1 mass parts when the resin used in the present invention is 100 parts by mass. A part or less is preferable, 0.5 mass part or less is more preferable, and 0.2 mass part or less is still more preferable.

An antioxidant commonly known for the purpose of preventing oxidation may be blended with the resin of the present invention as needed. As such antioxidant, for example, the compounds shown below can be employed, but compounds other than these can also be employed. For example, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol- Bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4- Hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5- di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-Hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl Ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis(2,4-di-tert-butylphenyl) , 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetra and oxaspiro (5,5) undecane. Said antioxidant may be used individually by 1 type, and may use 2 or more types together. When the compounding quantity of these antioxidants makes resin of this invention 100 mass parts, 0.0001 mass part or more is preferable, and 0.5 mass part or more is preferable.

In addition, in the resin of the present invention, a UV absorber, a mold release agent, an antistatic agent, a slip agent, a lubricant, a plasticizer, a compatibilizer, a nucleating agent, a flame retardant, an inorganic filler, an impact modifier that are commonly used in the range that does not impair the object of the present invention , foaming agent, dye pigment, etc. may be included.

In addition, the resin of the present invention is an aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acryl, amorphous polyolefin, ABS for the purpose of modifying properties such as mechanical properties and solvent resistance of the resin. , AS, polylactic acid, polybutylene succinate, etc., synthetic resins, such as rubber, or the like may be used as a polymer alloy obtained by kneading with one or two or more kinds.

The above additives or modifiers can be prepared by mixing the above components with the resin of the present invention at the same time or in any order by a mixer such as a tumbler, V-blender, Nauta mixer, Banbury mixer, kneading roll, or extruder, Especially, it is preferable from a viewpoint of a dispersibility improvement to knead|mix with an extruder, especially a twin screw extruder.

The resin obtained as described above has low birefringence, is excellent in heat resistance and moldability, and has little coloration and high transparency. It is suitably used as a film.

<The manufacturing method of an unstretched film>

As a method of forming an unstretched film using the resin of the present invention, a casting method in which the resin is dissolved in a solvent and cast, and then the solvent is removed, or a melt film forming method in which the resin is melted without using a solvent to form a film law can be adopted. Specific examples of the melt film forming method include a melt extrusion method using a T die, a calender molding method, a hot press method, a coextrusion method, a co-melting method, a multilayer extrusion method, and an inflation molding method. Although the film forming method of an unstretched film is not specifically limited, Since there exists a possibility that the problem by residual solvent may arise in the casting method, Preferably, it is a melt film forming method, especially, from the easiness of subsequent extending|stretching process, melt extrusion method using T-die This is preferable.

When forming an unstretched film by the melt film forming method, the molding temperature is preferably 270°C or lower, more preferably 265°C or lower, and particularly preferably 260°C or lower. When molding temperature is too high, the defect by generation|occurrence|production of the foreign material and bubble in the film obtained may increase, or a film may color. However, when the molding temperature is too low, the melt viscosity of the resin becomes excessively high, making it difficult to form a raw film, and there is a possibility that it may be difficult to produce an unstretched film having a uniform thickness, so the lower limit of the molding temperature is usually 200°C or higher, preferably 210°C or higher, and more preferably 220°C or higher. Here, the shaping|molding temperature of an unstretched film is the temperature at the time of shaping|molding in the melt film forming method, and is the value which measured the temperature of the die outlet which extrudes molten resin normally.

Moreover, when a foreign material exists in a film, when it is used as a polarizing plate, it will be recognized as faults, such as light leakage. In order to remove foreign substances in the resin, it is preferable to attach a polymer filter to the back of the extruder, filter the resin, and then extrude from a die to form a film. In that case, it is necessary to connect an extruder, a polymer filter, and a die|dye to piping, and to transfer molten resin, but in order to suppress thermal deterioration in piping as much as possible, it is important to arrange|position each facility so that a residence time may be shortest. Moreover, the conveyance and winding process of the film after extrusion are performed in a clean room, and the best caution is calculated|required so that a foreign material may not adhere to a film.

The thickness of the unstretched film is determined according to the stretching conditions such as the design of the film thickness of the retardation film after stretching and the stretching ratio. It is usually 30 µm or more, preferably 40 µm or more, more preferably 50 µm or more, and is usually 200 µm or less, preferably 160 µm or less, more preferably 120 μm or less. In addition, if there is a non-uniformity (deviation) of thickness in the unstretched film, since it causes retardation non-uniformity of the retardation film, the thickness of the portion used as the retardation film is preferably ±3 µm or less, and the set thickness is ±2 µm or less. It is more preferable, and it is especially preferable that it is less than or equal to the set thickness ±1 mu m.

The length of the unstretched film in the longitudinal direction is preferably 500 m or more, more preferably 1000 m or more, and particularly preferably 1500 m or more. From the viewpoint of productivity or quality, when manufacturing the retardation film of the present invention, it is preferable to extend continuously, but in general, condition adjustment is necessary in order to match a predetermined retardation at the start of stretching, and the length of the film is When it is too short, the quantity of the product which can be acquired after conditioning will decrease. In addition, in this specification, "long" means that the dimension in the longitudinal direction is sufficiently larger than the width direction of a film, and it means the thing of the extent which can be made into coil shape by winding in the longitudinal direction substantially. More specifically, it means that the dimension in the longitudinal direction of the film is 10 times or more larger than the dimension in the width direction.

It is preferable that an internal haze is 3 % or less, and, as for the unstretched film obtained as mentioned above, it is more preferable that it is 2 % or less, It is especially preferable that it is 1 % or less. When the internal haze of an unstretched film is larger than the said upper limit, when scattering of light arises, for example, and laminating|stacking with a polarizer, it may become a cause which produces polarization cancellation. Although the lower limit of an internal haze is not specifically set, Usually, it is 0.1 % or more. For the measurement of the internal haze, a transparent film with an adhesive, which has been previously measured for haze, is pasted on both sides of an unstretched film, and a sample in a state in which the influence of the external haze is removed is used, Let the value obtained by subtracting the haze value of the transparent film from the measured value of the sample be the value of the internal haze.

It is preferable that the b* value of an unstretched film is 3 or less. When the b* value of a film is too large, problems, such as coloring, will arise. The b* value is more preferably 2 or less, particularly preferably 1 or less.

Regardless of the thickness of the unstretched film, the total light transmittance of the film itself is preferably 85% or more, more preferably 90% or more, still more preferably 91% or more, and particularly preferably 92% or more. When the transmittance is more than the above lower limit, a film with little coloring is obtained, and when it is bonded to a polarizing plate, it becomes a circularly polarizing plate with a high degree of polarization and transmittance, and when used for an image display device, it becomes possible to realize high display quality. In addition, although there is no restriction|limiting in particular in the upper limit of the total light transmittance of the film of this invention, Usually, it is 99 % or less.

In addition to making the said haze and b* value low, also by making the refractive index of resin low, the reflection of a film surface can be suppressed and a total light transmittance can be improved. When the resin of the present invention is used for a circular polarizing plate for preventing reflection of external light, increasing the total light transmittance leads to reducing the reflectance of external light. It is preferable that the refractive index in sodium d line|wire (589 nm) of resin used for this invention is 1.49 - 1.56. Moreover, as for the said refractive index, it is more preferable that it is 1.50 - 1.55, It is still more preferable that it is 1.51 - 1.54, It is especially preferable that it is 1.51 - 1.53. Since the resin used in the present invention contains an oligofluorene structural unit, the refractive index becomes high compared with the total aliphatic polymer, but by not using an aromatic compound in the copolymerization component, the refractive index can be put in the above range.

The resin of the present invention preferably has a photoelastic coefficient of 25 × 10 ^-12 Pa ^-1 or less, more preferably 20 × 10 ^-12 Pa ^-1 or less, and particularly preferably 15 × 10 ^-12 Pa ^{-1 or less.} . When the photoelastic coefficient is excessively large and the retardation film is bonded to a polarizing plate, there is a possibility that the image quality deteriorates in which the periphery of the screen becomes white. In particular, when used for a large-sized display device, this problem appears remarkably.

It is preferable that the said unstretched film does not brittle fracture in the bending test mentioned later. In the film which brittle fracture generate|occur|produces, the fracture|rupture of a film occurs easily at the time of film forming or extending|stretching of a film, and there exists a possibility of worsening the yield of manufacture. In order to make a film which does not brittle fracture, it is important to design the molecular weight, melt viscosity, and glass transition temperature of the resin used for this invention in the above-mentioned preferable range. Moreover, the method of adjusting the characteristic of a film by copolymerizing or blending the component which can provide softness|flexibility is also effective.

It is preferable that the resin of this invention has a saturated water absorption larger than 1.0 mass %. When a saturated water absorption is larger than 1.0 mass %, when bonding this film together with another film etc., there exists a tendency which can ensure adhesiveness easily. For example, when bonding with a polarizing plate, since a film is hydrophilic, the contact angle of water is also low, and it is easy to design an adhesive agent freely, and high adhesion|attachment design can be performed. When the saturated water absorption is 1.0 mass % or less, it becomes hydrophobic, the contact angle of water is also high, and adhesive design becomes difficult. Moreover, when a film becomes easy to charge and it mounts to a circular polarizing plate and an image display apparatus, such as mixing of a foreign material, there exists a tendency for the problem that an external appearance defect increases. On the other hand, when the saturated water absorption ratio becomes larger than 3.0 mass %, since durability of the optical characteristic in a humid environment tends to worsen, it is unpreferable. It is preferable that saturated water absorption is larger than 1.0 mass %, and, as for the resin of this invention, it is more preferable that it is 1.1 mass % or more, It is preferable that it is 3.0 mass % or less, It is more preferable that it is 2.5 mass % or less. On the other hand, it is good also considering the saturated water absorption as 1.0 mass % or less depending on the usage conditions of a film and the image display apparatus using it.

<Method for producing retardation film>

Retardation film can be obtained by extending|stretching orientating the said unstretched film. As an extending|stretching method, well-known methods, such as longitudinal uniaxial stretching, lateral uniaxial stretching using a tenter etc., or simultaneous biaxial stretching and sequential biaxial stretching which combined them can be used. Although extending|stretching may be implemented by a batch type, it is preferable in productivity to carry out continuously. Moreover, compared with a batch type, the retardation film with few dispersion|variation in the retardation in a film plane in the continuous direction is obtained.

The stretching temperature is in the range of (Tg-20°C) to (Tg+30°C) with respect to the glass transition temperature (Tg) of the resin used as the raw material, preferably (Tg-10°C) to (Tg+20°C) , more preferably (Tg -5°C) to (Tg+15°C). Although the draw ratio is determined by the target retardation value, it is 1.2 times - 4 times each vertically and horizontally, More preferably, they are 1.5 times - 3.5 times, More preferably, they are 2 times - 3 times. When a draw ratio is too small, the effective range from which the orientation degree and orientation angle made into desired will become narrow. On the other hand, when a draw ratio is too large, there exists a possibility that a film may fracture|rupture or a wrinkle may generate|occur|produce during extending|stretching.

The stretching rate is also appropriately selected depending on the purpose, but is usually 50% to 2000%, preferably 100% to 1500%, more preferably 200% to 1000%, particularly preferably 250% at a strain rate represented by the following formula. It can select so that it may become % - 500 %. When the stretching rate is excessively large, there is a possibility that fracture at the time of stretching may be caused or the fluctuation of the optical properties due to long-term use under high temperature conditions may become large. Moreover, when an extending|stretching speed is too small, not only productivity will fall, but in order to acquire a desired phase difference, a draw ratio may have to be made large too much.

Deformation rate (%/min) = {stretching rate (mm/min)/length of raw film (mm)} x 100

After extending|stretching a film, you may perform a heat setting process with a heating furnace as needed, control the width|variety of a tenter, or adjust a roll peripheral speed, and may implement a relaxation|relaxation process. As temperature of a heat setting process, 60 degreeC - (Tg) with respect to the glass transition temperature (Tg) of resin used for an unstretched film, Preferably it implements in the range of 70 degreeC - (Tg-5 degreeC). When the heat treatment temperature is too high, the orientation of the molecules obtained by stretching is disturbed, and there is a possibility that the orientation is greatly reduced from the desired phase difference. Moreover, when providing a relaxation|relaxation process, the stress which generate|occur|produced in a stretched film can be removed by shrinking|contracting 95% - 100% with respect to the width|variety of the film extended by extending|stretching. The treatment temperature applied to the film at this time is the same as the heat setting treatment temperature. By implementing the above heat setting treatment and relaxation process, the fluctuation|variation of the optical characteristic by long-term use under high temperature conditions can be suppressed.

The retardation film using resin of this invention can be manufactured by selecting and adjusting suitably the processing conditions in such an extending process.

The retardation film using the resin of the present invention preferably has an in-plane birefringence (Δn) of 0.002 or more at a wavelength of 550 nm, more preferably 0.0025 or more, and particularly preferably 0.003 or more. Since the retardation is proportional to the thickness (d) of the film and the birefringence (Δn), by setting the birefringence to the above specific range, it becomes possible to express the retardation as designed in a thin film, and a film suitable for a thin device can be easily manufactured can do. In order to express high birefringence, the orientation degree of polymer molecules must be increased by lowering the stretching temperature or increasing the stretching ratio. The better the better.

Although the retardation film using the resin of this invention also changes with the design value of retardation, it is preferable that thickness is 60 micrometers or less. Moreover, as for the thickness of retardation film, it is more preferable that it is 50 micrometers or less, It is still more preferable that it is 45 micrometers or less, It is especially preferable that it is 40 micrometers or less. On the other hand, if the thickness is excessively thin, handling of the film becomes difficult, and wrinkles or breakage occur during manufacture. Therefore, the lower limit of the thickness of the retardation film of the present invention is preferably 10 µm or more, Preferably it is 15 micrometers or more.

The retardation film using the resin of the present invention has a wavelength dispersion (R450/R550) that is a ratio of the retardation (R450) measured at a wavelength of 450 nm to the retardation (R550) measured at a wavelength of 550 nm is 0.75 or more and 0.93 or less to be. It is more preferable that they are 0.78 or more and 0.91 or less, and it is especially preferable that they are 0.80 or more and 0.89 or less. If the value of the wavelength dispersion is within this range, ideal retardation characteristics can be obtained in a wide wavelength range of the visible region. For example, by manufacturing a retardation film having such wavelength dependence as a quarter-wave plate and bonding it to a polarizing plate, a circular polarizing plate etc. can be manufactured, and a polarizing plate and a display device with little wavelength dependence of color can be realized. . On the other hand, when the ratio is outside this range, the wavelength dependence of the color becomes large, and optical compensation is not made in all wavelengths of the visible region, so that the coloration or contrast is lowered due to light leaking into the polarizing plate or the display device, etc. of the problem arises.

<Example of use of retardation film using resin of the present invention>

The said retardation film becomes a circularly polarizing plate by laminating|stacking a well-known polarizing film, and cutting|disconnecting to a desired dimension. Such a circularly polarizing plate is, for example, for viewing angle compensation of various displays (liquid crystal display device, organic electroluminescent display device, plasma display device, FED field emission display device, SED surface field display device), for external light reflection prevention, for color compensation , for converting linearly polarized light to circularly polarized light. In particular, when used for a circular polarizing plate for preventing external light reflection of an organic EL display, a clean black display becomes possible and the reliability of the quality is excellent. In addition, it has the capability to cope with future thinning of the device.

As said polarizing film, the polarizing film which has an absorption axis in either a width direction or a longitudinal direction is employable. Specifically, a dichroic substance such as iodine or a dichroic dye is adsorbed to a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene/vinyl acetate copolymer-based partially saponified film, and the uniaxial and polyene-based oriented films such as a stretched film, a dehydration-treated product of polyvinyl alcohol, and a dehydrochloric acid-treated product of polyvinyl chloride. Among these, a long polarizing film obtained by adsorbing a dichroic substance such as iodine to a polyvinyl alcohol-based film and uniaxially stretching is particularly preferable because of a high polarization dichroism ratio. Although the thickness in particular of these long polarizing films is not restrict|limited, Generally, it is about 1-80 micrometers.

A polarizing film obtained by adsorbing iodine to a polyvinyl alcohol-based film and uniaxially stretching it can be produced by, for example, immersing polyvinyl alcohol in an aqueous solution of iodine, dyeing it, and stretching it to 3 to 7 times its original length. The said aqueous solution may contain boric acid, zinc sulfate, zinc chloride, etc. as needed. Moreover, polyvinyl alcohol can also be immersed in aqueous solutions, such as potassium iodide.

Moreover, you may immerse a polyvinyl alcohol-type film in water and wash with water before dyeing as needed. By washing the polyvinyl alcohol-based film with water, it is possible to wash the contamination and blocking agent on the surface of the polyvinyl alcohol-based film. Moreover, since a polyvinyl alcohol-type film swells, it also has the effect of preventing nonuniformity, such as uneven coloring of dyeing. After extending|staining with iodine, you may perform extending|stretching, dyeing|staining, you may extend|stretch, and after extending|stretching, you may dye|stain with iodine. It can be extended|stretched also in aqueous solutions, such as boric acid and potassium iodide, or a water bath.

In the circular polarizing plate, the angle between the slow axis of the retardation film and the width direction of the polarizing film is preferably 38° or more and 52° or less, more preferably 40° or more and 50° or less, and 42° or more and 48° or less. It is particularly preferred. When it falls outside the above range, the external light reflectance, which will be described later, increases or the reflected light is colored, so that the display quality of the image may be deteriorated.

The said retardation film and the said polarizing film may be laminated|stacked through an adhesive agent. As an adhesive agent, if the optical characteristic of the said laminated|multilayer film is not impaired, a well-known adhesive agent can be used.

The said circularly polarizing plate is comprised so that it can be used suitably for the apparatus which precision, thinness, and homogeneity are requested|required while being equipped with sufficient optical characteristic as mentioned above. Therefore, the said circularly polarizing plate can be used suitably for the liquid crystal panel used for a liquid crystal display, the organic electroluminescent panel used for organic electroluminescent display, etc., for example. In particular, since the organic EL panel has a metal layer that easily reflects external light, problems such as external light reflection and background projection are likely to occur. In order to prevent such external light reflection etc., it is effective to form the said circular polarizing plate on a light emitting surface.

≪Invention 2≫

Hereinafter, the trifluorenediester of this invention 2, the oligofluorenediester composition containing it, and the resin composition containing the polymer which has a novel repeating unit derived from trifluorenediester, and the stretched film obtained using the same , a circularly polarizing plate and an image display device will be described in detail.

In addition, (general) formulas (1), (1a)-(1e), (2)-(11), (21) described below demonstrate each structure in this invention 2nd.

<1 trifluorene diester>

The trifluorene diester of this invention contains three fluorene units a which may have a substituent.

In trifluorene diester, the fluorene unit a is a direct bond between the carbon atoms at position 9, or an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent. They are interposed in a chain form.

Thus, since the structure of the trifluorene diester of this invention is rigid by the lamination|stacking structure of a fluorene ring, it is thought that it becomes what has heat resistance better than a difluorene compound.

<1.1 Alkylene group, arylene group, aralkylene group>

In the trifluorenediester of the present invention, the alkylene group bonding the fluorene unit a is not particularly limited, but from the viewpoint of increasing the fluorene ratio described later, the carbon number is usually 1 or more, and usually It is 10 or less, Preferably it is 5 or less, More preferably, it is 3 or less.

Specific structures of the alkylene group include, but are not limited to, linear types such as methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, and n-hexylene group. of alkylene group; methylmethylene group, dimethylmethylene group, ethylmethylene group, propylmethylene group, butylmethylene group, (1-methylethyl)methylene group, 1-methylethylene group, 2-methylethylene group, 1-ethylethylene group , 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1,1-dimethylethylene group, 2,2-dimethylpropylene group, alkylene group containing a branched chain such as 3-methylpropylene group ( The numerical value of the substitution position is assumed to be attached from the carbon on the fluorene ring side); having a bond of a linear or branched alkylene group at any two points of the alicyclic structure as shown in the following group [A] alicyclic alkylene group

[Formula 34]

(The substitution positions of two bonds in each ring structure shown in the group [A] are arbitrary, and two bonds may be substituted on the same carbon.); A heterocyclic alkylene group having a bond of a linear or branched alkylene group at any two points in the heterocyclic structure

[Formula 35]

(The substitution positions of two bonds in each ring structure shown in the group [B] are arbitrary, and two bonds may be substituted on the same carbon.);

The specific structure of the bond of the linear or branched alkylene group which the alicyclic structure as shown in the said group [A] or the heterocyclic structure as shown in the said group [B] has at two arbitrary positions is mentioned below, but is not limited thereto, linear alkylene groups such as methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group; 1- Methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1,1-dimethylethylene group, 2,2-dimethylpropylene group, and an alkylene group containing a branched chain such as a 3-methylpropylene group (wherein, the numerical value of the substitution position is attached from the carbon bonded to the ring structure).

Examples of the substituent that the alkylene group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkoxy group having 1 to 10 carbon atoms (eg, a methoxy group, an ethoxy group, etc.); 10 acyl group (eg, acetyl group, benzoyl group, etc.); acylamide group having 1 to 10 carbon atoms (eg, acetamide group, benzoylamide group, etc.); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg methyl group, ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg methoxy group, ethoxy group, etc.), 1 to carbon atoms 1 to 3 substituents selected from an acyl group of 10 (eg, an acetyl group, a benzoyl group, etc.), an acylamide group having 1 to 10 carbon atoms (eg, an acetamide group, a benzoylamide group, etc.), a nitro group, a cyano group, etc. The C6-C10 aryl group (For example, a phenyl group, a naphthyl group, etc.) etc. which you may have are mentioned. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Specific examples of the optionally substituted alkylene group include alkyl group-substituted alkylene groups such as cyclobutylmethylene group, cyclopentylmethylene group, cyclohexylmethylene group and 1-cyclohexylpropylene group; phenylmethylene group, 1-phenylethylene group, Aryl group-substituted alkylene group such as 1-phenylpropylene group; Halogen atom-substituted alkylene group such as 1,1,2,2-tetrafluoroethylene group, trichloromethylmethylene group and trifluoromethylmethylene group; Alkoxy group-substituted alkylene groups, such as a oxymethyl- 2-methylpropylene group, etc. are mentioned (The numerical value of a substitution position shall attach from carbon on the side of a fluorene ring).

Moreover, in the trifluorene diester of this invention, although the arylene group which couple|bonds the fluorene unit a is not specifically limited, From a viewpoint of increasing the fluorene ratio mentioned later, the carbon number is 4 or more normally, and, Usually, it is 10 or less, Preferably it is 8 or less, More preferably, it is 6 or less.

Specific structures of the arylene group include, but are not limited to, phenylene groups such as 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene; 1,5-naph Naphthylene groups, such as a tylene group and a 2, 6- naphthylene group; Heteroarylene groups, such as a 2, 5- pyridylene group, a 2, 4- thienylene group, and a 2, 4- furylene group, are mentioned.

Examples of the substituent that the arylene group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, an isopropyl group, etc.); to 10 alkoxy group (eg, methoxy group, ethoxy group, etc.); acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); acylamide group having 1 to 10 carbon atoms (eg acetamide group, benzoyl group) Amide group etc.); Nitro group; Cyano group etc. are mentioned. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Specific examples of the optionally substituted arylene group include 2-methyl-1,4-phenylene group, 3-methyl-1,4-phenylene group, 3,5-dimethyl-1,4-phenylene group, 3-methyl Toxy-1,4-phenylene group, 3-trifluoromethyl-1,4-phenylene group, 2,5-dimethoxy-1,4-phenylene group, 2,3,5,6-tetrafluoro-1 ,4-phenylene group, 2,3,5,6-tetrachloro-1,4-phenylene group, 3-nitro-1,4-phenylene group, 3-cyano-1,4-phenylene group, and the like. have.

Further, in the trifluorenediester of the present invention, the aralkylene group bonding the fluorene unit a is not particularly limited, but from the viewpoint of increasing the fluorene ratio described later, the carbon number is usually 6 or more, and Usually, it is 10 or less, Preferably it is 9 or less, More preferably, it is 8 or less.

Specific structures of the aralkylene group include, but are not limited to, an aralkylene group as shown in the following group [C].

[Formula 36]

can be heard

Examples of the substituent that the aralkylene group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, an isopropyl group, etc.); to 10 alkoxy group (eg, methoxy group, ethoxy group, etc.); acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); acylamide group having 1 to 10 carbon atoms (eg acetamide group, benzoyl group) amide group); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), 1 carbon atom A to 10 alkoxy group (eg, methoxy group, ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (eg acetyl group, benzoyl group, etc.), an acylamide group having 1 to 10 carbon atoms (eg acetamide group, benzoyl group) amide group), a C6-C10 aryl group (eg, a phenyl group, a naphthyl group, etc.) which may have 1 to 3 substituents selected from a nitro group, a cyano group, etc. are mentioned. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Specific examples of the optionally substituted aralkylene group include 2-methyl-1,4-xylylene group, 2,5-dimethyl-1,4-xylylene group, and 2-methoxy-1,4-xylylene group. Rene group, 2,5-dimethoxy-1,4-xylylene group, 2,3,5,6-tetrafluoro-1,4-xylylene group, α,α-dimethyl-1,4-xylylene group , α,α,α′,α′-tetramethyl-1,4-xylylene group, and the like.

Among these, an alkylene group is preferable from a viewpoint of increasing a fluorene ratio and rigidity, a methylene group, an ethylene group, a phenylene group, or a 1, 4- xylylene group is more preferable, A methylene group is still more preferable. In particular, a methylene group is particularly preferable because synthesis of an oligofluorene having one reactive functional group selectively is easy.

<1.2 Substituent group which fluorene unit a may have>

In the trifluorenediester of the present invention, as a substituent which the fluorene unit a may have, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg , methyl group, ethyl group, isopropyl group, etc.); Alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.); Acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); 10 acylamide group (eg, acetamide group, benzoylamide group, etc.); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg. , methyl group, ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg methoxy group, ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (eg acetyl group, benzoyl group, etc.), 1 to carbon atoms An aryl group having 6 to 10 carbon atoms which may have 1 to 3 substituents selected from a 10 acylamide group (eg, acetamide group, benzoylamide group, etc.), nitro group, cyano group, etc. (eg phenyl group, naphthyl group, etc.) ) and the like. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

<1.3 Ester group>

In the trifluorenediester of the present invention, among the three fluorene units a, substituents α ¹ and α ² are bonded to the carbon atoms at position 9 of the fluorene unit a located at both terminals, respectively, and the substituents α ¹ and It can be set as what the ester group ^couple| bonded with (alpha)2. In this case, α ¹ and α ² may be the same or different. Further, the substituents α ¹ and α ² include a direct bond, that is, an ester group may be directly bonded to the carbon atom at the 9th position of the fluorene unit a.

Although it does not specifically limit as the ester group which the trifluorenediester of this invention has, From a viewpoint that it can obtain industrially cheaply, it is preferable that a terminal group is an ester group of a C1-C10 organic substituent.

Specific examples of the organic substituent having 1 to 10 carbon atoms include, but are not limited to, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-decyl group linear alkyl groups such as; alkyl groups containing branched chains such as isopropyl group, 2-methylpropyl group, 2,2-dimethylpropyl group and 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group Cyclic alkyl groups, such as a sil group and a cyclooctyl group; Aryl groups, such as a phenyl group, 1-naphthyl group, 2-naphthyl group; Heteroaryl groups, such as a 2-pyridyl group, 2-thienyl group, 2-furyl group; A benzyl group , an aralkyl group such as a 2-phenylethyl group and a p-methoxybenzyl group.

Among these, it is preferable that it is a C1-C6 alkyl group from a viewpoint that it can obtain industrially cheaply. In this case, from the viewpoint of being easy to hydrolyze during synthesis and easy to produce carboxylic acid, it is preferable that carbon number is 2 or more, and by removing low-boiling alcohol generated by transesterification with a dihydroxy compound, poly From a viewpoint of being able to synthesize|combine ester and polyester carbonate efficiently, it is preferable that it is 4 or less, and it is more preferable that it is 2 or less. A particularly preferable substituent is an ethyl group.

On the other hand, in the case of an aryl group having 6 to 8 carbon atoms, since the transesterification reaction proceeds easily, the preferred polymer poly Since ester carbonate can be synthesize|combined in one step, it is preferable. In this case, it is preferable that carbon number is 8 or less from a viewpoint that molecular weight is small and distillation is easy, and it is more preferable that it is 6 or less. In particular, the phenyl group which can be distilled off as phenol after polyester carbonate synthesis|combination is especially preferable. Moreover, in the case of an aryl group, it is preferable to use the diaryl carbonates mentioned later as a diester carbonate from a reactive viewpoint at the time of polymerization, and from a viewpoint that a by-product can be easily removed, the aryl group in the ester group , it is more preferable that the aryl groups in the diaryl carbonates are the same.

<1.4 Substituents α ¹ and α ² >

The substituents α ¹ and α ² are not particularly limited, but a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted arral having 6 to 10 carbon atoms. At least two groups selected from the group consisting of a alkylene group or an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, and an optionally substituted aralkylene group having 6 to 10 carbon atoms; and an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom, or a group linked by a carbonyl group.

As "the optionally substituted C1-C10 alkylene group", what was illustrated as an alkylene group which couple|bonds the fluorene unit a can be used preferably. In this case, it is preferable to use a C2 or more thing from a viewpoint of expressing reverse wavelength dispersion property. On the other hand, it is preferable to make the carbon number into 1 from a viewpoint of expressing flat dispersibility. In addition, in the case of expressing reverse wavelength dispersion, the number of carbon atoms is preferably 5 or less, and 4 or less from the viewpoint of making it easy to fix the orientation of the fluorene ring with respect to the main chain and efficiently obtaining reverse wavelength dispersion characteristics. It is more preferable, it is still more preferable that it is 3 or less, It is especially preferable that it is 2 or less. On the other hand, from the viewpoint of imparting flexibility to the resin composition, the carbon number is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more.

As "the optionally substituted arylene group having 4 to 10 carbon atoms", those exemplified as the arylene group to which the fluorene unit a is bonded can be preferably used. Similarly, as "the optionally substituted aralkylene group having 6 to 10 carbon atoms", those exemplified as the aralkylene group bonding the fluorene unit a can be preferably used.

"At least two groups selected from the group consisting of an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, and an aralkylene group having 6 to 10 carbon atoms which may be substituted are an oxygen atom; The specific structure of "the optionally substituted sulfur atom, the optionally substituted nitrogen atom, or the group linked by a carbonyl group" is listed below, but is not limited thereto, but a divalent group as shown in the following group [D]

[Formula 37]

can be heard Among these, preferably, two or more groups selected from an alkylene group, an arylene group, or an aralkylene group, which can impart flexibility while maintaining the transparency and stability of the resin composition, are linked by an oxygen atom, more preferably , which can increase the glass transition temperature of the resin composition while imparting flexibility, and is a group in which an alkylene group as shown in the following group [E] is linked by an oxygen atom.

[Formula 38]

Moreover, when setting it as these linked groups from a viewpoint of raising a fluorene ratio, it is preferable to set it as 2 or more, Moreover, it is preferable to set it as 6 or less, It is more preferable to set it as 4 or less.

Among these, ^{when at least one of the substituents α 1} and α ² is a direct bond, or when at least one of the substituents α ¹ and α ² has 2 or more carbon atoms, the fluorene ring (fluorene unit a) is substantially perpendicular to the main chain In order to orientate to , even if the ratio of the divalent trifluorene in the resin composition is small, there exists a tendency for reverse wavelength dispersion property to become easy to express. In the latter case, from the same viewpoint, ^{it is preferable that both of α 1} and α ² have 2 or more carbon atoms. On the other hand, when ^{both of the substituents α 1} and α ² are C1 (that is, a methylene group which may be substituted), the fluorene ring (fluorene unit) is not oriented substantially perpendicular to the main chain. , in order to orient with a large inclination, even if the ratio of divalent trifluorene in a resin composition is changed in a wide range, there exists a tendency for flat dispersibility with a small difference in retardation in a broad band to become easy.

Among these, it is preferably a direct bond, optionally substituted alkylene group having 1 to 10 carbon atoms, optionally substituted arylene group having 4 to 10 carbon atoms, or optionally substituted alkylene group having 1 to 10 carbon atoms, which may be substituted. At least two groups selected from the group consisting of an arylene group having 4 to 10 carbon atoms and an optionally substituted aralkylene group having 6 to 10 carbon atoms are linked to an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group it's gi

More preferably, a direct bond, a linear alkylene group, an alkylene group containing a branched chain, or a linear or branched alkylene group at any two points of the alicyclic structure as shown in group [A] above An alicyclic alkylene group having a bond of Two or more groups selected from the group consisting of are groups connected by an oxygen atom.

More preferably, a direct bond, methylene group, ethylene group, n-propylene group, n-butylene group, methylmethylene group, which tends to achieve the low photoelastic modulus required for the optical film by not having an aromatic ring group, 1-methylethylene group, 2-methylethylene group, 2,2-dimethylpropylene group, 2-methoxymethyl-2-methylpropylene group, or an alicyclic alkylene group as shown in the following group [F]

[Formula 39]

(The substitution positions of two bonds in each ring structure shown in the group [F] are arbitrary, and two bonds may be substituted on the same carbon.)

Even more preferably, they are a direct bond, a methylene group, an ethylene group, n-propylene group, n-butylene group, a methylmethylene group, 1-methylethylene group, 2-methylethylene group, or a 2,2-dimethylpropylene group. . Particularly preferably, they are a methylene group, an ethylene group, or an n-propylene group.

If the chain length is long, the glass transition temperature tends to be low, so a short-chain group, for example, a group having 2 or less carbon atoms is preferable. Further, since the molecular structure becomes small, the concentration (fluorene ratio) of the fluorene ring in the repeating unit tends to be high, so that desired optical properties can be efficiently expressed. Moreover, even if it is contained in an arbitrary mass with respect to the mass of the entire resin composition, it tends to be flat dispersion with small wavelength dispersion of the retardation, and it can also be introduced industrially at low cost in a single step. Since there is also a certain superiority, it is preferable that it is a methylene group.

On the other hand, for the purpose of improving the mechanical strength and reliability at high temperature of the obtained film, an arylene group having 4 to 10 carbon atoms, which can increase the glass transition temperature of the resin composition, or an alkylene group having 1 to 10 carbon atoms which may be substituted and a group in which two or more groups selected from the group consisting of an arylene group having 4 to 10 carbon atoms which may be substituted are preferably linked by an oxygen atom, 1,4-phenylene group, 1,5-naphthylene group, 2,6-naph A tylene group or a divalent group as shown in the following group [D2] is more preferable.

[Formula 40]

Moreover, when applying to the retardation film which has reverse wavelength dispersion property, it is important to select ^{substituent (alpha)1} and (alpha) ^{2 suitably.} For example, since a group of 1 carbon atom represented by a methylene group tends to have unexpectedly low reverse wavelength dispersion ^{, it is preferable that R 1} and R ² are a direct bond, or that at least one of them is a group having 2 or more carbon atoms.

More preferably, a direct bond, optionally substituted C2-10 alkylene group, optionally substituted C4-C10 arylene group, or optionally substituted C1-C10 alkylene group, optionally substituted C4 At least two groups selected from the group consisting of an arylene group of to 10 and an optionally substituted aralkylene group having 6 to 10 carbon atoms are a group linked to an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom, or a carbonyl group .

More preferably, a direct bond, a linear alkylene group, an alkylene group including a branched chain, or a linear or branched alkylene group at any two points of the alicyclic structure as shown in group [A] above It consists of an alicyclic alkylene group having a bond, a phenylene group, or an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, and an optionally substituted aralkylene group having 6 to 10 carbon atoms. Two or more groups selected from the group are groups connected by an oxygen atom.

Even more preferably, a direct bond, ethylene group, n-propylene group, n-butylene group, methylmethylene group, 1-methyl group, which can achieve a low photoelastic modulus required for an optical film by not having an aromatic ring Ethylene group, 2-methylethylene group, 2,2-dimethylpropylene group, 2-methoxymethyl-2-methylpropylene group or alicyclic alkylene group as shown in the group [F] above, or glass transition of the resin composition At least two groups selected from the group consisting of a 1,4-phenylene group capable of raising the temperature, an optionally substituted C1-C10 alkylene group, and an optionally substituted C4-C10 arylene group are oxygen atoms is a connected group.

Particularly preferably, they are a direct bond, an ethylene group, an n-propylene group, an n-butylene group, a methylmethylene group, a 1-methylethylene group, a 2-methylethylene group, or a 2,2-dimethylpropylene group.

Most preferably, it is an ethylene group or an n-propylene group. If the chain length is long, the glass transition temperature tends to be low, so a short-chain group, for example, a group having 3 or less carbon atoms is preferable. Moreover, since the molecular structure becomes small, the density|concentration (fluorene ratio) of the fluorene ring in a repeating unit can be made high, and desired optical properties can be expressed efficiently.

In addition, the substituents α ¹ and α ² are preferably the same for facilitating production.

<1.5 Specific Structure>

As the trifluorenediester of the present invention, specifically, those represented by the following general formula (1) can be preferably used.

[Formula 41]

(during the meal,

R ¹ and R ² are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ^3a and R ^3b are each independently an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 6 to 10 carbon atoms.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, a substituent a vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is an organic substituent having 1 to 10 carbon atoms.)

In addition, in General formula (1), R ^3a and R ^3b may be respectively same or different. ^{Moreover, R<4>} -R<^{9> which} exists each in General formula (1) may be same or different, respectively. ^{Similarly, two R 10} in General Formula (1) may be the same or different, respectively.

^{In R 1} and R ² of the above general formula (1), as the “alkylene group having 1 to 4 carbon atoms which may have a substituent”, those exemplified in the group ^{of R 1} and R ^{2 in the aforementioned <Invention 1>} It can be used preferably.

Similarly, as R ^3a and R ^3b , those exemplified in <1.1 alkylene group, arylene group, aralkylene group> can be preferably used. In addition, in this specification, R ^3a and R ^3b may be collectively described as R ^{3 .}

Moreover, as R ^<10 >, what was illustrated as a C1-C10 organic substituent in <1.3 ester group> can be used preferably.

In R ⁴ to R ⁹ , the specific structure of “the optionally substituted alkyl group having 1 to 10 carbon atoms” is given below, but is not limited thereto, but a methyl group, an ethyl group, n-propyl group, n-butyl group, linear alkyl groups such as n-pentyl group, n-hexyl group, and n-decyl group; branched chains such as isopropyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 2-ethylhexyl group Alkyl group contained; Cyclic alkyl groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, are mentioned.

It is preferable that it is 4 or less, and, as for carbon number in the C1-C10 alkyl group which may be substituted, it is more preferable that it is 2 or less. If it is in this range, steric hindrance between fluorene rings does not generate|occur|produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired.

Examples of the substituent that the alkyl group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkoxy group having 1 to 10 carbon atoms (eg, a methoxy group, an ethoxy group, etc.); of acyl group (eg, acetyl group, benzoyl group, etc.); acylamide group having 1 to 10 carbon atoms (eg, acetamide group, benzoylamide group, etc.); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.), 1 to 10 carbon atoms having 1 to 3 substituents selected from an acyl group (eg, an acetyl group, a benzoyl group, etc.), an acylamide group having 1 to 10 carbon atoms (eg, an acetamide group, a benzoylamide group, etc.), a nitro group, a cyano group, etc. and optionally an aryl group having 6 to 10 carbon atoms (eg, a phenyl group, a naphthyl group, etc.). Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Specific examples of the optionally substituted alkyl group include a trifluoromethyl group, a benzyl group, a 4-methoxybenzyl group, and a methoxymethyl group.

In R ⁴ to R ⁹ , the specific structure of “an optionally substituted aryl group having 4 to 10 carbon atoms” is given below, and is not limited thereto, but includes a phenyl group, 1-naphthyl group, 2-naphthyl group, etc. Aryl group; Heteroaryl groups, such as a 2-pyridyl group, 2-thienyl group, and 2-furyl group, are mentioned.

It is preferable that it is 8 or less, and, as for carbon number in the C4-C10 aryl group which may be substituted, it is more preferable that it is 7 or less. If it is in this range, steric hindrance between fluorene rings does not generate|occur|produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired.

Examples of the substituent which the aryl group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, an isopropyl group, etc.); Alkoxy group of 10 (eg, methoxy group, ethoxy group, etc.); Acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); Acylamide group having 1 to 10 carbon atoms (eg, acetamide group, benzoylamide) group, etc.); nitro group; cyano group etc. are mentioned. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Specific examples of the optionally substituted aryl group include a 2-methylphenyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a 4-benzoylphenyl group, a 4-methoxyphenyl group, a 4-nitrophenyl group, and a 4-cyanophenyl group. , 3-trifluoromethylphenyl group, 3,4-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-methylfuryl group, and the like. have.

The specific structure of the "acyl group having 1 to 10 carbon atoms which may be substituted" for R ⁴ to R ⁹ is given below, but is not limited thereto, but a formyl group, an acetyl group, a propionyl group, and 2-methyl aliphatic acyl groups such as propionyl, 2,2-dimethylpropionyl, and 2-ethylhexanoyl; aromatic acyl groups such as benzoyl, 1-naphthylcarbonyl, 2-naphthylcarbonyl and 2-furylcarbonyl; have.

It is preferable that it is 4 or less, and, as for carbon number in the C1-C10 acyl group which may be substituted, it is more preferable that it is 2 or less. If it is in this range, steric hindrance between fluorene rings does not generate|occur|produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired.

Examples of the substituent that the acyl group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, an isopropyl group, etc.); 10 alkoxy group (eg, methoxy group, ethoxy group, etc.); acylamide group having 1 to 10 carbon atoms (eg, acetamide group, benzoylamide group, etc.); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg methyl group, ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg methoxy group, ethoxy group, etc.), 1 to carbon atoms 1 to 3 substituents selected from an acyl group of 10 (eg, an acetyl group, a benzoyl group, etc.), an acylamide group having 1 to 10 carbon atoms (eg, an acetamide group, a benzoylamide group, etc.), a nitro group, a cyano group, etc. The C6-C10 aryl group (For example, a phenyl group, a naphthyl group, etc.) etc. which you may have are mentioned. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Specific examples of the optionally substituted acyl group include a chloroacetyl group, a trifluoroacetyl group, a methoxyacetyl group, a phenoxyacetyl group, a 4-methoxybenzoyl group, a 4-nitrobenzoyl group, and a 4-cyanobenzoyl group. diyl, 4-trifluoromethylbenzoyl group, etc. are mentioned.

In R ⁴ to R ⁹ , the specific structure of “the optionally substituted alkoxy group or aryloxy group having 1 to 10 carbon atoms” is given below, but is not limited thereto, but a methoxy group, an ethoxy group, an isopropoxy group Alkoxy groups, such as a group, t-butoxy group, a trifluoromethoxy group, and a phenoxy group; Aryloxy groups, such as a phenoxy group, are mentioned.

Among the optionally substituted C1-C10 alkoxy group or aryloxy group, an alkoxy group is preferable, and, as for carbon number of an alkoxy group, it is preferable that it is 4 or less, It is more preferable that it is 2 or less. If it is in this range, steric hindrance between fluorene rings does not generate|occur|produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired.

In R ⁴ to R ⁹ , the specific structure of “the amino group which may be substituted” is given below, and is not limited thereto, but is not limited to an amino group; N-methylamino group, N,N-dimethylamino group, N-ethylamino group, Aliphatic amino groups such as N,N-diethylamino group, N,N-methylethylamino group, N-propylamino group, N,N-dipropylamino group, N-isopropylamino group, N,N-diisopropylamino group; N- Aromatic amino groups such as phenylamino group and N,N-diphenylamino group; Acylamide groups such as formamide group, acetamide group, decanoylamide group, benzoylamide group and chloroacetamide group; benzyloxycarbonylamino group, tert- Alkoxy carbonylamino groups, such as a butyloxy carbonylamino group, etc. are mentioned.

Among these, a N,N-dimethylamino group, N-ethylamino group, or N,N-diethylamino group is preferable because it does not have a proton with high acidity, has a small molecular weight, and tends to increase the fluorene ratio. And, it is more preferable that it is a N,N- dimethylamino group.

In R ⁴ to R ⁹ , specific structures of the “sulfur atom having a substituent” include, but are not limited to, a sulfo group; a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group Alkylsulfonyl groups such as; Arylsulfonyl groups such as phenylsulfonyl group and p-tolylsulfonyl group; Alkylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group and isopropylsulfinyl group; phenylsulfinyl group, p-tolyl group Arylsulfinyl groups such as sulfinyl group; Alkylthio groups such as methylthio group and ethylthio group; Arylthio groups such as phenylthio group and p-tolylthio group; Alkoxysulfonyl groups such as methoxysulfonyl group and ethoxysulfonyl group ; Aryloxysulfonyl group such as phenoxysulfonyl group; Aminosulfonyl group; N-methylaminosulfonyl group, N-ethylaminosulfonyl group, N-tert-butylaminosulfonyl group, N,N-dimethylaminosulfonyl group, N and alkylsulfonyl groups such as ,N-diethylaminosulfonyl group; arylaminosulfonyl groups such as N-phenylaminosulfonyl group and N,N-diphenylaminosulfonyl group. In addition, the sulfo group may form a salt with lithium, sodium, potassium, magnesium, ammonium, etc.

Among these, a methylsulfinyl group, an ethylsulfinyl group, or a phenylsulfinyl group is preferable, and a methylsulfinyl group is more preferable because it does not have a high acidity proton, has a small molecular weight, and tends to increase the fluorene ratio. do.

Examples ^{of the "halogen atom" for R 4} to R ⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among these, a fluorine atom, a chlorine atom, or a bromine atom is preferable, and a chlorine atom or a bromine atom is preferable in terms of a tendency to increase the reactivity of the fluorene 9 position because it is a relatively easy introduction and is an electron-withdrawing substituent. desirable.

In this way, by making R ⁴ to R ^{9 a} specific atom or substituent as described above, there is little steric hindrance between the main chain and the fluorene ring or between the fluorene rings, and desired optical properties derived from the fluorene ring tends to get

Of these R ⁴ to R ⁹ , all are preferably hydrogen atoms, or R ⁴ and/or R ⁹ are any selected from the group consisting of a halogen atom, an acyl group, a nitro group, a cyano group, and a sulfo group, and R ⁵ to R ⁸ are hydrogen atoms. When all are hydrogen atoms, it can be derived from fluorene, which is industrially inexpensive. Further, when R ⁴ and/or R ⁹ is any one selected from the group consisting of a halogen atom, an acyl group, a nitro group, a cyano group, and a sulfo group, and R ⁵ to R ⁸ are a hydrogen atom, fluorene 9 Because the reactivity of the site is improved, various inductive responses tend to be adaptable. More preferably, all hydrogen atoms, or R ⁴ and/or R ⁹ are any selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and a nitro group, and R ⁵ to R ⁸ are a hydrogen atom, Particularly preferably, they are all hydrogen atoms. Moreover, by setting it as said thing, a fluorene ratio can be raised and steric hindrance between fluorene rings does not generate|occur|produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired.

<Specific example of 1.6 trifluorenediester>

As a specific example of the trifluorenediester of this invention, a structure as shown to the following [H] group is mentioned.

[Formula 42]

[Formula 43]

<1.7 Physical properties of trifluorene diester>

Although the physical-property value of the trifluorenediester of this invention is not specifically limited, It is preferable that it is what satisfy|fills the physical-property value illustrated below.

It is preferable that the chlorine content rate in the trifluorenediester of this invention is 100 mass ppm or less in Cl conversion mass. Furthermore, it is preferable that it is 10 mass ppm or less. When there is much content rate of a chlorine component, the catalyst used for a polymerization reaction will be deactivated, superposition|polymerization may not advance to a desired molecular weight, or reaction may become unstable and productivity may deteriorate. Moreover, a chlorine component may remain|survive also in the obtained polymer, and there exists a possibility of reducing the thermal stability of a polymer.

It is preferable that the content rate of the trifluorene monoester body in the trifluorene diester of this invention is 10 mass % or less of the mass of all the trifluorene compounds. Furthermore, it is preferable that it is 2 mass % or less. When the trifluorene monoester is inserted into the polymer through a polymerization reaction, it becomes a terminal blocking group. If the amount of the trifluorene monoester increases, the polymerization does not proceed to the desired molecular weight, or the residual amount of low molecular weight components such as oligomers in the polymer It increases, and there exists a possibility of reducing the mechanical strength and heat resistance of the obtained polymer. Moreover, the possibility of reducing the quality of a product is considered, such as a low molecular component bleed out from a molded object. In addition, the monoester means that any one of the terminal ester groups of trifluorene diester becomes a group other than a polymerization-reactive group.

In the trifluorenediester of the present invention, long-period periodic table metals such as sodium and potassium derived from a process of hydroxymethylation by reacting formaldehydes in the presence of a base, and second metals such as calcium Group metal may be contained, and it is preferable that these content ratio is 500 mass ppm or less, More preferably, it is 200 mass ppm or less, More preferably, it is 50 mass ppm or less, Especially preferably, it is 10 mass ppm or less. When there are many metal components, when processing a polymerization reaction or resin, there exists a possibility that a polymer may become easy to color. Moreover, there exists a possibility that the metal component contained may show a catalytic action or a catalyst deactivation action, and superposition|polymerization may become unstable.

Transition of titanium, copper, iron, etc. resulting from the step of transesterifying the trifluorenediester of the present invention, particularly the trifluorenediaryl ester, in the presence of a transesterification reaction catalyst by reacting diaryl carbonates Metals, metals of group 1 of the long-period periodic table such as sodium and potassium, metals of group 2 such as magnesium and calcium, metals of group 12 such as zinc and cadmium, and metals of group 14 such as tin It may contain, and it is preferable that these content rates are 500 mass ppm or less, More preferably, it is 200 mass ppm or less, More preferably, it is 50 mass ppm or less, Especially preferably, it is 10 mass ppm or less. When there are many metal components, when processing a polymerization reaction or resin, there exists a possibility that a polymer may become easy to color. Moreover, there exists a possibility that the metal component contained may show a catalytic action or a catalyst deactivation action, and superposition|polymerization may become unstable.

It is preferable that the color tone of the trifluorenediester of this invention of a 10 mass % tetrahydrofuran solution is 50 or less. Furthermore, it is preferable that it is 10 or less. The absorption edge of trifluorenediester extends to a region close to visible light, and has a property of being easily colored when exposed to high temperatures due to polymerization or resin processing. In order to obtain a polymer having a good color, it is preferable that the trifluorenediester used for the polymerization reaction has as little coloration as possible. Since a color tone is proportional to a density|concentration, it may be a value measured at different density|concentrations and normalized to 10 mass % density|concentration. Here, the color tone (APHA value) of trifluorenediester is in accordance with JIS-K0071-1 (1998), a solution prepared by diluting a chromaticity standard solution (1000 degrees) manufactured by Kishida Chemical Co., Ltd. and trifluorene diester It can measure by putting it into a colorimetric tube with an inner diameter of 20 mm and comparing.

It is preferable that the 5% weight loss temperature in thermogravimetry is 230 degreeC or more, and, as for the trifluorenediester of this invention, it is more preferable that it is 250 degreeC or more. Furthermore, it is especially preferable that it is 270 degreeC or more. Fluorene has a very electron-rich structure, and the reactivity of the substituent bonded to the fluorene ring is high, and thermal decomposition is likely to occur. When trifluorene diester having a low thermal decomposition temperature is used for the polymerization reaction, thermal decomposition occurs during polymerization, so that polymerization does not proceed to a desired molecular weight, or there is a fear that the resulting polymer may be colored.

In addition, the trifluorenediester of the present invention has a decomposition temperature measured in a nitrogen atmosphere of preferably 250°C or higher, more preferably 300°C or higher, still more preferably 330°C or higher, and usually 380°C or lower. . Since the trifluorenediester of the present invention has a rigid structure due to the stacked structure of fluorene rings, the decomposition temperature tends to satisfy the above range. As described above, when the decomposition temperature satisfies the above range, the thermal stability of the polyester and polycarbonate obtained from trifluorenediester tends to be improved. The decomposition temperature can be measured, for example, by TG-DTA.

Moreover, it is preferable that melting|fusing point (m.p.) of the trifluorenediester of this invention is 120 degreeC or more, It is more preferable that it is 130 degreeC or more, It is more preferable that it is 150 degreeC or more, It is 200 degrees C or less normally. The trifluorene diester of the present invention has a rigid structure due to the laminated structure of the fluorene rings, and therefore the melting point tends to satisfy the above range. Thus, when melting|fusing point satisfy|fills the said range, there exists a tendency which can improve the glass transition temperature of the polyester obtained from trifluorenediester, and a polycarbonate. The melting point can be measured, for example, by TG-DTA.

<1.8 Manufacturing method of trifluorenediester>

Although the manufacturing method of the trifluorenediester used by this invention, especially the trifluorenediester represented by the said General formula (1) is not limited at all, For example, Methods, such as manufacturing method A or manufacturing method B shown in the following formula can be manufactured by

In addition, difluorene diester can be produced under the same conditions as in Production Method C after obtaining a difluorene compound by adjusting the amount of reagent corresponding to ^{R 3} according to the production method of the trifluorene compound (II). .

[Formula 44]

In the formula, R ¹ and R ² are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ^3a and R ^3b are each independently an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 6 to 10 carbon atoms;

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, substituted an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 1 to 10 carbon atoms, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom, a nitro group or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is an organic substituent having 1 to 10 carbon atoms.

<1.8.1 Recipe A>

Production method A uses fluorenes (I) as a raw material, converts it to 9-hydroxymethylfluorenes (IV), and then reacts the olefin compound (V) synthesized by dehydration with fluorenyl anion; This is a method for producing a trifluorene compound (IIa) in which ^{R 3} is a methylene group by purification from a mixture of oligofluorenes by column purification or the like. In addition, unsubstituted 9-hydroxymethylfluorene is commercially available as a reagent. From the trifluorene compound (II) obtained here, according to the process (ii) of manufacturing method C, an ester group can also be introduce|transduced and it can also be set as trifluorene diester (1).

For example, a method of synthesizing a mixture of oligofluorenes by anionic polymerization after converting 9-hydroxymethylfluorene into dibenzofulvene is known (J. Am. Chem. Soc., 123, 2001, 9182-9183.). The trifluorene compound (II) can be manufactured by purifying these from the inside of a mixture with reference to these.

<1.8.2 Recipe B>

Manufacturing method B synthesizes trifluorene compound (II) by carrying out a crosslinking reaction (step (i)) of fluorenes (I) as raw materials, and then introduces an ester group (step (ii)) to triple It is a method for manufacturing luorendiester (1).

[Formula 45]

In the formula, R ¹ ~ R ¹⁰ is the same meaning as R ¹ ~ R ¹⁰ in the formula (1).

Hereinafter, the manufacturing method B is divided into the manufacturing method of the process (i) trifluorene compound (II), and the manufacturing method of the process (ii) trifluorene diester (1), and is described.

<1.8.3 step (i): manufacturing method of trifluorene compound (II)>

[Formula 46]

In the formula, R ³ ~ R ⁹ are as defined and R ³ ~ R ⁹ in the formula (1).

Hereinafter, the manufacturing method of the trifluorene compound (II) in the process (i) is divided into the case ^{of R<3> and is described.}

<1.8.3.1 When R ³ is a direct bond: 9,9′: 9′,9″-terfluorenyl production method>

The synthesis method of 9,9':9',9"-terfluorenyl is known and can be synthesized from fluorenone (Eur. J. Org. Chem. 1999, 1979-1984.).

<1.8.3.2 Step (ia): ^{Manufacturing method when R 3} is a methylene group>

The trifluorene compound having a methylene bridge represented by the following general formula (IIa) can be produced from fluorenes (I) and formaldehydes in the presence of a base according to the reaction represented by the following formula.

[Formula 47]

In the formula, R ⁴ R ~ ⁹ is the formula (1) is the same as defined in R ⁴ R ~ ^9.

<1.8.3.2.1 Formaldehydes>

The formaldehyde used in step (ia) is not particularly limited as long as it is a substance capable of supplying formaldehyde to the reaction system, and gaseous formaldehyde, aqueous formaldehyde solution, paraformaldehyde obtained by polymerization of formaldehyde, trioxane, etc. are mentioned. can Paraformaldehyde is more preferable from the point of view that it is industrially inexpensive, and since it is in powder form, operability is easy and accurate weighing is possible. On the other hand, since it is industrially cheap and it is liquid, from a viewpoint that there is little risk of exposure at the time of addition, formalin is more preferable.

(Definition of Theoretical Quantity)

When manufacturing the target trifluorene compound (IIa), the theoretical amount (molar ratio) of formaldehyde with respect to the fluorenes (I) of a raw material is represented by 2/3.

(The reason why it is better not to exceed the theoretical amount)

With respect to the fluorenes (I), when more than the theoretical amount of formaldehydes is used, an oligofluorene compound in which fluorene is crosslinked more than the target trifluorene compound (IIa) tends to be produced. As the number of fluorene rings in the oligofluorene compound increases, solubility decreases. Therefore, it was found that the purification load tends to increase when an oligofluorene compound having four or more fluorene rings crosslinked is present in the target product. Therefore, normally, it is preferable that the usage-amount of formaldehyde is 2/3 times mole or less used as the theoretical amount made into the objective.

(The reason why it is better not to significantly lower the theoretical amount)

Further, when the amount of formaldehyde used is significantly less than 2/3 of the theoretical amount, a difluorene compound having fewer crosslinking numbers of fluorene rings than the target trifluorene compound (IIa) becomes the main product, or a raw material It turned out that since the fluorenes (I) of (I) remained unreacted, there exists a tendency for a yield to fall largely.

Therefore, the optimal amount of formaldehyde to be used is specifically, 0.5 times mole or more, preferably 0.55 times mole or more, more preferably 0.6 times mole or more, with respect to the fluorenes (I) of the raw material, Moreover, it is 0.67 times mole or less normally, Preferably it is 0.65 times mole or less, More preferably, it is 0.63 times mole or less. As such, it can be seen that the structure of the main product and the ratio of the product change significantly depending on the amount of formaldehyde used, and by using the amount of formaldehyde under limited conditions, the target trifluorene compound (IIa) tends to be obtained in high yield.

<1.8.3.2.2 base>

Examples of the base used in step (ia) include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide, and carbonates of alkali metals such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate. , alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate and potassium phosphate, organic lithium salts such as n-butyllithium and tert-butyllithium, sodium methoxide, sodium Alkoxide salts of alkali metals such as oxide and potassium tert-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; tertiary amines such as triethylamine and diazabicycloundecene; tetramethylammonium hydroxide; tetramethylammonium hydroxide; Quaternary ammonium hydroxides, such as butylammonium hydroxide, etc. are used. These may be used individually by 1 type, and may use 2 or more types together.

When the reaction is carried out in a homogeneous system, among these, an alkali metal alkoxide having sufficient basicity in the present reaction is preferable, and industrially inexpensive sodium methoxide or sodium ethoxide is more preferable. Here, a powdery thing may be used for the alkoxide of an alkali metal, and liquid things, such as an alcohol solution, may be used for it. Moreover, you may prepare it by making an alkali metal and alcohol react.

On the other hand, when the reaction is carried out in a two-step system, an aqueous solution of an alkali metal hydroxide having sufficient basicity in this reaction is preferable, and more preferably an industrially inexpensive aqueous solution of sodium hydroxide or potassium hydroxide. , more preferably an aqueous solution of sodium hydroxide.

In addition, the concentration of the aqueous solution is usually 10 wt/wt% or more, preferably 25 wt/wt% or more, because when a particularly preferable aqueous sodium hydroxide solution is used, the reaction rate is significantly lowered when the concentration is softened; More preferably, an aqueous solution of 40 wt/wt% or more is used.

When the reaction is carried out in a homogeneous system, the amount of the base used is not particularly upper limit with respect to the raw material fluorenes (I), but if the amount used is too large, the purification load after stirring or reaction tends to increase, so usually, It is 10 times mole or less, Preferably it is 5 times mole or less, More preferably, it is 1 times mole or less of the orene (I). On the other hand, when the amount of the base used is too small, the progress of the reaction tends to be slow, so the lower limit is usually 0.01 times mole or more, preferably 0.1 times mole or more, relative to the fluorenes (I) of the raw material; More preferably, it is 0.2 times mole or more.

On the other hand, in the case of carrying out the reaction in a two-step system, there is no upper limit for the amount of the base to be used with respect to the raw material fluorenes (I). , 10 times mole or less, preferably 5 times mole or less, more preferably 2 times mole or less of the fluorenes (I). On the other hand, when the amount of the base used is too small, the progress of the reaction tends to be slow, so the lower limit is usually 0.1 times mole or more, preferably 0.3 times mole or more, relative to the fluorenes (I) of the raw material; More preferably, it is 0.4 times mole or more.

<1.8.3.2.3 solvent>

It is preferable to carry out a process (ia) using a solvent. Specific examples of the solvent that can be used include acetonitrile, propionitrile, etc. as the alkylnitrile solvent, and diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, and the like as the ether solvent. Examples of the halogen-based solvent such as tert-butyl methyl ether include 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane, and examples of the halogen-based aromatic hydrocarbon include chlorobenzene, 1, Examples of the amide solvent such as 2-dichlorobenzene include N,N-dimethylformamide, N,N,-dimethylacetamide, and N-methylpyrrolidone. Examples of the sulfoxide solvent include dimethyl sulfoxide and sulfolane. Examples of the cyclic aliphatic hydrocarbon include monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and cyclooctane; methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, and 1,2-, which are derivatives thereof. Dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1, 2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc.; Polycyclic aliphatic hydrocarbons such as decalin; n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, Acyclic aliphatic hydrocarbons, such as n-decane, n-dodecane, and n-tetradecane, as aromatic hydrocarbons, toluene, p-xylene, o-xylene, m-xylene, etc. , ethanol, isopropanol, n-butanol, tert-butanol, hexanol, octanol, cyclohexanol, and the like.

In a homogeneous reaction, the solubility of the anion generated from the fluorenes (I) is high, and since the progress of reaction tends to be favorable, the amide type solvent of a polar solvent, or a sulfoxide type solvent is preferable. Among them, N,N-dimethylformamide is particularly preferable. This is because the solubility of the trifluorene compound (IIa) in N,N-dimethylformamide is low, and the target product is precipitated quickly after production, further reaction progress is suppressed, and the selectivity of the target product tends to increase. Because.

In a two-layer reaction, it forms two layers with a basic aqueous solution, the solubility of anions generated from fluorenes (I) is high, and the reaction tends to proceed favorably, so that the ether solvent of a polar solvent; Or a halogen-based solvent is preferable. Among them, tetrahydrofuran is particularly preferable. This is because the solubility of the trifluorene compound (IIa) in tetrahydrofuran is low, the target product precipitates quickly after formation, and further reaction progress is suppressed, and the selectivity of the target product tends to increase.

These solvents may be used individually by 1 type, and may mix and use 2 or more types.

As an upper limit of the usage-amount of a solvent, the quantity used is normally 10 times volume amount of the fluorenes (I) of a raw material, Preferably it is 7 times volume amount, More preferably, the quantity used as 4 times volume amount is used. On the other hand, when the amount of the solvent used is too small, stirring becomes difficult and the progress of the reaction tends to be slow. is used in an amount that is 2 times the volume, more preferably 3 times the volume.

<1.8.3.2.4 Reaction format>

When carrying out the step (ia), the reaction format may be a batch reaction, a flow-through reaction, or a combination thereof, and the format can be adopted without particular limitation.

<1.8.3.2.5 Reaction conditions>

In the process (ia), in order to suppress the formation of the compound in which the fluorene ring crosslinked rather than the trifluorene compound (IIa), it is preferable to react at as low temperature as possible. On the other hand, when the temperature is too low, there is a possibility that a sufficient reaction rate cannot be obtained.

Therefore, as a specific reaction temperature, an upper limit is 40 degreeC normally, Preferably it is 30 degreeC, More preferably, it implements at 20 degreeC. On the other hand, the lower limit is -50°C, preferably -20°C, more preferably 0°C or higher.

As for the general reaction time in the step (ia), the lower limit is usually 30 minutes, preferably 60 minutes, more preferably 2 hours, and the upper limit is not particularly limited, but usually 20 hours, preferably 10 hours. hours, more preferably 5 hours.

<1.8.3.2.6 separation/purification of target substance>

After completion of the reaction, the target trifluorene compound (IIa) can be isolated by adding the reaction solution to acidic water such as dilute hydrochloric acid, or adding acidic water such as dilute hydrochloric acid to the reaction solution for precipitation.

Moreover, after completion of the reaction, a solvent in which the trifluorene compound (IIa) is soluble as the target product and water may be added to the reaction solution for extraction. The target substance extracted with the solvent can be isolated by a method of concentrating the solvent, a method of adding a poor solvent, or the like. However, since the solubility of the trifluorene compound (IIa) with respect to a solvent tends to be very low at room temperature, the method of making it contact with acidic water and making it deposit normally is preferable.

Although it is also possible to use the obtained trifluorene compound (IIa) as a raw material of a process (ii) as it is, after refine|purifying, you may use it for a process (ii). As a purification method, a conventional purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be employ|adopted without limitation.

<1.8.3.3 Step (ib): ^{Manufacturing method when R 3} is other than a direct bond>

The trifluorene compound represented by the following general formula (IIb) is produced from fluorenes (I) as a raw material, in the presence of an alkylating agent (VIIIa) and a base, according to the reaction represented by the following step (ib).

[Formula 48]

In the formula, R ³ , R ^3a , and R ^3b are an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 6 to 10 carbon atoms. , R ~ ⁴ R ⁹ are as defined and R ~ ⁴ R ⁹ in the formula (1). X represents a leaving group. Examples of the leaving group include a halogen atom (however, excluding fluorine), a mesyl group, or a tosyl group.

The trifluorene compound (IIb) is prepared by using n-butyllithium as a base, generating an anion of the fluorenes (I), and then coupling with an alkylating agent (VIIIa) (J. Am. Chem. Soc. , 2007, 129, 8458.) can be synthesized by referring to. However, industrial production by the method using these n-butyllithium tends to be very difficult in terms of safety and cost.

Examples of the alkylating agent used in step (ib) include diiodomethane, 1,2-diiodoethane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,6- Diiodohexane, dibromomethane, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-di Bromohexane, dichloromethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1-bromo-3-chloro Linear alkyldihalides such as propane (excluding fluorine atoms), 2,2-dimethyl-1,3-dichloropropane, etc. branched alkyldihalides (excluding fluorine atoms) 1, Aralkyldihalides such as 4-bis(bromomethyl)benzene and 1,3-bis(bromomethyl)benzene (excluding fluorine atoms), ethylene glycol dimesylate, ethylene glycol ditosylate, and propylene glycol dihalides Disulfonates of glycols, such as mesylate and tetramethylene glycol dimesylate, etc. are mentioned.

<1.8.4 Manufacturing method of trifluorenediester (1)>

Hereinafter, the manufacturing method of the trifluorenediester (1) in process (ii) shown by a following formula is divided for every kind ^{of R<1> and is described.}

[Formula 49]

Wherein, R ¹ ~ R ¹⁰ is formula (1) means the same as in R ¹ ~ R ^10. R _i , R _ii and R _iii are each independently a hydrogen atom, an optionally substituted C1-C10 alkyl group, an optionally substituted C4-C10 aryl group, or optionally substituted C6-C10 Ar represents an alkyl group.

<1.8.4.1 Step (iia): Manufacturing method by Michael addition>

A trifluorenediester represented by the following general formula (1a) is prepared from a trifluorene compound (II) and an α,β-unsaturated ester (VI) in the presence of a base according to the reaction represented by the following step (iia) do.

[Formula 50]

Wherein, R ³ ~ R ¹⁰ is formula (1) means the same as in R ³ ~ R ^10. R _i , R _ii and R _iii are each independently a hydrogen atom, an optionally substituted C1-C10 alkyl group, an optionally substituted C4-C10 aryl group, or an optionally substituted C6-C10 alkyl group represents an aralkyl group.

<1.8.4.1.1 α,β-unsaturated ester>

The α,β-unsaturated ester as a reaction reagent is represented by the general formula (VI) in the step (iia), in the general formula (VI), R _i , R _ii and R _iii are each independently a hydrogen atom and a carbon number A 1-10 alkyl group, a C4-C10 aryl group which may be substituted, or a C6-C10 aralkyl group which may be substituted is shown. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclohexyl group (which may be straight or branched), such as an alkyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 2-thienyl group Aralkyl groups, such as an aryl group, such as a benzyl group, 2-phenylethyl group, and p-methoxybenzyl group, are mentioned.

As α,β-unsaturated ester (VI), methyl acrylate, ethyl acrylate, phenyl acrylate, allyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol Acrylic acid esters such as monoacrylate, methyl methacrylate, ethyl methacrylate, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, methacrylic acid ester such as 2-hydroxyethyl methacrylate and α-substituted unsaturated esters such as methyl 2-ethyl acrylate and methyl 2-phenyl acrylate, and β-substituted unsaturated esters such as methyl cinnamate, ethyl cinnamate, methyl crotonate, and ethyl crotonate. Among them, an unsaturated carboxylic acid ester represented by the following general formula (VI-1) into which a polymerization-reactive group can be introduced directly.

[Formula 51]

(In the formula, R ¹⁰ represents an organic substituent having 1 to 10 carbon atoms, R _iii is optionally an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydrogen atom, having 4 to 10 carbon atoms which may be optionally substituted aryl, or substituted which represents an aralkyl group having a carbon number of 6-10.) it is preferable, and there are, acrylic acid esters, methacrylic acid esters or substituted α- unsaturated esters are more preferably contained in, and R _iii is a hydrogen atom or a methyl group; Acrylic acid esters or methacrylic acid esters are more preferable from a viewpoint of reaction rate and reaction selectivity. As for R ¹⁰ , smaller ones are industrially inexpensive, and distillation purification is also easy, and since reactivity is high, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate, or phenyl methacrylate is particularly preferable. do.

On the other hand, when the unsaturated carboxylic acid ester (VI-1) is an ester having a hydroxyalkyl group such as 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, or 1,4-cyclohexanedimethanol monoacrylate group , since it is possible to obtain polyester carbonate and a raw material of polyester in one step, it is particularly preferable.

Although two or more different types of α,β-unsaturated esters (VI) may be used, it is preferable to use one type of α,β-unsaturated esters (VI) from the viewpoint of simplicity of purification.

Since the α,β-unsaturated ester (VI) has high polymerization activity, when it exists at a high concentration, it tends to polymerize easily by external stimuli such as light, heat, and acid/base. In that case, since it accompanies large heat_generation|fever, it may become very dangerous. Therefore, the amount of the α,β-unsaturated ester (VI) to be used is preferably not excessively used from the viewpoint of safety. Usually, it is 10 times mole or less with respect to the trifluorene compound (II) which is a raw material, Preferably it is 5 times mole or less, More preferably, it is 3 times mole or less. Since a lower limit is 2 times mole in theoretical amount with respect to a raw material, it is 2 times mole or more normally. In order to speed up the reaction and not leave the raw material or intermediate, the amount of the α,β-unsaturated ester (VI) to be used is 2.2 times moles or more, more preferably 2.5 times the amount of the trifluorene compound (II) as the raw material. It's more than a mole.

<1.8.4.1.2 base>

Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide; carbonates of alkali metals such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate; magnesium carbonate; calcium carbonate; of alkaline earth metal carbonates, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate and potassium phosphate, organic lithium salts such as n-butyllithium and tert-butyllithium, sodium methoxide, sodium ethoxide, potassium tert-butoxy Alkoxide salts of alkali metals such as seed, alkali metal hydrides such as sodium hydride and potassium hydride, tertiary amines such as triethylamine and diazabicycloundecene, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl Quaternary ammonium hydroxides, such as trimethylammonium hydroxide, are used. These may be used individually by 1 type, and may use 2 or more types together.

In the case where R ³ is a methylene group, and in the case where it is other than that, the reactivity of the trifluorene compound (II) tends to differ greatly. Therefore, the case where R ³ is a methylene group and the case other than that are described separately.

When R ³ is a methylene group, the trifluorene compound (II) undergoes a decomposition reaction easily in a solvent and in the presence of a base. Therefore, when the reaction is carried out in two layers of the organic layer and the aqueous layer, it is preferable to use a water-soluble inorganic base from the viewpoint of suppressing side reactions such as decomposition reaction. Among them, an aqueous solution of an alkali metal hydroxide is preferable from the viewpoint of cost and reactivity, an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is more preferable, and an aqueous solution of sodium hydroxide is still more preferable.

In addition, the concentration of the aqueous solution is usually 10 wt/wt% or more, preferably 30 wt/wt or more, since, when a particularly preferable aqueous sodium hydroxide solution is used, the reaction rate tends to decrease remarkably when the concentration is soft. % or more, more preferably 40 wt/wt% or more of an aqueous solution is particularly preferred.

When R ³ is other than a methylene group, the reaction proceeds even in a two-layer system of an organic layer and an aqueous layer. It is preferable to use Among these, preferably, it is an alkali metal alkoxide which has sufficient basicity in this reaction, More preferably, they are industrially cheap sodium methoxide or sodium ethoxide. Here, a powdery thing may be used for the alkoxide of an alkali metal, and liquid things, such as an alcohol solution, may be used for it. Moreover, you may prepare it by making an alkali metal and alcohol react.

When R ³ is a methylene group, the amount of the base used is not particularly limited with respect to the raw material trifluorene compound (II), but if the amount used is too large, the purification load after stirring or reaction may increase, so a particularly preferable base When an aqueous sodium hydroxide solution of 40 wt/wt% or more of phosphorus is used, it is usually 10 times or less by volume, preferably 5 times or less by volume, more preferably 2 times or less with respect to trifluorene (II). . When there is too little amount of a base, since reaction rate will fall remarkably, normally, a base is 0.1 times volume amount or more with respect to the trifluorene compound (II) of a raw material. Preferably it is 0.2 times volume amount or more, More preferably, it is 0.5 times volume amount or more.

When R ³ is other than a methylene group, the amount of the base used is not particularly limited with respect to the raw material trifluorene compound (II), but if the amount used is too large, the purification load after stirring or reaction may increase, When sodium methoxide or sodium ethoxide, which are particularly preferred bases, is used, usually 5 times mole or less, preferably 2 times mole or less, more preferably 1 times mole or less relative to the trifluorene compound (II); Especially preferably, it is 0.5 times mole or less. Since there exists a tendency for a reaction rate to fall remarkably when there is too little amount of a base, normally, a base is 0.005 times mole or more with respect to trifluorene (II) of a raw material. Preferably it is 0.01 times mole or more, More preferably, it is 0.05 times mole or more, Especially preferably, it is 0.1 times mole or more.

<1.8.4.1.3 Phase Transfer Catalyst>

In the step (iia), when the reaction is carried out in a two-layer system of an organic layer and an aqueous layer, in order to increase the reaction rate, it is preferable to use a phase transfer catalyst.

Examples of the phase transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, benzyltrimethylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium iodine, acetyltrimethylammonium bromide, benzyl Halides of quaternary ammonium salts such as triethylammonium chloride (excluding fluorine), N,N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodine, N-butyl-N-methylpyrrolidinium Halides of quaternary pyrrolidinium salts such as bromide, N-benzyl-N-methylpyrrolidinium chloride and N-ethyl-N-methylpyrrolidinium bromide (excluding fluorine), N-butyl-N-methylmorphol Halides of quaternary morpholinium salts such as nium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide (excluding fluorine), N-methyl-N-benzylpipe Lidinium chloride, N-methyl-N-benzylpiperidinium bromide, N,N-dimethylpiperidinium iodine, N-methyl-N-ethylpiperidinium acetate, N-methyl-N-ethylpiperidinium iodine, etc. halides of quaternary piperidinium salts (excluding fluorine), crown ethers, and the like. It is preferably a quaternary ammonium salt, more preferably tetrabutylammonium bromide, benzyltrimethylammonium chloride, or benzyltriethylammonium chloride.

These may be used individually by 1 type, and may use 2 or more types together.

When the amount of the phase transfer catalyst used is too large with respect to the trifluorene compound (II) as a raw material, the progress of side reactions such as hydrolysis of ester and successive Michael reaction tends to be remarkable, and also from the viewpoint of cost, it is usually Therefore, it is 5 times mole or less, preferably 2 times mole or less, more preferably 1 times mole or less with respect to the trifluorene compound (II). When there is too little usage-amount of a phase transfer catalyst, since the reaction rate tends to fall remarkably, normally, the usage-amount of a phase transfer catalyst is 0.01 times mole or more with respect to the trifluorene compound (II) of a raw material. Preferably it is 0.1 times mole or more, More preferably, it is 0.5 times mole or more.

<1.8.4.1.4 solvent>

It is preferable to carry out the process (iia) using a solvent.

Specifically, the usable solvent is acetonitrile, propionitrile, etc. as the alkylnitrile solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. as the ketone solvent, and methyl acetate and acetic acid as the ester solvent. Linear esters such as ethyl, propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, 3-methoxymethylpropionate, 3-ethoxymethylpropionate, methyl lactate, ethyl lactate; γ- Cyclic esters such as butyrolactone and caprolactone; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol-1-monomethyl ether acetate, propylene glycol-1-mono Ether esters, such as ethyl ether acetate, etc. As an ether solvent, diethyl ether, tetrahydrofuran, 1, 4- dioxane, methylcyclopentyl ether, tert-butyl methyl ether, etc. As a halogen-type solvent, 1 ,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, etc., halogen-based aromatic hydrocarbons, such as chlorobenzene, 1,2-dichlorobenzene, and amide solvents, N, N-dimethylformamide, N,N,-dimethylacetamide, etc., as a sulfoxide solvent, dimethyl sulfoxide, sulfolane, etc., as a cyclic aliphatic hydrocarbon, cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc. of monocyclic aliphatic hydrocarbons; methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, and iso Propylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc.; decalin, etc.; of polycyclic aliphatic hydrocarbons; acyclic aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane, aromatic Examples of the hydrocarbon include toluene, p-xylene, o-xylene, and m-xylene, and the aromatic heterocyclic ring includes pyridine, Examples of the alcohol-based solvent include methanol, ethanol, isopropanol, n-butanol, tert-butanol, hexanol, octanol, and cyclohexanol.

It turns out that when R<^3> is a methylene group, there exists a tendency which can suppress side reactions, such as a decomposition reaction of a trifluorene compound (II), by using water and the solvent which phase-separates. In addition, since the progress of the reaction tends to be good when a solvent that readily dissolves the trifluorene compound (II) of the raw material is used, a solvent in which the solubility of the trifluorene compound (II) of the raw material is 0.5 mass% or more is used. It is preferable to use, More preferably, 1.0 mass % or more, Especially preferably, 1.5 mass % or more of solvent is used. Specifically, a halogen-based aliphatic hydrocarbon, a halogen-based aromatic hydrocarbon, an aromatic hydrocarbon, or an ether-based solvent is preferable, and dichloromethane, chlorobenzene, chloroform, 1,2-dichlorobenzene, tetrahydrofuran, and 1,4-dioxane are preferable. , or methylcyclopentyl ether is particularly preferred.

These solvents may be used individually by 1 type, and may mix and use 2 or more types.

The amount of the solvent to be used is not particularly limited, but considering the production efficiency of the target product per reactor, it is usually 20 times the volume of the raw material trifluorene compound (II), preferably 15 times the volume, more preferably Usually, an amount equal to 10 times the volume is used. On the other hand, when the amount of the solvent used is too small, the solubility of the reagent worsens, stirring becomes difficult, and the progress of the reaction tends to be slow. An amount that is a volume amount, preferably a volume amount twice, more preferably a volume amount of 4 times is used.

When R ³ is other than a methylene group, it can be seen that the solubility of the organic base and the trifluorene compound (II) tends to greatly affect the reaction rate, and in order to secure the solubility, a solvent having a dielectric constant greater than or equal to a certain value It is preferable to use As a solvent which readily dissolves the organic base and the trifluorene compound (II), an aromatic heterocyclic ring, an alkylnitrile-based solvent, an amide-based solvent and a sulfoxide-based solvent are preferable, and pyridine, acetonitrile, N,N-dimethylform Particular preference is given to amides, N,N-dimethylacetamide, dimethylsulfoxide and sulfolane.

These solvents may be used individually by 1 type, and may mix and use 2 or more types.

The amount of the solvent to be used is not particularly limited, but considering the production efficiency of the target product per reactor, it is usually 20 times the volume of the raw material trifluorene (II), preferably 15 times the volume, more preferably is used in an amount that is 10 times the volume. On the other hand, when the amount of the solvent used is too small, the solubility of the reagent worsens, stirring becomes difficult, and the progress of the reaction tends to be slow. amount, preferably in an amount that is two times the volume, more preferably four times the volume.

<1.8.4.1.5 Reaction format>

When carrying out the step (iia), the reaction format may be a batch reaction, a flow-through reaction, or a combination thereof, and the format can be adopted without particular limitation.

In the case of batch type, when the reaction reagent is introduced into the reactor, α,β-unsaturated ester (VI) is present at a high concentration when the α,β-unsaturated ester (VI) is added as a batch at the start of the reaction. , the polymerization reaction of the side reaction tends to proceed. Therefore, after adding the raw material trifluorene compound (II), a phase transfer catalyst, a solvent, and a base, it is preferable to sequentially add the ?,?-unsaturated ester (VI) in small portions.

<1.8.4.1.6 Reaction conditions>

In the step (iia), when the temperature is too low, a sufficient reaction rate cannot be obtained, and conversely, when the temperature is too high, the polymerization reaction of the α,β-unsaturated ester (VI) tends to proceed easily, so temperature control is important do. Therefore, as a reaction temperature, specifically, normally, a minimum is 0 degreeC, Preferably it is 10 degreeC, More preferably, it implements at 15 degreeC. On the other hand, the upper limit is usually carried out at 40°C, preferably at 30°C, more preferably at 20°C.

As for the general reaction time in the step (iia), the lower limit is usually 30 minutes, preferably 1 hour, more preferably 2 hours, and the upper limit is not particularly limited, but usually 20 hours, preferably 10 hours. hours, more preferably 5 hours.

<1.8.4.1.7 Separation and purification of target substance>

After completion of the reaction, the target product, trifluorenediester (1a), is obtained by filtering the by-product metal halide and the remaining inorganic base from the reaction solution and then concentrating the solvent or adding a poor solvent of the target product. It can be isolated by employing a method or the like to precipitate trifluorenediester (1a) as the target product.

Moreover, you may add and extract acidic water and the solvent in which the trifluorenediester (1a) which is a target object is soluble to a reaction liquid after completion|finish of reaction. The target substance extracted with the solvent can be isolated by a method of concentrating the solvent, a method of adding a poor solvent, or the like.

The solvent that can be used for extraction may be any solvent in which the target product, trifluorenediester (1a), is dissolved, and there is no particular limitation, but aromatic hydrocarbon compounds such as toluene and xylene, dichloromethane and halogen-based solvents such as chloroform, etc. 1 type or 2 or more types are used suitably.

The trifluorenediester (1a) obtained here can be used as it is as a polyester or as a polyester carbonate raw material monomer, or as a precursor of a polycarbonate raw material monomer, but may be used after purification. As a purification method, a conventional purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be employ|adopted without limitation. It is also possible to dissolve the trifluorenediester (1a) in a suitable solvent and treat it with activated carbon. The solvent usable in that case is the same as the solvent usable at the time of extraction.

<1.8.4.2 step (iib): production method by alkylation>

The trifluorenediester (1b) can be produced by a method of subjecting the trifluorene compound (II) to an alkylation reaction of the alkylating agents (VIIIb) and (VIIIc).

[Formula 52]

Wherein, R ¹ ~ R ⁹ is the formula (1) the same as defined in R ¹ ~ R ^9. X represents a leaving group. Examples of the leaving group include a halogen atom (however, excluding fluorine), a mesyl group, or a tosyl group.

The alkylation reaction of fluorenes is widely known, for example, 9,9-bis(haloalkyl) such as 9,9-bis(bromohexyl)fluorene or 9,9-bis(iodohexyl)fluorene Fluorene has been reported (J. Org. Chem., 2010, 75, 2714.). From these findings, by using the trifluorene compound (II) as a raw material, the synthesis|combination of trifluorene diester (1b) is possible.

Examples of the alkylating agent used in the step (iib) include methyl chloroacetate, methyl bromoacetate, methyl iodide, ethyl chloroacetate, ethyl bromoacetate, ethyl iodide, propyl chloroacetate, n-butyl chloroacetate, and tert chloroacetate. -Butyl, tert-butyl bromoacetate, tert-butyl iodine acetate, methyl 2-chloropropionate, methyl 2-bromopropionate, methyl 2-iodopropionate, ethyl 2-chloropropionate, tert-butyl 2-chloropropionate, 2 -tert-butyl bromopropionate, 2-ethyl bromopropionate, 2-ethyl iodopropionate, 3-methyl chlorobutyrate, 3-methyl bromobutyrate, 3-methyl iodobutyrate, 3-chlorobutyrate ethyl, 3-chlorobutyric acid Alkyl haloalkanoates such as ethyl, 3-ethyl iodobutyrate and tert-butyl 2-iodopropionate, aryl haloalkanates such as phenyl chloroacetate, phenyl bromoacetate, and phenyl iodide acetate, 4-chloromethyl methyl benzoate, 4- Alkyl haloalkyl benzoate, such as methyl bromomethyl benzoate, 4-chloromethyl ethyl benzoate, 4-bromomethyl ethyl benzoate, 3-chloromethyl methyl benzoate, 3-bromomethyl methyl benzoate, etc. are mentioned.

<1.8.4.3 Manufacturing method of trifluorenediaryl ester of general formula (1c) (After synthesis of trifluorenediester compound (1), manufacturing method of trifluorenediaryl ester compound (1c) by transesterification reaction )>

The trifluorenediaryl ester compound (1c) is a transesterification reaction between the step (step (iia) or step (iib) for synthesizing the trifluorenediester compound (1) and the subsequent diaryl carbonates (11a)) (Step (iic)).

[Formula 53]

Wherein, R ¹ ~ R ¹⁰ is formula (1) means the same as in R ¹ ~ R ^10. Ar ¹ represents an optionally substituted aryl group having 4 to 10 carbon atoms.

<1.8.4.3.1 Method for producing trifluorenediaryl ester of general formula (1c) (Method for producing trifluorenediaryl ester compound (1c) by transesterification)>

The ^{trifluorenediaryl ester compound (1c), wherein Ar 1} is an optionally substituted aryl group having 4 to 10 carbon atoms, is prepared from the trifluorenediester compound (1) and the diaryl carbonates (11a) in the presence of a transesterification catalyst; It is prepared according to the reaction shown in step (iic).

<1.8.4.3.1.1 Diaryl carbonates>

Diaryl carbonates as the reaction reagent include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-crezyl carbonate, dinaphthyl canate, bis (biphenyl) carbonate, and the like. Among them, diphenyl carbonate which is inexpensive and can be obtained industrially is preferable. These diaryl carbonates may be used individually by 1 type, and may mix and use 2 or more types.

There is no upper limit in particular for the usage-amount of diaryl carbonates with respect to the trifluorenediester (1) used as a raw material, but if the usage-amount is too large, since the purification load after reaction tends to become large, normally, it is 20 It is fold mole or less, Preferably it is 10 times mole or less, More preferably, it is 5 times mole or less.

On the other hand, if the amount of the base used is too small, trifluorene diester (1) as a raw material or an intermediate, trifluorene monoaryl ester (1e) as shown below may remain. As a lower limit, usually , 1 times mole or more, preferably 1.5 times mole or more, more preferably 2 times mole or more with respect to the trifluorenediester (1) of the raw material.

[Formula 54]

Wherein, R ¹ ~ R ¹⁰ is formula (1) means the same as in R ¹ ~ R ^10. Ar ¹ represents an optionally substituted aryl group having 4 to 10 carbon atoms.

<1.8.4.3.1.2 Transesterification Catalyst>

Examples of the transesterification reaction catalyst include tetrabutoxy titanium, tetraisobutoxy titanium, tetramethoxy titanium, tetraisopropoxy titanium, tetraethoxy titanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxy titanium , tetraphenoxy titanium, titanium (IV) acetylacetonate, titanium (IV) diisopropoxide bis (acetylacetnato), and other titanium compounds; lithium carbonate, dibutylaminolithium, lithium acetylacetonate, sodium phenoxide , Alkali metal compounds such as potassium phenoxide; Cadmium compounds such as cadmium acetylacetonate and cadmium carbonate; Zirconium compounds such as zirconium acetylacetonate and zirconocene; Lead sulfide, lead hydroxide, lead acid salt, zincate, lead carbonate, Lead compounds, such as lead acetate, tetrabutyl lead, tetraphenyl lead, triphenyl lead, dimethoxy lead, and diphenoxy lead; Copper acetate, copper bisacetylacetonate, copper oleate, butyl copper, dimethoxy copper, copper chloride, etc. Copper compounds; Iron compounds such as iron hydroxide, iron carbonate, triacetoxy iron, trimethoxy iron and triphenoxy iron; zinc bisacetylacetonate, diacetoxy lead, dimethoxy zinc, diethoxy zinc, diphenoxy iron, etc. of zinc compounds; din-butyltin oxide, diphenyltin oxide, din-octyltin oxide, din-butyltin dimethoxide, din-butyltin diacrylate, din-butyltin dimethacrylate organic tin compounds such as , din-butyltin dilaurate, tetramethoxytin, tetraphenoxytin, tetrabutyl-1,3-diacetoxydistanoxane; aluminum acetate, aluminum methoxide, aluminum ethoxide; Aluminum compounds, such as aluminum phenoxide; Vanadium compounds, such as vanadium dichloride, vanadium trichloride, vanadium tetrachloride, and vanadium sulfate; Phosphonium salts, such as tetraphenylphosphonium phenoxide, etc. are mentioned. These may be used individually by 1 type, and may use 2 or more types together.

Among these, it is preferable to use a phosphonium salt, a lithium compound, a zirconium compound, an organotin compound, or a titanium compound, etc. from the viewpoint of being industrially inexpensive and having a superiority in reaction operation, and among them, an organotin compound or titanium Compounds are particularly preferred.

The amount of the transesterification catalyst used is not particularly upper limit with respect to the raw material trifluorenediester (1), but if the amount used is too large, the purification load after the reaction tends to increase, so usually 20 mol% or less of fluorene , Preferably it is 10 mol% or less, More preferably, it is 5 mol% or less.

On the other hand, when the amount of the transesterification catalyst used is too small, the reaction time may become too long. As a lower limit, usually 0.1 mol% or more, preferably 0.5 mol, relative to the trifluorenediester of the raw material. % or more, more preferably 1 mol% or more.

<1.8.4.3.1.3 solvent>

In step (iic), although a reaction solvent may be used, it is preferable to carry out reaction only with trifluorenediester (1) of raw materials, diaryl carbonates, and transesterification catalyst without using a reaction solvent. However, when trifluorenediester (1) of a raw material and diaryl carbonate are solid at normal temperature, and stirring is difficult, you may use a reaction solvent. In the case of using the reaction solvent, as long as it is a solvent capable of suitably dissolving and/or dispersing the trifluorenediester (1), diaryl carbonate, and transesterification reaction catalyst of the above-mentioned raw materials, the type is arbitrary. .

Specifically, the solvent that can be used is an alkylnitrile solvent, such as acetonitrile, propionitrile, a ketone solvent, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and an ether solvent, diethyl ether, As a halogen-based solvent such as tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, tert-butylmethyl ether, 1,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetra Chloroethane and the like, halogen-based aromatic hydrocarbons, such as chlorobenzene and 1,2-dichlorobenzene, and amide solvents, N,N-dimethylformamide, N,N,-dimethylacetamide, and the like, sulfoxide solvents Examples of the cyclic aliphatic hydrocarbon include dimethyl sulfoxide and sulfolane; monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and cyclooctane; methylcyclopentane, ethylcyclopentane, and methylcyclohexane derivatives thereof. , ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane Hexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc.; Polycyclic aliphatic hydrocarbons such as decalin; n-pentane, n-hexane, n-heptane, n -Acyclic aliphatic hydrocarbons such as octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane, and aromatic hydrocarbons include toluene, p-xylene, o-xylene, m-xylene , 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-tetrahydronaphthalene, etc. As an aromatic heterocyclic ring, a pyridine etc. are mentioned.

Since this reaction is usually preferably carried out at a high temperature of 100 ° C. or higher, among the above solvents, chlorobenzene, 1,2-dichlorobenzene, trichlorobenzene, toluene, p-xylene, o -xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-tetrahydronaphthalene, decahydronaphthalene, N,N-dimethylformamide , N,N-dimethylacetamide, dimethylsulfoxide, or sulfolane is preferable, the raw material trifluorenediester (1) can be suitably dissolved, the boiling point is 130°C or higher, and the reaction at a higher temperature From this point, 1,2-dichlorobenzene, xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, or 1,2,3,4-tetrahydronaphthalene, decahydronaphthalene This is particularly preferred.

These solvents may be used individually by 1 type, and may mix and use 2 or more types.

The amount of the solvent used is not particularly limited in the upper limit, but considering the production efficiency of the target product per reactor, it is usually 15 times the volume of the raw material trifluorenediester (1), preferably 10 times the volume, more Preferably, an amount that is five times by volume is used. On the other hand, when there is too little usage-amount of a solvent, since the solubility of a reagent worsens and stirring becomes difficult and there exists a tendency for advancing of reaction to become slow, as a lower limit, normally, it is 1 of trifluorenediester (1) of a raw material. A double volume amount, preferably a double volume amount, more preferably an amount which becomes a 4 times volume amount is used.

<1.8.4.3.1.4 Reaction format>

When carrying out the step (iic), the reaction mode may be a batch reaction, a flow-through reaction, or a combination thereof, and the format can be adopted without particular limitation.

<1.8.4.3.1.5 Reaction conditions>

In the step (iic), if the temperature is too low, a sufficient reaction rate tends not to be obtained, so the lower limit is usually 50°C, preferably 70°C, more preferably 100°C. On the other hand, an upper limit is 250 degreeC normally, Preferably it is 200 degreeC, More preferably, it implements at 180 degreeC.

As for the general reaction time in the step (iic), the lower limit is usually 1 hour, preferably 2 hours, more preferably 3 hours, and the upper limit is not particularly limited, but usually 30 hours, preferably 20 hours. hours, more preferably 10 hours.

In the step (iic), the reaction may be carried out while distilling off the by-products under reduced pressure in order to shift the equilibrium to the product side. The pressure in the case of reducing the pressure is usually 20 kPa or less, preferably 10 kPa or less, and more preferably 5 kPa or less. On the other hand, if the pressure reduction degree is too high, there is a possibility of sublimation to the diaryl carbonates used as reagents, so it is usually 0.1 kPa or more, preferably 0.5 kPa or more, more preferably 1.0 kPa or more.

<1.8.4.3.1.6 Separation and purification of target substance>

After completion of the reaction, the target product, trifluorenediaryl ester (1c), can be isolated by adding a poor solvent to the reaction solution and precipitating it.

Moreover, after completion of the reaction, a solvent in which trifluorenediaryl ester (Ic) is soluble as the target product and water may be added to the reaction solution for extraction. The target substance extracted with the solvent can be isolated by a method of concentrating the solvent, a method of adding a poor solvent, or the like.

The obtained trifluorenediaryl ester (1c) is a polycarbonate raw material containing polyester carbonate, or a polyester raw material, and can also be used for superposition|polymerization as it is. As a purification method, a conventional purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be employ|adopted without limitation.

<2 oligofluorene diester composition>

The oligofluorenediester composition of this invention contains the above-mentioned trifluorenediester and difluorenediester. By including not only trifluorenediester but difluorenediester, it exists in the tendency which becomes possible to easily adjust heat resistance and an optical characteristic to a desired thing.

<2.1 Difluorenediester>

The difluorenediester contained in the oligofluorenediester composition of the present invention contains two fluorene units b which may have a substituent, and the carbon atoms at the 9th position of the fluorene unit b are directly bonded; Alternatively, they are bonded in a chain form via an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent.

As the fluorene unit b, those exemplified as the fluorene unit a can be preferably used. The fluorene unit b in the difluorenediester contained in the oligofluorenediester composition may be the same as or different from the fluorene unit a in the contained trifluorenediester.

As the alkylene group bonding the fluorene unit b, those exemplified as the alkylene group bonding the fluorene unit a can be preferably used. Even if the alkylene group bonding the fluorene unit b in the difluorenediester contained in the oligofluorenediester composition is the same as the alkylene group bonding the fluorene unit a in the contained trifluorenediester, and may be different.

Similarly, as the arylene group bonding the fluorene unit b, those exemplified as the arylene group bonding the fluorene unit a can be preferably used. Even if the arylene group bonding the fluorene unit b in the difluorenediester contained in the oligofluorenediester composition is the same as the arylene group bonding the fluorene unit a in the contained trifluorenediester, and may be different.

Moreover, as an aralkylene group which couple|bonds the fluorene unit b, what was illustrated as an aralkylene group which couple|bonds the fluorene unit a can be used preferably. Even if the aralkylene group bonding the fluorene unit b in the difluorenediester contained in the oligofluorenediester composition is the same as the aralkylene group bonding the fluorene unit a in the contained trifluorenediester, and may be different.

^{The difluorenediester contained in the oligofluorenediester composition of the present invention has substituents α 3} and α ⁴ bonded to the carbon atom at position 9 of the fluorene unit b positioned at both terminals, respectively, and the substituent α ³ and an ester group bonded to ^{α 4 .} In this case, α ³ and α ⁴ may be the same or different. Further, the substituents α ³ and α ⁴ include a direct bond, that is, an ester group may be directly bonded to the carbon atom at the 9th position of the fluorene unit a. As the substituents α ³ and α ⁴ , those ^{exemplified as the substituents α 1} and α ² can be preferably used. Similarly, as an ester group, what was illustrated as an ester group in trifluorenediester can be used preferably.

<2.2 Specific structure of difluorenediester>

As difluorenediester contained in the oligofluorenediester composition of this invention, specifically, what is specifically represented by the following general formula (2) can be used preferably.

[Formula 55]

In the formula, R ¹ and R ² are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ³ is each independently an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 6 to 10 carbon atoms;

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, substituted An optionally substituted acyloxy group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 1 to 10 carbon atoms, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom , a nitro group or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is an organic substituent having 1 to 10 carbon atoms.

In addition, in Formula (2), R<^4>-R<^{9> which} exists two at a time may be respectively same or different. ^{Similarly, two R 10} in Formula (2) may be the same or different, respectively.

As R ¹ to R ¹⁰ in the formula (2), those ^{exemplified as R 1} to R ¹⁰ in the formula (1) can be preferably used.

<2.3 Specific example of difluorenediester>

As a specific example of the difluorenediester contained in the oligofluorenediester composition of this invention, a structure as shown to the following group [I] is mentioned.

[Formula 56]

[Formula 57]

<2.4 Physical properties of difluorene diester>

Although the physical property value of the difluorenediester contained in the oligofluorenediester composition of this invention is not specifically limited, It is preferable that it is what satisfy|fills the physical property value illustrated below.

It is preferable that the decomposition temperature of the difluorenediester of this invention measured in nitrogen atmosphere is 250 degreeC or more, It is more preferable that it is 270 degreeC or more, It is more preferable that it is 290 degreeC or more, It is 300 degrees C or less normally. Since the difluorenediester of the present invention has a rigid structure due to the laminated structure of fluorene rings, the decomposition temperature tends to satisfy the above range. As described above, when the decomposition temperature satisfies the above range, the thermal stability of polyester and polycarbonate obtained from difluorenediester tends to be improved. The decomposition temperature can be measured, for example, by TG-DTA.

Moreover, it is preferable that melting|fusing point (m.p.) of the difluorenediester of this invention is 100 degreeC or more, It is more preferable that it is 120 degreeC or more, It is more preferable that it is 140 degreeC or more, It is 150 degrees C or less normally. Since the difluorenediester of the present invention has a rigid structure due to the layered structure of fluorene rings, the melting point tends to satisfy the above range. Thus, when melting|fusing point satisfy|fills the said range, there exists a tendency which can improve the thermal stability of polyester obtained from difluorenediester and polycarbonate. The melting point can be measured, for example, by TG-DTA.

<2.5 Composition of Oligofluorenediester Composition>

Although it does not specifically limit about the content rate of trifluorenediester contained in the oligofluorenediester composition of this invention, From a viewpoint of improving heat resistance and obtaining desired optical properties with a smaller amount, the composition With respect to the total mass of , and is usually 30% by mass or less.

On the other hand, the content rate of difluorenediester contained in the oligofluorenediester composition is not particularly limited, but from the viewpoint of flexibility and adjustment of optical properties, it is 0.1 mass% or more with respect to the total mass of the composition. Preferably, it is more preferably 0.3 mass % or more, more preferably 1 mass % or more, still more preferably 3 mass % or more, particularly preferably 5 mass % or more, and from the viewpoint of improving heat resistance, 50 It is preferable that it is mass % or less, It is more preferable that it is 40 mass % or less, It is more preferable that it is 30 mass % or less.

Moreover, although it does not specifically limit about the content rate of difluorenedie and trifluorenediester contained in an oligofluorenediester composition, From a viewpoint of adjustment of a flexibility and optical characteristic, difluorene contained in a composition The molar ratio of diester and trifluorenediester (number of moles of difluorenediester/number of moles of trifluorenediester) is preferably 0.001 or more, more preferably 0.003 or more, still more preferably 0.01 or more, and 0.03 It is more preferable that it is more than that, and it is especially preferable that it is 0.05 or more, and from a viewpoint of improving heat resistance, it is preferable that it is 0.5 or less, It is more preferable that it is 0.4 or less, It is still more preferable that it is 0.3 or less.

The number of moles of difluorenediester and trifluorenediester contained in the oligofluorenediester composition can be estimated using a calibration curve from the area% of HPLC analysis, for example.

<3 resin composition>

The resin composition of this invention is a resin composition containing the polymer which has divalent trifluorene as a repeating unit.

Thus, the resin composition of this invention may contain the other polymer mentioned later other than the polymer which has divalent trifluorene as a repeating unit, and may contain the additive etc. Moreover, the resin composition of this invention may consist of a polymer which has divalent trifluorene as a repeating unit.

<3.1 Divalent Trifluorene>

The polymer contained in the resin composition of this invention has divalent trifluorene as a repeating unit. In this way, by having divalent trifluorene as a repeating unit, desired optical properties can be obtained by using a small amount of trifluorene, and there is a tendency that good heat resistance can be exhibited.

In addition, the polymer contained in the resin composition of this invention may have divalent difluorene as a repeating unit further so that it may mention later. Both trifluorene and difluorene may be collectively referred to as oligofluorene.

The divalent trifluorene contains three fluorene units a which may have a substituent, and the carbon atoms at the 9th position of the fluorene unit a are directly bonded to each other, or the fluorene unit a Carbon atoms at position 9 are bonded in a chain form via an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent.

As the fluorene unit a, those exemplified as the fluorene unit a of trifluorenediester can be preferably used.

Similarly, as the alkylene group bonding the fluorene unit a, those exemplified as the alkylene group bonding the fluorene unit a of trifluorene diester can be preferably used. Moreover, as an arylene group which couple|bonds the fluorene unit a, what was illustrated as an arylene group which couple|bonds the fluorene unit a of trifluorene diester can be used preferably. Moreover, as an aralkylene group which couple|bonds the fluorene unit a, what was illustrated as an aralkylene group which couple|bonds the fluorene unit a of trifluorenediester can be used preferably.

^{In the above divalent trifluorene, substituents α 1} and α ² are bonded to the carbon atom at position 9 of the fluorene unit a positioned at both terminals among the three fluorene units a, respectively, and the substituents α ¹ and α ² are It can also be made into a bivalent flag. In this case, α ¹ and α ² may be the same or different. Further, the substituents α ¹ and α ² include a direct bond, that is, the carbon atom at the 9th position of the fluorene unit a may be a divalent group. Roneun substituents α ¹ and α ^2, it may be preferably used that exemplified as the substituent α ¹ and α ² of the triple base fluorene diester.

In particular, when the carbon atom at position 9 of the fluorene unit a positioned at both terminals is a divalent group, or substituents α ¹ and α ^{2 respectively bonded to the carbon atom at position 9 of the fluorene unit a positioned at both terminals} When it is a divalent group and ^{at least one of α 1} and α ² has 2 or more carbon atoms, since the fluorene ring (fluorene unit a) is oriented substantially perpendicular to the main chain, 2 in the resin composition Even if the ratio of valent oligofluorene is small, there exists a tendency for reverse wavelength dispersion property to become easy to express. In the latter case, from the same viewpoint, ^{it is preferable that both of α 1} and α ² have 2 or more carbon atoms. ^{On the other hand, α 1} and α ² each bonded to the carbon atom at position 9 of the fluorene unit a at both terminals are divalent groups, ^{and both α 1} and α ² are carbon atoms 1 (that is, even if substituted) methylene group), since the fluorene ring (fluorene unit a) is not oriented substantially perpendicularly to the main chain, but is oriented at a large inclination, the ratio of the divalent oligofluorene in the resin composition is set within a wide range. Even if it changes, there exists a tendency for flat dispersion with a small difference in phase difference in a broad band to become easy.

As described above, the resin composition of the present invention contains a polymer having a repeating unit in which the carbon atoms at the 9th position of the three fluorene units a are linked by a specific carbon-carbon bond, thereby exhibiting optical properties derived from the fluorene ring. can be obtained more effectively.

As said divalent trifluorene, specifically, what is represented by the following general formula (11) can be used preferably.

[Formula 58]

In the formula, R ¹ and R ² are each independently a direct bond or an optionally substituted alkylene group having 1 to 4 carbon atoms,

R ^3a and R ^3b are each independently an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 6 to 10 carbon atoms;

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, substituted An optionally substituted acyloxy group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 1 to 10 carbon atoms, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom , a nitro group or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

In addition, R ^3a and R ^3b in Formula (11) may be respectively same or different. Further, in each of 3 ~ R ⁴ R ⁹ in formula (11) it may be the same or different, respectively.

^{As R 1} to R ⁹ in the formula (11), those ^{exemplified as R 1} to R ⁹ in the formula (1) can be preferably used.

<3.2 Divalent Difluorene>

The polymer in the resin composition of the present invention may further have divalent difluorene as a repeating unit. By including divalent difluorene in addition to divalent trifluorene, it tends to become possible to easily adjust heat resistance and optical properties to a desired one.

Divalent difluorene contains two fluorene units b which may have a substituent, and carbon atoms at the 9th position of the fluorene unit b are directly bonded to each other, or 9 of the fluorene unit b Carbon atoms at the positions are bonded in a chain form via an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent.

As the fluorene unit b, those exemplified as the fluorene unit b of difluorenediester can be preferably used.

Similarly, as the alkylene group bonding the fluorene unit b, those exemplified as the alkylene group bonding the fluorene unit b of difluorenediester can be preferably used. Moreover, as an arylene group which couple|bonds the fluorene unit b, what was illustrated as an arylene group which couple|bonds the fluorene unit b of difluorene diester can be used preferably. Moreover, as an aralkylene group which couple|bonds the fluorene unit b, what was illustrated as an aralkylene group which couple|bonds the fluorene unit b of difluorene diester can be used preferably.

^{In the divalent difluorene, substituents α 3} and α ⁴ may be bonded to the carbon atom at position 9 of the fluorene unit b positioned at both terminals, respectively, and the substituents α ³ and α ⁴ may be divalent groups. In this case, α ³ and α ⁴ may be the same or different. Further, the substituents α ³ and α ⁴ include a direct bond, that is, the carbon atom at the 9th position of the fluorene unit b may be a divalent group. Roneun substituents α ³ and α ^4, can be preferably used that exemplified as the substituent α ^3, and α ⁴ of the fluorene di-diester.

In particular, when the carbon atom at position 9 of the fluorene unit b positioned at both terminals is a divalent group, or substituents α ³ and α ^{4 each bonded to the carbon atom at position 9 of the fluorene unit b positioned at both terminals} When it is a divalent group and the ^{number of carbon atoms in at least one of α 3} and α ⁴ is 2 or more, since the fluorene ring (fluorene unit b) is oriented substantially perpendicular to the main chain, 2 in the resin composition Even if the ratio of valent oligofluorene is small, it exists in the tendency for reverse wavelength dispersion property to become easy to express. In the latter case, from the same viewpoint, ^{it is preferable that both of α 3} and α ⁴ have 2 or more carbon atoms. ^{On the other hand, α 3} and α ⁴ each bonded to the carbon atom at position 9 of the fluorene unit b at both terminals are divalent groups, ^{and both α 3} and α ⁴ have 1 carbon atom (that is, even if substituted) methylene group), since the fluorene ring (fluorene unit b) is not oriented substantially perpendicularly to the main chain, but oriented at a large inclination, the ratio of the divalent oligofluorene in the resin composition is set within a wide range. Even if it changes, there exists a tendency for flat dispersion with a small difference in phase difference in a broad band to become easy.

As said divalent difluorene, what is specifically, represented with the following general formula (21) can be used preferably.

[Formula 59]

In the formula, R ¹ and R ² are each independently a direct bond or an optionally substituted alkylene group having 1 to 4 carbon atoms,

R ³ is each independently an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 6 to 10 carbon atoms;

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, substituted An optionally substituted acyloxy group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 1 to 10 carbon atoms, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom , a nitro group or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

Roneun R ¹ ~ R ⁹ in the formula (21) can be preferably used that exemplified as the R ¹ ~ R ⁹ in the formula (2).

In addition, in Formula (21), R<^4>-R<^{9> which} exists two at a time may be respectively same or different.

<3.3 Polymer>

The polymer contained in the resin composition of this invention has divalent trifluorene as a repeating unit. For example, the polymer in which bivalent trifluorene was connected by arbitrary coupling groups is mentioned. Moreover, the copolymer which has divalent difluorene or arbitrary repeating units other than those may be sufficient as the polymer.

<3.4 connector>

Although the specific structure of the linking group used in the said polymer is mentioned below, Although it is not limited to these, The linking group shown in the following [J] group

[Formula 60]

(In each linking group shown in the group [J] above, Z represents a site to which the repeating unit connects, and Y represents a binding site to another linking group, or a site to which arbitrary structural units that bond the linking groups to each other are linked. ) is mentioned, and you may use multiple types together among these coupling groups. Moreover, when a linking group is asymmetric, you may connect a linking group in arbitrary directions with respect to a repeating unit. Among these, the linking group shown in the following group [K] is preferable, which comprises polyester, polycarbonate, and polyester carbonate excellent in the balance between heat resistance, melt workability, and mechanical strength.

[Formula 61]

In each linking group shown in the group [K], Z represents a site to which the repeating unit connects.

A coupling group may be used individually by 1 type of thing, and may use multiple types of coupling groups together.

As a polymer in which repeating units are linked by a linking group, specifically, a polymer containing polyolefin, polyester, polycarbonate, polyamide, polyimide, polyurethane, epoxy resin, polyacrylate, polymethacrylate, or polysulfone; Polymers using them together are mentioned, Preferably, it is a polymer containing generally high transparency polyolefin, polyester, polycarbonate, an epoxy resin, or polyacrylate, Especially preferably, heat resistance, melt processability, and mechanical properties are preferable. It is a polymer containing polyester or polycarbonate which is excellent in balance with strength, Especially preferably, it is a polymer containing polycarbonate which is generally excellent in heat resistance and chemical-resistance.

In the case of a polymer using multiple types of linking groups in combination, the combination of linking groups is not particularly limited, but for example, a polymer using a carbonate structure and an ester structure together as a linking group, a polymer using a carbonate structure and a urethane structure together as a linking group, Although the polymer etc. which used the ester structure and amide together are mentioned as a linking group, Preferably, the polymer which used the carbonate structure and ester structure together as a linking group is mentioned. Here, as a specific example of the polymer using a plurality of types of linking groups together, polyester carbonate, polyurethane having a carbonate bond, polyester amide, polyester imide, etc. are mentioned, and among these, heat resistance and melt processability are preferable. It is polyester carbonate excellent in balance with mechanical strength. In the present specification, a polymer having a carbonate bond is called a polycarbonate, and in addition to a polymer having only a carbonate bond as a linking group, polyester carbonate (a polymer having an ester bond and a carbonate bond), a polyurethane having a carbonate bond, and the like are also included. Here, the ratio of carbonate bonds in the polymer containing polycarbonate may be any value, but in order to impart excellent properties such as heat resistance and chemical resistance resulting from carbonate bonds to the resin composition, it is preferably not less than a certain ratio, and the total The mole fraction of carbonate bonds in the linking group is preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, particularly preferably 70% or more, and is usually 100% or less.

<3.5 Copolymer>

The polymer having divalent trifluorene as a repeating unit may be a copolymer further including any divalent organic group (except for divalent trifluorene and divalent difluorene) as a repeating unit. In this case, it is preferable that repeating units are what connected by the above-mentioned coupling group.

The copolymer WHEREIN: As arbitrary divalent organic groups which may be used together with divalent trifluorene, the divalent represented by the following general formula (3) from a viewpoint of controlling in the range of optical properties and physical properties required for a resin composition. An organic group can be used preferably. In this case, as arbitrary divalent organic groups, you may further use together divalent organic groups other than the divalent organic group represented by General formula (3).

[Formula 62]

In the formula, R ²⁰ is an optionally substituted alkylene group having 2 to 20 carbon atoms, an optionally substituted arylene group having 4 to 20 carbon atoms, an optionally substituted alkylene ether group having 2 to 100 carbon atoms, or an optionally substituted C4 alkylene group. An organic group having an alicyclic structure of to 20 or an organic group having an optionally substituted heterocyclic structure having 4 to 20 carbon atoms is shown.

When a polymer contains the divalent organic group represented by the said General formula (3), in addition to being able to take on the function of providing positive refractive index anisotropy to a resin composition, optical properties, such as wavelength dispersion property of retardation and a photoelastic coefficient, , mechanical strength, heat resistance, melt processability, etc., there is a tendency that the physical properties of the resin composition can be arbitrarily controlled, such as controlling various resin properties within a preferable range.

Moreover, it is known that a resin composition which does not have an aromatic ring orientated perpendicularly to a main chain, or has such an aromatic ring, in the whole resin composition with a small ratio generally shows positive refractive index anisotropy. Also in the repeating unit of the divalent organic group represented by the said General formula (3), except having an aromatic ring in a side chain, since all are structures showing positive refractive index anisotropy, the divalent organic group represented by the said General formula (3) It is thought that the resin composition containing 50 mol% or more shows positive refractive index anisotropy.

<3.6 Specific Examples of Organic Groups>

^{As described above, R 20} in the general formula (3) is an optionally substituted C2-C20 alkylene group, an optionally substituted C4-C20 arylene group, or optionally substituted C2-C100 alkylene group. An alkylene ether group, an organic group having an optionally substituted C4-C20 alicyclic structure, or an optionally substituted organic group having a C4-C20 heterocyclic structure is represented.

The specific structure of the "alkylene group having 2 to 20 carbon atoms which may be substituted" is given below, and although not limited to these, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n- Linear alkylene groups, such as a hexylene group; 1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 2; and alkylene groups containing branched chains such as 2-dimethylpropylene group and 3-methylpropylene group. The carbon number is 2 or more, and it is preferable that it is 12 or less, and it is more preferable that it is 6 or less. Among these, it is preferably a linear alkylene group represented by the following general formula (5), which has moderate hydrophobicity and flexibility, and tends to impart a low photoelastic coefficient.

[Formula 63]

(In the formula, R ^2-11 represents an optionally substituted linear alkylene group having 0 to 18 carbon atoms.)

The specific structure of "the optionally substituted linear alkylene group having 0 to 18 carbon atoms" is given below, but is not limited thereto, but an ethylene group, n-propylene group, n-butylene group, and n-pentylene group , n-hexylene group, etc. are mentioned. It is preferable that it is 2 or more, and, as for the carbon number, it is preferable that it is 10 or less, It is more preferable that it is 4 or less.

The specific structure of the "arylene group having 4 to 20 carbon atoms which may be substituted" is given below, and although not limited thereto, a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group phenylene groups such as; 1,5-naphthylene group and naphthylene groups such as 2,6-naphthylene group; 2,5-pyridylene group, 2,4-thienylene group, 2,4-furylene group, etc. A heteroarylene group is mentioned. The carbon number is 4 or more, and it is preferable that it is 8 or less, and it is more preferable that it is 6 or less. Among these, a 1,2-phenylene group, a 1,3-phenylene group, or a 1, 4- phenylene group is preferable from a viewpoint that it can obtain industrially cheaply.

"The optionally substituted C2-C20 alkylene group", "The optionally substituted C0-C18 linear alkylene group", and "The optionally substituted C4-C20 arylene group" is a substituent which may have is a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, an isopropyl group, etc.); an alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.); an acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); an acylamide group having 1 to 10 carbon atoms (eg, acetamide group, benzoylamide group, etc.); nitro group; cia No group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg methoxy group, ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (eg acetyl group, benzoyl group, etc.), an acylamide group having 1 to 10 carbon atoms (eg acetamide group, benzoylamide group, etc.), nitro group, cya and a C6-C10 aryl group (eg, a phenyl group, a naphthyl group, etc.) which may have a 1-3 substituent selected from a no group etc. are mentioned. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Specific examples of the alkylene group having a substituent include a phenylethylene group, a 1-phenylpropylene group, a 1-cyclohexylpropylene group, and a 1,1,2,2-tetrafluoroethylene group.

Specific examples of the arylene group having a substituent include 2-methyl-1,4-phenylene group, 5-methyl-1,3-phenylene group, 2,5-dimethyl-1,4-phenylene group, 2-methoxy -1,4-phenylene group, 2-trifluoromethyl-1,4-phenylene group, 2,5-dimethoxy-1,4-phenylene group, 2,3,5,6-tetrafluoro-1, Substituted arylene groups, such as a 4-phenylene group, are mentioned.

The specific structure of "the optionally substituted C6-C20 aralkylene group" is mentioned below, Although it is not limited to these, An aralkylene group as shown in the following [L] group is mentioned.

[Formula 64]

The carbon number is 6 or more, and it is preferable that it is 10 or less, and it is more preferable that it is 8 or less. Among these, o-xylylene group, m-xylylene group, or p-xylylene group is preferable from a viewpoint that it can obtain industrially cheaply.

Examples of the substituent which the "aralkylene group having 6 to 20 carbon atoms which may be substituted" may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group). , ethyl group, isopropyl group, etc.); Alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.); Acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); acylamide group (eg, acetamide group, benzoylamide group, etc.); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg, methyl group) , ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg methoxy group, ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (eg acetyl group, benzoyl group, etc.), having 1 to 10 carbon atoms An aryl group having 6 to 10 carbon atoms which may have 1 to 3 substituents selected from an acylamide group (eg, acetamide group, benzoylamide group, etc.), nitro group, cyano group, etc. (eg phenyl group, naphthyl group, etc.) can be heard Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

"The optionally substituted C2-C100 alkylene ether group" is a divalent group which has one or more alkylene groups and an ethereal oxygen atom. The carbon number is preferably 4 or more, more preferably 6 or more, more preferably 60 or less, more preferably 50 or less, still more preferably 40 or less, and particularly preferably 30 or less. More specifically, the following general formula (7)

[Formula 65]

(wherein, R ^2-13 represents an optionally substituted alkylene group having 2 to 10 carbon atoms, and p is an integer of 1 to 40.)

[Formula 66]

(wherein, R ^2-14 represents an optionally substituted alkylene group having 2 to 10 carbon atoms, and R ^2-15 represents an optionally substituted arylene group having 12 to 30 carbon atoms.)

In the general formulas (7) and (8), R ^2-13 and R ^2-14 represent an optionally substituted C2-C10 alkylene group. The specific structure is given below, and although it is not limited to these, Linear alkylene groups, such as an ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene; 1- Branches of methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 2,2-dimethylpropylene group, 3-methylpropylene group, etc. and an alkylene group containing a chain (the numerical value of the substitution position is assumed to be attached from the carbon on the terminal side), and the like.

The carbon number is 2 or more, and it is preferable that it is 8 or less, and it is more preferable that it is 4 or less.

As a substituent which the "optionally substituted alkylene ether group having 2 to 100 carbon atoms" and "alkylene group having 2 to 10 carbon atoms which may be substituted" may have, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom) , iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.); an alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.); an acyl group having 1 to 10 carbon atoms ( For example, an acetyl group, a benzoyl group, etc.); an acylamide group having 1 to 10 carbon atoms (eg, an acetamide group, a benzoylamide group, etc.); a nitro group; a cyano group; a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom) , iodine atom), an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg methoxy group, ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms ( For example, an acetyl group, a benzoyl group, etc.), an acylamide group having 1 to 10 carbon atoms (eg, an acetamide group, a benzoylamide group, etc.), a nitro group, a cyano group, etc. -10 aryl groups (eg, a phenyl group, a naphthyl group, etc.) etc. are mentioned. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Specific examples of the alkylene group having a substituent include a phenylethylene group, a 1-phenylpropylene group, a 1-cyclohexylpropylene group, and a 1,1,2,2-tetrafluoroethylene group.

Among these R ^2-13 and R ^2-14 , it is preferably a linear alkylene group that does not have a negative point, and thus the quality of the monomer is easy to control, and more preferably is industrially inexpensive. It is an ethylene group that can be introduced and can impart flexibility and water absorption.

In general formula (7), although p is an integer of 1-40, Preferably it is 1 or more, More preferably, it is 2 or more, More preferably, it is 30 or less, More preferably, it is 20 or less.

In the general formula (8), R ^2-15 represents an optionally substituted C12-30 arylene group. Although the specific structure is mentioned below, Although it is not limited to these, From a viewpoint that the glass transition temperature of a resin composition can be made high, as shown in the following [M] group, an arylene group is mentioned preferably.

[Formula 67]

Examples of the substituent that the "arylene group having 12 to 30 carbon atoms which may be substituted" may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group; ethyl group, isopropyl group, etc.); Alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.); Acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); Acyl group having 1 to 10 carbon atoms Amide group (eg, acetamide group, benzoylamide group, etc.); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg methoxy group, ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (eg acetyl group, benzoyl group, etc.), acyl group having 1 to 10 carbon atoms an aryl group having 6 to 10 carbon atoms which may have 1 to 3 substituents selected from an amide group (eg, acetamide group, benzoylamide group, etc.), nitro group, cyano group, etc. (eg phenyl group, naphthyl group, etc.) can be heard Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Although the specific structure of Formula (7) is mentioned to the following and is not limited to these, An alkylene ether group as shown in the following [N] group

[Formula 68]

(In the group [N], any diastereomer or a diastereomer mixture may be sufficient for a structure capable of diastereomers.);

Although the specific structure of Formula (8) is mentioned to the following and is not limited to these, An alkylene ether group as shown in the following group [O]

[Formula 69]

(In the group [O], any diastereomer or a diastereomer mixture may be sufficient for a structure capable of diastereomers.);

Specific structures of "an optionally substituted organic group having an alicyclic structure having 4 to 20 carbon atoms or an organic group having an optionally substituted heterocyclic structure having 4 to 20 carbon atoms" include, but are not limited to, the following. , since there is a tendency that the glass transition temperature can be made high and the photoelastic modulus can be made low, linear or branched at any two points of the alicyclic or heterocyclic structure as shown in the following [P] group An organic group having a bond of the type alkylene group is preferably mentioned.

[Formula 70]

(The substitution positions of two bonds in each ring structure shown in the group [P] are arbitrary, and two bonds may be substituted on the same carbon.) Here, the bond is a direct bond or carbon number. It is a linear or branched alkylene group of 1-5, and the length of two bonds may differ. A preferable bond is a direct bond with little decrease in glass transition temperature, or a methylene group.

As a substituent which the "organic group having an optionally substituted C4-C20 alicyclic structure or an optionally substituted organic group having a C4-C20 heterocyclic structure" may have, a halogen atom (eg, a fluorine atom, chlorine atom, bromine atom, iodine atom); Alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.); Alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.); 10 acyl group (eg, acetyl group, benzoyl group, etc.); acylamide group having 1 to 10 carbon atoms (eg, acetamide group, benzoylamide group, etc.); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg methyl group, ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg methoxy group, ethoxy group, etc.), 1 to carbon atoms 1 to 3 substituents selected from an acyl group of 10 (eg, an acetyl group, a benzoyl group, etc.), an acylamide group having 1 to 10 carbon atoms (eg, an acetamide group, a benzoylamide group, etc.), a nitro group, a cyano group, etc. The C6-C10 aryl group (For example, a phenyl group, a naphthyl group, etc.) etc. which you may have are mentioned. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Preferred specific structures of "an optionally substituted organic group having an alicyclic structure having 4 to 20 carbon atoms or an organic group having an optionally substituted heterocyclic structure having 4 to 20 carbon atoms" are listed below, However, the following general formula (4), which tends to impart high transparency and glass transition temperature, absorption, birefringence, and low modulus of photoelasticity

[Formula 71]

A group represented by the following general formula (6)

[Formula 72]

(In the formula, R ^2-12 represents an optionally substituted cycloalkylene group having 4 to 20 carbon atoms.) A group represented by, or the following general formula (9)

[Formula 73]

(wherein, R ^2-16 represents a group having an optionally substituted C2-C20 acetal ring.);

In the general formula (6), R ^2-12 represents an optionally substituted C4-C20 cycloalkylene group. The specific structure is given below, and although it is not limited to these, since there exists a tendency which can make a glass transition temperature high and can make a photoelastic coefficient low, cycloalkyl as shown in the following [Q] group Rengi

[Formula 74]

(In the group [Q], any diastereomer may be used, or a diastereomer mixture may be sufficient for a structure capable of diastereomer.) is preferably exemplified.

Examples of the substituent that the "cycloalkylene group having 4 to 20 carbon atoms which may be substituted" may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group). , ethyl group, isopropyl group, etc.); Alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.); Acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); acylamide group (eg, acetamide group, benzoylamide group, etc.); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg, methyl group) , ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg methoxy group, ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (eg acetyl group, benzoyl group, etc.), having 1 to 10 carbon atoms An aryl group having 6 to 10 carbon atoms which may have 1 to 3 substituents selected from an acylamide group (eg, acetamide group, benzoylamide group, etc.), nitro group, cyano group, etc. (eg phenyl group, naphthyl group, etc.) can be heard Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

The specific structure of general formula (6) is mentioned below, Although it is not limited to these, An organic group which has an alicyclic structure as shown in the following group [R]

[Formula 75]

(In the group [R], any diastereomer or a diastereomer mixture may be sufficient for a structure capable of diastereomers.); Among these, the organic group which has an alicyclic structure shown in the following [R-2] group from a viewpoint that it can obtain industrially cheaply is preferable.

[Formula 76]

In the general formula (9), R ^2-16 represents a group having an optionally substituted C2-C20 acetal ring. The specific structure is given below, and although it is not limited to these, since there exists a tendency that a glass transition temperature and birefringence can be made high, and a photoelastic coefficient can be made low, as shown in the following [S] group, group having an acetal ring

[Formula 77]

(In the group [S], any diastereomer may be used for structures capable of diastereomers.)

Examples of the substituent that the "optionally substituted acetal ring having 2 to 20 carbon atoms" may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group; ethyl group, isopropyl group, etc.); Alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.); Acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); Acyl group having 1 to 10 carbon atoms Amide group (eg, acetamide group, benzoylamide group, etc.); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg methoxy group, ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (eg acetyl group, benzoyl group, etc.), acyl group having 1 to 10 carbon atoms an aryl group having 6 to 10 carbon atoms which may have 1 to 3 substituents selected from an amide group (eg, acetamide group, benzoylamide group, etc.), nitro group, cyano group, etc. (eg phenyl group, naphthyl group, etc.) can be heard Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Among the divalent organic groups represented by the general formula (3), preferred ones do not have an aromatic ring in the main chain or contain many partial structures other than the aromatic ring in the main chain, so the low photoelastic coefficient required for the optical film These are an optionally substituted alkylene group, an optionally substituted alkylene ether group, an organic group having an optionally substituted alicyclic structure, or an organic group having an optionally substituted heterocyclic structure, which tends to be attainable. More preferably, the following general formula (4), which tends to impart high transparency, glass transition temperature, absorptivity, birefringence, and low photoelastic coefficient

[Formula 78]

Or, having moderate hydrophobicity and flexibility, and tending to impart a low photoelastic modulus, the following general formula (5)

[Formula 79]

(In the formula, R ^2-11 represents an optionally substituted linear alkylene group having 0 to 18 carbon atoms.) Or the following general formula ( 6)

[Formula 80]

(In the formula, R ^2-12 represents an optionally substituted cycloalkylene group having 4 to 20 carbon atoms.) Or the following general formula (7), which tends to impart flexibility, water absorption and low photoelastic coefficient.

[Formula 81]

(In the formula, R ^2-13 represents an optionally substituted alkylene group having 2 to 10 carbon atoms, and p is an integer of 1 to 40.) Alternatively, the following general which tends to impart high transparency and glass transition temperature Equation (8)

[Formula 82]

(In the formula, R ^2-14 represents an optionally substituted alkylene group having 2 to 10 carbon atoms, and R ^2-15 represents an optionally substituted arylene group having 12 to 30 carbon atoms.) Or high transparency and glass transition Temperature, which tends to give birefringence, the following general formula (9)

[Formula 83]

(In the formula, R ^2-16 represents a group having an optionally substituted C2-C20 acetal ring.). More preferably, it is group represented by the said General formula (4) which tends to provide the physical property excellent as retardation film by providing high transparency, a glass transition temperature, absorptivity, and a low photoelastic coefficient.

The divalent organic group represented by General formula (3) may be used individually by 1 type of thing, and may be used in combination of 2 or more types. From the viewpoint of quality control such as reducing lot-to-lot variation in optical properties and mechanical properties, it is preferable to use one type alone. On the other hand, it is preferable to use two or more types together from a viewpoint of making an optical characteristic and a mechanical property compatible, Moreover, it is usually 4 types or less, and it is preferable to use it in 3 types or less.

When using in combination of 2 or more types of divalent organic groups represented by General formula (3), it does not specifically limit about the combination. For example, for the purpose of imparting high transparency, glass transition temperature, and birefringence, the organic group represented by the general formula (4) or the organic group represented by the general formula (9) is preferable, and for the purpose of imparting flexibility, The organic group represented by the general formula (5) or the organic group represented by the general formula (7) is preferable, and, on the other hand, for the purpose of imparting high transparency, a glass transition temperature, and moderate flexibility, it is represented by the general formula (6) The organic group shown is preferable, and what is necessary is just to select the combination of the organic group corresponding to it according to the combination of the objective requested|required among these. Specifically, a repeating unit derived from ISB (isosorbide) corresponding to the organic group represented by the general formula (4) and CHDM (1,4-cyclohexanedimethanol) corresponding to the organic group represented by the general formula (6) A combination of repeating units derived from a repeating unit, or a combination of a repeating unit derived from SPG (spiroglycol) corresponding to the organic group represented by the general formula (9) and a repeating unit derived from CHDM corresponding to the organic group represented by the formula (6) it is preferable

<3.7 Copolymer composition>

As described above, in the case of using a copolymer containing at least divalent trifluorene, divalent difluorene, and a divalent organic group represented by the general formula (3) as a repeating unit, divalent trifluorene, divalent Difluorene and the divalent organic group represented by General formula (3) may be contained in the said copolymer by arbitrary mass as long as it exists in the range which the optical physical property mentioned later expresses.

The total of the content ratio of divalent trifluorene and divalent difluorene is 5 mass % or more with respect to the mass of the whole copolymer in order to express reverse wavelength dispersion and to maintain melt workability and mechanical strength. It is preferable, it is more preferable that it is 10 mass % or more, It is more preferable that it is 12 mass % or more, It is especially preferable that it is 15 mass % or more, It is preferable that it is 90 mass % or less, It is more preferable that it is 80 mass % or less, It is more preferable that it is 70 mass % or less, and it is especially preferable that it is 60 mass % or less.

Further, from the viewpoint of obtaining desired optical properties with a smaller amount of use, the content of divalent trifluorene is preferably 1 mass% or more, more preferably 3 mass% or more, with respect to the mass of the entire copolymer, It is still more preferably 5 mass % or more, and it is especially preferable that it is 10 mass % or more, Moreover, it is preferable that it is 50 mass % or less, It is more preferable that it is 40 mass % or less, It is still more preferable that it is 30 mass % or less.

Further, from the viewpoint of imparting positive refractive index anisotropy, the preferable content of the divalent organic group represented by the general formula (3) is preferably 10 mass% or more, more preferably 20 mass% or more, with respect to the mass of the entire copolymer. and more preferably 30 mass % or more, particularly preferably 40 mass % or more, more preferably 95 mass % or less, more preferably 90 mass % or less, still more preferably 88 mass % or less, and still more preferably 85 mass % or less. % or less is particularly preferred, and 80 mass% or less is most preferred.

<3.8 Polymer Blend>

The resin composition of this invention contains the polymer which has divalent trifluorene as a repeating unit. Moreover, the resin composition of this invention may contain other components other than the polymer.

The resin composition of this invention expects expression of the other effect resulting from a blend, and may contain arbitrary polymers as another component. That is, you may coexist any polymer other than the polymer which has divalent trifluorene as a repeating unit.

Here, the coexistence means that two or more types of polymers are present in the resin composition, regardless of the method, but includes a method of mixing two or more types of polymers in a solution state or a molten state, including one or more polymers and a method of advancing polymerization in a solution or a molten solution.

For example, the polymer which has a divalent organic group represented by General formula (3) as a repeating unit may be blended, and the polymer which has arbitrary repeating units may be blended. The polymer having a divalent organic group represented by the general formula (3) as a repeating unit may further have a divalent organic group other than the general formula (3) as a repeating unit, and the divalent organic group represented by the general formula (3) What has two or more types of groups as a repeating unit may be sufficient. Here, as a divalent organic group represented by General formula (3), what was illustrated preferably in a copolymer can be used.

In particular, from the viewpoint of being suitably used as a retardation film, it is preferable to coexist a blend or copolymer of a polymer or oligomer exhibiting positive refractive index anisotropy, the optical performance is good, and melt film formation or solution cast film formation can be performed Since it tends to exist, it is more preferable to make a thermoplastic resin coexist. Specific examples of coexistence include polycondensation polymers, olefin polymers, and addition polymerization polymers, and polycondensation polymers are preferred. Examples of the polycondensation polymer include polyester, polyamide, polyester carbonate, polyamide, and polyimide, and among them, polyester or polycarbonate is preferable.

More specifically, olefinic polymers such as polyethylene and polypropylene; polycarbonate having structural units derived from bisphenol A, bisphenol Z, isosorbide, etc.; polyethylene terephthalate, polybutylene terephthalate, polynaphthalene dicarboxylate Polyester, such as polycyclohexane dimethylene cyclohexane dicarboxylate and polycyclohexane dimethylene terephthalate, etc. are mentioned, You may use 2 or more types of polymers together among these.

When the resin composition of the present invention is film-molded, since it is preferable that the film is optically transparent, the polymer to be blended has a polymer having divalent trifluorene as a repeating unit and has a refractive index close to that of a polymer, but a combination having compatibility is selected It is preferable to do

<3.9 Composition of the resin composition>

From the viewpoint of expressing reverse wavelength dispersion and maintaining melt processability and mechanical strength, the total content of divalent trifluorene and divalent difluorene in the resin composition is determined by the total mass of the resin composition. It is preferably 5 mass % or more, more preferably 10 mass % or more, still more preferably 12 mass % or more, particularly preferably 15 mass % or more, most preferably 20 mass % or more, and 90 mass % It is preferable that it is less than, it is more preferable that it is 80 mass % or less, It is still more preferable that it is 70 mass % or less, It is especially preferable that it is 60 mass % or less. Moreover, from the same viewpoint, the preferable content ratio of the divalent organic group represented by the general formula (3) is preferably 10 mass% or more, more preferably 20 mass% or more, and 30 mass% or more with respect to the total mass of the resin composition. More preferably, it is more preferably 40 mass% or more, particularly preferably 95 mass% or less, more preferably 90 mass% or less, still more preferably 88 mass% or less, particularly preferably 85 mass% or less, , it is most preferably 80 mass% or less.

Moreover, the resin composition of this invention may contain two or more types of divalent organic groups represented by the said General formula (3), For example, a repeating unit derived from ISB (isosorbide) and CHDM (1,4- In the case of using a combination of repeating units derived from cyclohexanedimethanol), the content ratio is not particularly limited, but from the viewpoint of high glass transition temperature, birefringence, and water absorption, the mole fraction of the repeating units derived from ISB with respect to the resin composition, It is preferable that it is 20 mass % or more, It is more preferable that it is 30 mass % or more, It is still more preferable that it is 40 mass % or more, It is also preferable that it is 95 mass % or less, It is more preferable that it is 90 mass % or less, It is 80 mass % or less more preferably.

In the case of using a combination of the repeating unit derived from ISB and the repeating unit derived from CHDM, the content is not particularly limited, but from the viewpoint of flexibility, the mole fraction of the repeating unit derived from CHDM with respect to the resin composition is 5% by mass. It is preferable that it is more than, it is more preferable that it is 10 mass % or more, It is more preferable that it is 15 mass % or more, It is also preferable that it is 60 mass % or less, It is more preferable that it is 50 mass % or less, It is still more preferable that it is 40 mass % or less. .

When using a combination of a repeating unit derived from SPG (spiroglycol) and a repeating unit derived from CHDM, the content ratio is not particularly limited, but from the viewpoint of high glass transition temperature, birefringence, and water absorption, SPG-derived for the resin composition The mole fraction of the repeating unit is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, and preferably 95 mol% or less, more preferably 90 mol% or less, , more preferably 85 mol% or less.

In the case of using a combination of the repeating unit derived from SPG and the repeating unit derived from CHDM, the content is not particularly limited, but from the viewpoint of flexibility, the mole fraction of the repeating unit derived from CHDM with respect to the resin composition is 5% by mass. It is preferable that it is more than, it is more preferable that it is 10 mass % or more, It is more preferable that it is 15 mass % or more, It is also preferable that it is 60 mass % or less, It is more preferable that it is 50 mass % or less, It is still more preferable that it is 40 mass % or less. .

<3.10 Physical Properties>

Although the physical-property value of the resin composition of this invention is not specifically limited, It is preferable to satisfy the physical-property value illustrated below.

<3.20 Abbe number>

When the resin composition of the present invention assumes a broadband zero-birefringent material such as an imaging system optical lens, it is preferable that the Abbe number is 35 or less. In order to design an imaging system optical lens using the resin composition of this invention, the one with a lower Abbe number is preferable. Accordingly, the Abbe number is more preferably 30 or less, particularly preferably 25 or less, and is usually 15 or more.

<3.21 Orientation of the fluorene ring>

In the resin composition of the present invention, ^{the strength ratio in the stretching direction and the vertical direction of absorption of 740 cm -1} derived from the orientation of the fluorene ring is preferably 1.2 or more, more preferably 1.3 or more, still more preferably 1.4 or more. , and is usually 2.0 or less. When the resin composition of the present invention is used as a reverse wavelength dispersion film use, the higher the strength ratio in the stretching direction and the vertical direction of absorption of ^{740 cm -1 derived from the orientation of the fluorene ring is the flu contained in the resin composition.} The repeating unit having an orene ring tends to exhibit at least reverse wavelength dispersion in its ratio. In addition, the said intensity ratio can be measured by the following method.

First, a stretched film is manufactured from the resin composition of this invention, and polarization|polarized-light ATR analysis is performed. As a result of the analysis, the strength ratio in the stretching direction and vertical direction (dichroic ratio: strength in stretching direction/strength in vertical direction) of the absorption of ^{1245 cm -1 derived from the carbonyl orientation was 1.2 or more, and the main chain was} It confirms that it is oriented in an extending|stretching direction. Next, the intensity ratio of the extending|stretching direction and the perpendicular|vertical direction of the absorption of ^{740 cm -1} derived from the orientation of a fluorene ring is computed.

<3.22 The angle between the main chain and fluorene>

In the resin composition of the present invention, the specific conformation (conformation) of divalent trifluorene is a case where the Goshu conformation is not a stable conformation, and the angle between the main chain of the trans conformation and the fluorene ring is 50° or more, preferably Preferably at 60° or more, more preferably at 70° or more, it can be expected that reverse wavelength dispersion is expressed.

Energy calculation of the specific configuration (conformation) of divalent trifluorene and calculation of the angle between the fluorene ring and the main chain in the configuration can be calculated as follows.

For the software, PC Spartan Pro 1.0.5 (Windows (registered trademark) 32 bit version) manufactured by Wavefunction Co., USA is used for the AM1 method. In addition, all input values related to calculation precision, such as procedure determination values, use the default values of the software.

Here, with respect to divalent trifluorene, in the case of a polycarbonate resin composition, both ends of the repeating unit are methyl carbonated, whereas in the case of a polyester or polyester carbonate resin composition, both ends of the repeating unit are methyl carbonate. Calculate for the esterified structure.

Using the AM1 method, the energy difference between the two side chains present in each monomer is in the trans conformation and the two types of Goshu conformational conformers are calculated. Further, the angle between the main chain and the fluorene ring is calculated for the trans conformation and the Goshu conformation (the stable one of the two types of Goshu conformation).

In addition, the angle which a principal chain and a fluorene ring make is determined as follows. First, let the straight line connecting the carbon atoms of the methyl groups at both terminals be the main chain direction, and the plane passing through the carbon atoms at the 3rd, 6th, and 9th positions of fluorene is the fluorene plane. At this time, although the straight line on the fluorene plane intersecting the main chain direction exists infinitely, the straight line on the fluorene plane whose angle with the main chain direction becomes the minimum is uniquely determined. Let the angle be the angle between the main chain and the fluorene ring.

<3.23 Method of introducing organic group>

As a method of introduce|transducing the divalent organic group represented by the said General formula (3) as a repeating unit into the resin composition of this invention, from a viewpoint of transparency and uniformity of the resin composition obtained,

1. A method of copolymerizing a dihydroxy compound having trifluorene and a dihydroxy compound represented by the following formula (21) having an organic group represented by the general formula (3);

2. After transesterifying a trifluorenediester compound with a dihydroxy compound represented by the following formula (21) having an organic group represented by the general formula (3), having an organic group represented by the general formula (3) A method of introducing a dihydroxy compound represented by the following formula (21) in two steps of copolymerization;

3. A method of copolymerizing a trifluorenediaryl ester compound and a dihydroxy compound represented by the following formula (21) having an organic group represented by the general formula (3);

4. A dihydroxy compound having trifluorene, a dicarboxylic acid compound represented by the following general formula (28) having an organic group represented by the general formula (3), and an organic group represented by the general formula (3) Method of copolymerizing a dihydroxy compound represented by the following general formula (21)

This is preferable.

HO-R ²⁰ -OH (21)

HOCOR ²⁰ -COOH (28)

In formulas (21) and (28), R ²⁰ is the same as that of the general formula (3).

Here, a single type of the divalent organic group represented by the said General formula (3) may be used, and may be used combining different multiple types of organic groups. The use of a plurality of different types of organic groups in combination is achieved by using a plurality of different types of the dihydroxy compound represented by the general formula (21) and/or the dicarboxylic acid compound represented by the general formula (28). do.

<3.24 phase difference ratio>

The resin composition of the present invention, assuming retardation film use, the ratio of the retardation (Re450) measured at a wavelength of 450 nm to the retardation (Re550) measured at a wavelength of 550 nm, that is, the retardation ratio satisfies the following formula (20) it is preferable

Re450/Re550 ≤ 1.0 (20)

Here, "in the resin composition of the present invention, the retardation ratio satisfies the formula (20)" means that when molded into a stretched film, the retardation (Re450) and the wavelength 550 measured at a wavelength of 450 nm under the following measurement conditions It means that the ratio of the phase difference (Re550) measured in nm satisfies the above formula (20).

The phase difference ratio is measured by the following method. A resin composition is pressed with a hot press machine, and a film is manufactured. The film is cut out to a predetermined size, free-end uniaxial stretching is carried out, and a stretched film is produced. The retardation (Re450) in wavelength 450nm and retardation (Re550) in wavelength 550nm of this stretched film are measured using the retardation measuring apparatus (KOBRA-WPR by Oji Instruments Co., Ltd.). With respect to the stretching direction, when the retardation ratio (Re450/Re550) satisfies the above formula (20), this resin composition exhibits useful wavelength dispersion as a retardation film.

In the resin composition of the present invention, when the use of a reverse wavelength dispersion film among the retardation films is assumed, the upper limit of the retardation ratio (Re450/Re550) is preferably 1.0 or less, more preferably less than 1.0, still more preferably 0.95 or less, , more preferably 0.93 or less, and particularly preferably 0.91 or less. The lower limit of the phase difference ratio (Re450/Re550) is preferably 0 or more, more preferably 0.50 or more, still more preferably more than 0.50, still more preferably 0.70 or more, particularly preferably 0.75 or more, and 0.80 or more. The above is most preferable.

When the value of the phase difference ratio (Re450/Re550) is within the above range, the longer the wavelength, the more the phase difference is expressed, and ideal phase difference characteristics can be obtained at each wavelength in the visible region. For example, using a retardation film obtained from the resin composition of the present invention having such a wavelength dispersion as a 1/4λ plate that changes the phase of polarized light vibrating in a direction perpendicular to each other by 1/4 wavelength (90°) , a circular polarizing plate etc. can be manufactured by bonding it with a polarizing plate, and realization of the circular polarizing plate and image display apparatus excellent in blackness which has an external light reflection prevention function in all wavelengths is possible. On the other hand, when the value of the phase difference ratio (Re450/Re550) is outside the above range, discoloration by wavelength becomes large, and there is a tendency that a problem of coloring occurs in a circularly polarizing plate or an image display device.

≪Invention 3≫

Hereinafter, the oligofluorene of this invention 3, the oligofluorene composition containing it, and the resin composition obtained using this oligofluorene are demonstrated in detail.

In addition, (general) formulas (1) to (5), (4-1), (2a), (2b), (2c-1), (2c-2), (2d), (7) described below ) to (9), (11), (A), (A-1) and (B) describe each structure in the present invention 3 .

<Oligofluorene compound A1 having one 1-reactive functional group>

In the oligofluorene having one reactive functional group of the present invention (hereinafter, it may be abbreviated as "oligofluorene A1"), the carbon atoms at the 9th position of two or more fluorene units a which may have a substituent are, an oligofluorene structural unit a bonded in a chain form via an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent;

In the oligofluorene structural unit a, it has a reactive functional group represented by the following formula (A) at the carbon atom at the 9-position of the fluorene unit a at one terminal, and at the 9-position of the fluorene unit a at the other end of the oligofluorene structural unit a It has a hydrogen atom on a carbon atom.

[Formula 84]

In the formula (A), R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted C 6 to 10 carbon atoms. is an aralkyl group, and X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group. * is a bond with the carbon atom at the 9th position of the fluorene unit a.

Thus, by making a reactive functional group into a specific structure, it becomes possible to obtain industrially, and it becomes possible to use suitably as a raw material of the monomer of the resin composition for optical use.

<1.1 Alkylene group, arylene group, aralkylene group>

It is the same as described in the section of <1.1 alkylene group, arylene group, aralkylene group> of <Invention 2>.

<1.2 Substituent group which fluorene unit a may have>

It is the same as that described in the section of <1.2 Substituents which the fluorene unit a may have> of <Invention 2>.

<1.3 Reactive functional group>

The oligofluorene A1 of this invention has a reactive functional group represented by a following formula (A) in the carbon atom of 9th-position of the fluorene unit a of either terminal. The reactive functional group is not only a group that can be used for polymerization as it is, but also a contribution that can be used for a polymerization reaction through a conversion reaction.

[Formula 85]

In the formula (A), R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted C 6 to 10 carbon atoms. is an aralkyl group, and X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group. * is a bond with the carbon atom at the 9th position of the fluorene unit a.

In the above R ^a to R ^c , the specific structure of “the optionally substituted alkyl group having 1 to 10 carbon atoms” is given below, but is not limited thereto, but a methyl group, ethyl group, n-propyl group, and n-butyl group straight-chain alkyl groups such as group, n-pentyl group, n-hexyl and n-decyl; branched chains such as isopropyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 2-ethylhexyl group Alkyl group contained; Cyclic alkyl groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, are mentioned.

It is preferable that it is 4 or less, and, as for carbon number in the C1-C10 alkyl group which may be substituted, it is more preferable that it is 2 or more. If it is in this range, there exists a tendency for introduction of a reactive functional group to be easy.

Examples of the substituent that the alkyl group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkoxy group having 1 to 10 carbon atoms (eg, a methoxy group, an ethoxy group, etc.); of acyl group (eg, acetyl group, benzoyl group, etc.); acylamide group having 1 to 10 carbon atoms (eg, acetamide group, benzoylamide group, etc.); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.), 1 to 10 carbon atoms having 1 to 3 substituents selected from an acyl group (eg, an acetyl group, a benzoyl group, etc.), an acylamide group having 1 to 10 carbon atoms (eg, an acetamide group, a benzoylamide group, etc.), a nitro group, a cyano group, etc. and optionally an aryl group having 6 to 10 carbon atoms (eg, a phenyl group, a naphthyl group, etc.). Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Specific examples of the substituted alkyl group include a trifluoromethyl group, a benzyl group, a 4-methoxybenzyl group, and a methoxymethyl group.

In the above R ^a to R ^c , the specific structure of “an optionally substituted aryl group having 4 to 10 carbon atoms” is given below, but is not limited thereto, but a phenyl group, 1-naphthyl group, and 2-naphthyl group Aryl groups, such as; Heteroaryl groups, such as a 2-pyridyl group, 2-thienyl group, and 2-furyl group, are mentioned.

It is preferable that it is 8 or less, and, as for carbon number in the C4-C10 aryl group which may be substituted, it is more preferable that it is 7 or less, It is preferable that it is 4 or more, It is more preferable that it is 5 or more. If it is in this range, there exists a tendency for introduction of a reactive functional group to become easy.

Examples of the substituent which the aryl group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, an isopropyl group, etc.); Alkoxy group of 10 (eg, methoxy group, ethoxy group, etc.); Acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); Acylamide group having 1 to 10 carbon atoms (eg, acetamide group, benzoylamide) group, etc.); nitro group; cyano group etc. are mentioned. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Specific examples of the substituted aryl group include 2-methylphenyl group, 4-methylphenyl group, 4-chlorophenyl group, 3,5-dimethylphenyl group, 4-benzoylphenyl group, 4-methoxyphenyl group, 4-nitrophenyl group, 4- Cyanophenyl group, 3-trifluoromethylphenyl group, 3,4-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-methylfuryl group, etc. can be heard

In the above R ^a to R ^c , the specific structure of “an optionally substituted aralkyl group having 6 to 10 carbon atoms” is given below, but is not limited thereto, but a benzyl group, 2-phenylethyl group, p-me Toxybenzyl group etc. are mentioned.

It is preferable that it is 9 or less, and, as for carbon number in the C6-C10 aralkyl group which may be substituted, it is more preferable that it is 8 or less, It is preferable that it is 6 or more, It is more preferable that it is 7 or more. If it is in this range, there exists a tendency for introduction of a reactive functional group to become easy.

Examples of the substituent that the aralkyl group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, an isopropyl group, etc.); to 10 alkoxy group (eg, methoxy group, ethoxy group, etc.); acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); acylamide group having 1 to 10 carbon atoms (eg acetamide group, benzoyl group) Amide group etc.); Nitro group; Cyano group etc. are mentioned. Although the number of the said substituents is not specifically limited, 1-3 pieces are preferable. When there are two or more substituents, the kind of substituent may be same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture cheaply industrially.

Specific examples of the substituted aralkyl group include a benzyl group, a 2-phenylethyl group, and a p-methoxybenzyl group.

Among these, the following general formula (A-1) in which ^{R a} and R ^b are hydrogen atoms is preferable from the viewpoint of easy introduction of the reactive functional group. Further, from the viewpoint that they are inexpensive to obtain a raw material in industry, R ^c is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[Formula 86]

Moreover, in X, although the specific structure of "ester group" is not specifically limited, For example, the ester group whose terminal group is a C1-C10 organic substituent is mentioned.

Specific examples of the organic substituent having 1 to 10 carbon atoms include, but are not limited to, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-decyl group linear alkyl groups such as; alkyl groups containing branched chains such as isopropyl group, 2-methylpropyl group, 2,2-dimethylpropyl group and 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group Cyclic alkyl groups, such as a sil group and a cyclooctyl group; Aryl groups, such as a phenyl group, 1-naphthyl group, 2-naphthyl group; Heteroaryl groups, such as a 2-pyridyl group, 2-thienyl group, 2-furyl group; A benzyl group , an aralkyl group such as a 2-phenylethyl group and a p-methoxybenzyl group.

Among these, it is preferable that it is a C1-C6 alkyl group from a viewpoint that it can obtain industrially cheaply. In this case, from the viewpoint of being easy to hydrolyze during synthesis and easy to produce carboxylic acid, it is preferable that carbon number is 2 or more, and by removing low-boiling alcohol generated by transesterification with a dihydroxy compound, poly From a viewpoint of being able to synthesize|combine ester and polyester carbonate efficiently, it is preferable that it is 4 or less, and it is more preferable that it is 2 or less. A particularly preferable substituent is an ethyl group.

On the other hand, in the case of an aryl group having 6 to 8 carbon atoms, since the transesterification reaction proceeds easily, the aryl ester compound, the dihydroxy compound, and the diester carbonate are added to the reactor in a batch to form a preferred polymer, polyester carbonate. Since it can synthesize|combine in one step, it is preferable. In particular, a phenyl group having a small molecular weight and capable of being distilled off as phenol after the synthesis of polyester carbonate is particularly preferable. Moreover, in the case of an aryl group, it is preferable to use the diaryl carbonates mentioned later as a diester carbonate from a reactive viewpoint at the time of polymerization, and from a viewpoint that a by-product can be easily removed, the aryl group in the ester group , it is more preferable that the aryl groups in the diaryl carbonates are the same.

Moreover, an ester group can be converted into alcohol useful as a raw material of polycarbonate or polyester by reducing.

Although the specific structure of the "amide group" for X is not particularly limited, for example, (i) a primary amide group having two hydrogen atoms at the nitrogen atom, (ii) a hydrogen atom at the nitrogen atom and 1 to 10 carbon atoms a secondary amide group having an organic substituent of (iii) a tertiary amide group each independently having two organic substituents having 1 to 10 carbon atoms on the nitrogen atom. As a C1-C10 organic substituent, what was illustrated as a C1-C10 organic substituent in "ester group" can be used preferably.

By reducing the amide group, it becomes an "amino group" and can be used as a raw material for polyamide or polyimide. Among these, reduction is easy, and a primary amide group and a secondary amide group are preferable from a viewpoint of the reactivity of the amino group after reduction, and it is more preferable that it is a primary amide group.

X is preferably an ester group or a carboxyl group, more preferably a methyl ester group, an ethyl ester group, a phenyl ester group, or a carboxyl group from the viewpoint of being able to use it as it is as a raw material for polyester or polyester carbonate.

<1.4 Specific Structure>

As oligofluorene A1 of this invention, specifically, what is represented by the following general formula (1) can be used preferably.

[Formula 87]

In formula (1),

R ³ is each independently a direct bond or a C1-C4 alkylene group which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, a substituent a vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms;

X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group.

n represents the integer value of 1-5.

In the formula (1), as R ³ and R ⁴ to R ⁹ , those exemplified in the group of the aforementioned <Invention 1> can be preferably used.

<1.5 Specific examples of oligofluorene A1 having one reactive functional group>

Specific examples of the oligofluorene A1 of the present invention include structures as shown in the following group [E].

[Formula 88]

[Formula 89]

<1.6 Physical properties of oligofluorene A1 having one reactive functional group>

Although the physical property value of oligofluorene A1 of this invention is not specifically limited, It is preferable that it is what satisfy|fills the physical property value illustrated below.

It is preferable that the chlorine content rate in oligofluorene A1 of this invention is 100 mass ppm or less in Cl conversion mass. Furthermore, it is preferable that it is 10 mass ppm or less. When the content of the chlorine component is high, the chlorine component is also included in a large amount in the monomer obtained by using the oligofluorene A1 as a raw material, the catalyst used for the polymerization reaction is deactivated, and the polymerization does not proceed to the desired molecular weight, or the reaction This destabilization may lead to deterioration of productivity. Moreover, a chlorine component may remain|survive also in the obtained polymer, and there exists a possibility of reducing the thermal stability of a polymer.

In the oligofluorene A1 of the present invention, in the presence of a base, formaldehydes are reacted with fluorenes to carry out a crosslinking reaction; Group 2 metals may be contained, and their content is preferably 500 mass ppm or less, more preferably 200 mass ppm or less, still more preferably 50 mass ppm or less, particularly preferably 10 mass ppm or less. is below. When there are many metal components, a large amount of a metal component is contained also in the monomer obtained using oligofluorene A1 as a raw material, and when processing a polymerization reaction or resin, there exists a possibility that a polymer may become easy to color. Moreover, there exists a possibility that the metal component contained may show a catalytic action or a catalyst deactivation action, and superposition|polymerization may become unstable.

Transition metals such as titanium, copper and iron resulting from the step of transesterifying the oligofluorene A1 of the present invention, particularly, in the oligofluorene monoaryl ester, in the presence of a transesterification catalyst, diaryl carbonates act upon it. However, it contains metals of Group 1 of the long-period periodic table such as sodium and potassium, metals of Group 2 such as magnesium and calcium, Group 12 metals such as zinc and cadmium, and Group 14 metals such as tin There is a possibility that the content thereof is preferably 500 mass ppm or less, more preferably 200 mass ppm or less, still more preferably 50 mass ppm or less, and particularly preferably 10 mass ppm or less. When there are many metal components, a metal component is contained abundantly also in the monomer obtained by oligofluorene as a raw material, and when processing a polymerization reaction or resin, there exists a possibility that a polymer may become easy to color. Moreover, there exists a possibility that the metal component contained may show a catalytic action or a catalyst deactivation action, and superposition|polymerization may become unstable.

As for the oligofluorene A1 of this invention, it is preferable that the color tone of a 10 mass % tetrahydrofuran solution is 50 or less. Furthermore, it is preferable that it is 10 or less. Oligofluorene A1 has an absorption edge extending to a region close to visible light, and tends to be colored when exposed to high temperatures due to polymerization or resin processing. In order to obtain a polymer having a good color, it is preferable that the monomer used for the polymerization reaction has as little coloration as possible, and from this point of view, it is preferred that the monomer raw material oligofluorene A1 has as little coloration as possible. Since a color tone is proportional to a density|concentration, it may be a value measured at different density|concentrations and normalized to 10 mass % density|concentration. Here, the color tone (APHA value) of oligofluorene A1 is in accordance with JIS-K0071-1 (1998), a solution prepared by diluting a chromaticity standard solution (1000 degrees) manufactured by Kishida Chemical Co., Ltd. and oligofluorene A1 have an inner diameter of 20 It can measure by putting it into a mm colorimetric tube and comparing.

It is preferable that the 5% weight loss temperature in thermogravimetry is 230 degreeC or more, and, as for oligofluorene A1 of this invention, it is more preferable that it is 250 degreeC or more. Furthermore, it is especially preferable that it is 270 degreeC or more. Fluorene has a very electron-rich structure, and the reactivity of the substituent bonded to the fluorene ring is high, and thermal decomposition tends to occur. If a monomer having a low thermal decomposition temperature is used in the polymerization reaction, thermal decomposition occurs during polymerization, polymerization does not proceed to a desired molecular weight, or there is a risk that the resulting polymer may be colored. It is preferable that the temperature is high.

<1.7 Method for producing oligofluorene A1 having one reactive functional group>

Although it does not specifically limit about the manufacturing method of oligofluorene A1 of this invention, For example, in the presence of a base, the oligofluorene represented by following formula (3) is an olefin which has an electron withdrawing group represented by following formula (4) and the method of manufacturing oligofluorene A1 represented by following formula (1) by making it react is mentioned.

[Formula 90]

In the formula, R ³ is each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, a substituent a vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms;

X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group.

n represents the integer value of 1-5.

In the formula (3) and ^{(4), R 3 ~ R} 9, R a ~ R c, X and n as is, R ³ ~ in the formula ^{(1) R 9, R a} ~ R c, X and those exemplified as n can be preferably used.

<1.7.1 Olefins having an electron-withdrawing group>

Examples of the olefin having an electron-withdrawing group represented by the formula (4) include methyl acrylate, ethyl acrylate, phenyl acrylate, allyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 1 Acrylic acid esters such as ,4-cyclohexanedimethanol monoacrylate, methyl methacrylate, ethyl methacrylate, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, 2-hydroxy methacrylate Methacrylic acid esters such as ethyl, α-substituted unsaturated esters such as methyl 2-ethyl acrylate and 2-phenyl methyl acrylate, β-substituted unsaturated esters such as methyl cinnamate, ethyl cinnamate, methyl crotonate, and ethyl crotonate , conjugated nitroolefins such as β-nitrostyrene, α,β-unsaturated nitriles such as acrylonitrile, and α,β-unsaturated aldehydes such as acrolein, methacrolein and crotonaldehyde. Among them, an unsaturated carboxylic acid ester represented by the following general formula (4-1) into which a reactive functional group can be introduced directly.

[Formula 91]

( ^{wherein, R c} is the same as ^{R c} in the formula (4), ^{and R g} represents an organic substituent having 1 to 10 carbon atoms.) is preferred. Here, with an organic substituent having 1 to 10 carbon atoms of R ^g can be preferably used in the exemplified as the organic substituent having 1 to 10 carbon atoms in the "ester group".

Among the unsaturated carboxylic acids represented by the general formula (4-1), acrylic acid esters, methacrylic acid esters or α-substituted unsaturated esters are more preferable, and R ^c is a hydrogen atom or a methyl group acrylic acid esters or methacrylic acid esters Acid esters are more preferable from the viewpoints of reaction rate and reaction selectivity. As for R ^g , smaller ones are industrially inexpensive, and distillation purification is also easy, and since the reactivity is high, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate, or phenyl methacrylate is particularly desirable.

On the other hand, the unsaturated carboxylic acid ester represented by Formula (4-1) is a hydroxyalkyl group such as 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate group. In the case of having esters, since polyester carbonate and raw materials for polyester can be obtained in one step, it is particularly preferable.

Although two or more types of olefins having an electron-withdrawing group may be used, it is preferable to use one type of olefins having an electron-withdrawing group from the viewpoint of the simplicity of purification.

Although it does not specifically limit about the usage-amount of the olefin which has an electron-withdrawing group, From a viewpoint of selectively obtaining a mono adduct, Preferably it is 0.1 equivalent or more, More preferably, 0.3 equivalent or more, More preferably, it is 0.5 equivalent or more, Especially Preferably it is 0.7 equivalent or more, More preferably, it is 2.0 equivalent or less, More preferably, it is 1.8 equivalent or less, More preferably, it is 1.5 equivalent or less, Especially preferably, it is 1.2 equivalent or less.

<1.7.2 base>

Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide; carbonates of alkali metals such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate; magnesium carbonate; calcium carbonate; of alkaline earth metal carbonates, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate and potassium phosphate, organic lithium salts such as n-butyllithium and tert-butyllithium, sodium methoxide, sodium ethoxide, potassium tert-butoxy Alkoxide salts of alkali metals such as seed, alkali metal hydrides such as sodium hydride and potassium hydride, tertiary amines such as triethylamine and diazabicycloundecene, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl Quaternary ammonium hydroxides, such as trimethylammonium hydroxide, are used. These may be used individually by 1 type, and may use 2 or more types together.

When R<^3> is a methylene group and when it is other than that, there exists a tendency for the reactivity of the oligofluorene represented by Formula (3) to have a big difference. Therefore, the case where R ³ is a methylene group and the case other than that are described separately.

When R ³ is a methylene group, the oligofluorene represented by Formula (3) undergoes a decomposition reaction easily in a solvent in the presence of a base. Therefore, since side reactions, such as a decomposition reaction, can be suppressed when reaction is performed in the two-layer system of an organic layer and an aqueous layer, it is preferable to use a water-soluble inorganic base. Among them, an alkali metal hydroxide is preferable from the viewpoint of cost and reactivity, and particularly sodium hydroxide or potassium hydroxide is more preferable.

In addition, the concentration of the aqueous solution is usually 5 wt/wt% or more, preferably 10 wt/wt% or more, since, when a particularly preferable aqueous sodium hydroxide solution is used, the reaction rate decreases significantly when the concentration is soft; More preferably, it is particularly preferable to use an aqueous solution of 25 wt/wt% or more.

When R ³ is other than a methylene group, the reaction proceeds even in a two-layer system of an organic layer and an aqueous layer, but when the reaction is carried out using an organic base dissolved in the organic layer, the reaction proceeds rapidly, so it is better to use an organic base desirable. Among these, preferably, it is an alkali metal alkoxide which has sufficient basicity in this reaction, More preferably, they are industrially cheap sodium methoxide or sodium ethoxide. Here, a powdery thing may be used for the alkoxide of an alkali metal, and liquid things, such as an alcohol solution, may be used for it. Moreover, you may prepare it by making an alkali metal and alcohol react.

When R ³ is a methylene group, the amount of the base used is not particularly limited with respect to the oligofluorene represented by formula (3) as a raw material, but if the amount used is too large, the purification load after stirring or reaction may increase, When an aqueous sodium hydroxide solution of 25 wt/wt% or more, which is a particularly preferable base, is used, usually 20 times the volume or less, preferably 10 times the volume or less, more preferably, with respect to the oligofluorene represented by the formula (3). It is less than 5 times the volume. When there is too little amount of a base, since reaction rate will fall remarkably, normally, a base is 0.2 times volume amount or more with respect to the oligofluorene represented by Formula (3) which is a raw material. Preferably it is 0.5 volume volume or more, More preferably, it is 1 volume volume or more.

When R ³ is other than a methylene group, the amount of the base used is not particularly limited with respect to the oligofluorene represented by the formula (3) as the raw material, but if the amount used is too large, the purification load after stirring or reaction may increase. Therefore, when sodium methoxide or sodium ethoxide, which are particularly preferred bases, is used, usually 5 times mole or less, preferably 2 times mole or less, more preferably 1 mole or less relative to the oligofluorene represented by the formula (3). It is fold mole or less, Especially preferably, it is 0.5 fold mole or less. When there is too little amount of a base, since reaction rate will fall remarkably, normally, a base is 0.005 times mole or more with respect to the oligofluorene represented by Formula (3) which is a raw material. Preferably it is 0.01 times mole or more, More preferably, it is 0.05 times mole or more, Especially preferably, it is 0.1 times mole or more.

<1.7.3 Phase Transfer Catalyst>

When carrying out the reaction in a two-layer system of an organic layer and an aqueous layer, it is preferable to use a phase transfer catalyst in order to increase the reaction rate.

Examples of the phase transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, benzyltrimethylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium iodine, acetyltrimethylammonium bromide, benzyl Halides of quaternary ammonium salts such as triethylammonium chloride (excluding fluorine), N,N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodine, N-butyl-N-methylpyrrolidinium Halides of quaternary pyrrolidinium salts such as bromide, N-benzyl-N-methylpyrrolidinium chloride and N-ethyl-N-methylpyrrolidinium bromide (excluding fluorine), N-butyl-N-methylmorphol Halides of quaternary morpholinium salts such as nium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide (excluding fluorine), N-methyl-N-benzylpipe Lidinium chloride, N-methyl-N-benzylpiperidinium bromide, N,N-dimethylpiperidinium iodine, N-methyl-N-ethylpiperidinium acetate, N-methyl-N-ethylpiperidinium iodine, etc. halides of quaternary piperidinium salts (excluding fluorine), crown ethers, and the like. Preferably it is a quaternary ammonium salt, More preferably, it is benzyl trimethyl ammonium chloride, or benzyl triethyl ammonium chloride. These may be used individually by 1 type, and may use 2 or more types together.

When the amount of the phase transfer catalyst used is too large with respect to the oligofluorene represented by the formula (3) as a raw material, the progress of side reactions such as hydrolysis of esters and successive Michael reaction tends to become remarkable, and also from the viewpoint of cost. , is usually 5 times mole or less, preferably 2 times mole or less, more preferably 1 times mole or less with respect to the oligofluorene represented by the formula (3). When the amount of the phase transfer catalyst used is too small, the reaction rate tends to decrease remarkably, so the amount of the phase transfer catalyst used is usually 0.01 times mole or more with respect to the oligofluorene of the raw material. Preferably it is 0.1 times mole or more, More preferably, it is 0.5 times mole or more.

<1.7.4 Solvent>

It is preferable to perform reaction of the olefin which has an electron-withdrawing group represented by said Formula (4) using a solvent.

Specifically, the usable solvent is acetonitrile, propionitrile, etc. as the alkylnitrile solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. as the ketone solvent, and methyl acetate and acetic acid as the ester solvent. Linear esters such as ethyl, propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, 3-methoxymethylpropionate, 3-ethoxymethylpropionate, methyl lactate, and ethyl lactate; γ- Cyclic esters such as butyrolactone and caprolactone; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol-1-monomethyl ether acetate, propylene glycol-1-mono Ether esters, such as ethyl ether acetate, etc. As an ether solvent, diethyl ether, tetrahydrofuran, 1, 4- dioxane, methylcyclopentyl ether, tert-butyl methyl ether, etc. As a halogen-type solvent, 1 ,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, etc., halogen-based aromatic hydrocarbons, such as chlorobenzene, 1,2-dichlorobenzene, and amide solvents, N, Examples of sulfoxide solvents such as N-dimethylformamide and N,N-dimethylacetamide include dimethyl sulfoxide and sulfolane, and examples of cyclic aliphatic hydrocarbons include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Monocyclic aliphatic hydrocarbons; Methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, and isopropyl derivatives thereof. Cyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc.; decalin, etc. Polycyclic aliphatic hydrocarbons; Acyclic aliphatic hydrocarbons and aromatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane Examples of the aromatic heterocyclic ring include toluene, p-xylene, o-xylene, m-xylene, and the like. Examples of the alcohol-based solvent include methanol, ethanol, isopropanol, n-butanol, tert-butanol, hexanol, octanol, and cyclohexanol.

It turns out that when R<^3> is a methylene group, there exists a tendency which can suppress side reactions, such as a decomposition reaction of the oligofluorene represented by Formula (3), by using water and the solvent which phase-separates. Moreover, when the solvent which dissolves well the oligofluorene represented by Formula (3) as a raw material is used, since advancing of reaction tends to become favorable, the solubility of the oligofluorene represented by Formula (3) as a raw material is 0.5 mass % or more of the solvent is preferably used, more preferably 1.0 mass% or more, and particularly preferably 1.5 mass% or more of the solvent. Specifically, a halogen-based aliphatic hydrocarbon, a halogen-based aromatic hydrocarbon, an aromatic hydrocarbon, or an ether-based solvent is preferable, and dichloromethane, chlorobenzene, chloroform, 1,2-dichlorobenzene, tetrahydrofuran, and 1,4-dioxane are preferable. , or methylcyclopentyl ether is particularly preferred.

On the other hand, when R ³ is a group other than a methylene group, it can be seen that the solubility of the organic base and the oligofluorene represented by the formula (3) tends to greatly affect the reaction rate, and a constant value to ensure the solubility It is preferable to use a solvent having a dielectric constant equal to or higher than that of the solvent. As a solvent which readily dissolves the organic base and the oligofluorene represented by the formula (3), an aromatic heterocyclic ring, an alkylnitrile solvent, an amide solvent, or a sulfoxide solvent is preferable, and pyridine, acetonitrile, N,N- Particular preference is given to dimethylformamide, N,N,-dimethylacetamide, dimethylsulfoxide and sulfolane.

The said solvent may be used individually by 1 type, and may mix and use 2 or more types.

The amount of the solvent used is not particularly limited in the upper limit, but considering the production efficiency of the target product per reactor, it is usually 20 times the volume of the oligofluorene represented by the formula (3) as the raw material, preferably 15 times the volume, More preferably, an amount that is ten times the volume is used. On the other hand, when the amount of the solvent used is too small, the solubility of the reagent worsens, stirring becomes difficult, and the progress of the reaction becomes slow. amount, preferably in an amount that is two times the volume, more preferably four times the volume.

<1.7.5 Reaction Format>

The reaction format may be a batch-type reaction, a flow-through reaction, or a combination thereof, and in particular, the format can be adopted without limitation.

In the case of batch type, when the reaction reagent is introduced into the reactor, when an olefin having an electron-withdrawing group is added as a batch at the start of the reaction, since the olefin having an electron-withdrawing group is present in a high concentration, the polymerization reaction of the side reaction is easy to proceed Therefore, after adding the oligofluorene represented by Formula (3) as a raw material, a phase transfer catalyst, a solvent, and a base, it is preferable to sequentially add the olefin which has an electron withdrawing group little by little.

<1.7.6 Reaction conditions>

When the temperature is too low, a sufficient reaction rate cannot be obtained, whereas when the temperature is too high, the polymerization reaction of the olefin having an electron-withdrawing group tends to proceed easily, so temperature control is very important. Therefore, as a reaction temperature, specifically, normally, a minimum is 0 degreeC, Preferably it is 10 degreeC, More preferably, it implements at 15 degreeC. On the other hand, the upper limit is usually carried out at 40°C, preferably at 30°C, more preferably at 20°C.

As for the general reaction time, the lower limit is usually 2 hours, preferably 4 hours, more preferably 6 hours, and the upper limit is not particularly limited, but usually 30 hours, preferably 20 hours, more preferably 10 hours. It's time.

<1.7.7 Separation and purification of target substances>

After completion of the reaction, the target product, oligofluorene A1 represented by the formula (1), is a method of concentrating the solvent after removing the by-produced metal halide and the remaining inorganic base from the reaction solution by filtration, or a poor solvent of the target product It can be isolated by employing a method of adding oligofluorene A1 represented by the above formula (1), which is a target product, by precipitating it.

Moreover, you may add and extract acidic water and the solvent in which the oligofluorene A1 represented by said Formula (1) which is a target object is soluble to a reaction liquid after completion|finish of reaction. The target substance extracted with the solvent can be isolated by a method of concentrating the solvent, a method of adding a poor solvent, or the like.

The solvent that can be used in the extraction may be any solvent that dissolves the oligofluorene A1 represented by the above formula (1) as the target substance, and is not particularly limited, but aromatic hydrocarbon compounds such as toluene and xylene; 1 type, or 2 or more types, such as a solvent, are used suitably.

In the oligofluorene A1 represented by Formula (1) obtained here, when X is an ester group, it can be used as a precursor of polyester or a polyester carbonate raw material monomer, etc., but may be used after purification. . As a purification method, a conventional purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be employ|adopted without limitation. It is also possible to dissolve the oligofluorene A1 in a suitable solvent and treat it with activated carbon. The solvent usable in that case is the same as the solvent usable at the time of extraction.

In the oligofluorene A1 represented by Formula (1) obtained here, when X is a carboxyl group, it is possible to use it as a precursor of polyester or a polyester carbonate raw material monomer as it is. Moreover, it can be converted into the oligofluorene whose X is an ester group by esterification reaction.

In the oligofluorene A1 represented by Formula (1) obtained here, when X is a nitro group or a cyano group, hydrogenation by a method such as palladium carbon in a hydrogen atmosphere, or hydride reduction with a reducing agent such as lithium aluminum hydride Thus, an oligofluorene having an amino group can be produced. Moreover, when X is a cyano group, it can convert into the oligofluorene of which X is an ester group by methods, such as the specification of US Patent 3280169 and US 3324084 specification.

<Oligofluorene compound A2 having two different reactive functional groups>

In the oligofluorene having two different reactive functional groups of the present invention (hereinafter, it may be abbreviated as "oligofluorene A2"), the carbon atoms at the 9th position of two or more fluorene units a which may have a substituent are An oligofluorene comprising an oligofluorene structural unit a bonded in a chain form via an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent,

It has a reactive functional group represented by the following formula (A) at the carbon atom at the 9-position of the fluorene unit a at one terminal of the oligofluorene structural unit a, and the carbon atom at the 9-position of the fluorene unit a at the other end of the oligofluorene structural unit a It is an oligofluorene characterized in that it has an optional reactive functional group different from the reactive functional group.

[Formula 92]

In the formula (A), R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted C 6 to 10 carbon atoms. is an aralkyl group, and X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group. * is a bond with the carbon atom at the 9th position of the fluorene unit a.

As the alkylene group, arylene group, and aralkylene group bonding the fluorene unit a, those exemplified in <1.1 alkylene group, arylene group, aralkylene group> can be preferably employed, respectively.

Similarly, as the substituent which the fluorene unit a may have, those exemplified in <1.2 Substituents which the fluorene unit a may have> are preferably employable.

^{Similarly, as R a} to R ^c and X in the formula (A), those exemplified in <1.3 reactive functional group> can be preferably employed, respectively.

<2.1 Optional Reactive Functional Group>

As described above, the oligofluorene A2 of the present invention has a reactive functional group represented by the formula (A) at the carbon atom at position 9 of the fluorene unit a at one terminal, and a fluorene unit a at the other terminal. It has an arbitrary reactive functional group different from that reactive functional group at the carbon atom of 9th position.

Although it does not specifically limit about said arbitrary reactive functional group, The thing which does not satisfy|fill the prescription|regulation of Formula (A), Moreover, although the prescription|regulation of Formula (A) is satisfied, it may not be the same as one reactive functional group.

In this way, when one oligofluorene has two different reactive functional groups, there exists a tendency that the specific physical property derived from two types of reactive functional groups can be easily provided to resin.

Specific structures of the optional reactive functional group may be exemplified below, but are not limited thereto, but are not limited thereto, but hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, hydroxybutyl group, 2,2-dimethyl- 3-hydroxypropyl group, 2-methoxymethyl-2-methylpropylene group, 4-hydroxyphenyl group, 4-hydroxy-3-methylphenyl group, 4-(2-hydroxyethoxy)phenyl group, (4- Hydroxyl groups such as (hydroxymethyl)cyclohexan-1-yl)methyl group; methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, ethoxycarbonylmethyl group, 2-(ethoxycarbonyl)ethyl group, 2-( Methoxycarbonyl)ethyl group, 2-(phenoxycarbonyl)ethyl group, 2-methyl-2-(ethoxycarbonyl)ethyl group, 2-methyl-2-(methoxycarbonyl)ethyl group, 2-methyl-2 Ester groups such as -(phenoxycarbonyl)ethyl group and 2-(methoxycarbonyl)propyl group; 2-hydroxyethoxycarbonyl group, 2-(2-hydroxyethoxy)carbonylethyl group, 2-methyl- 2-(2-hydroxyethoxy)carbonylethyl group, 2-(2-hydroxyethoxy)carbonylpropyl group, 2-(4-hydroxybutoxy)carbonylethyl group, 2-methyl-2-( 4-hydroxybutoxy)carbonylethyl group, 2-[[4-(hydroxymethyl)cyclohexan-1-yl]methoxy]carbonylethyl group, 2-methyl-2-[[4-(hydroxymethyl) ) hydroxyester groups such as cyclohexan-1-yl]methoxy]carbonylethyl group; carboxyl groups such as carboxyl group, carboxymethyl group, 2-carboxyethyl group, and 2-methyl-2-carboxylethyl group; aminomethyl group, 2 -Amino groups such as aminoethyl group and 3-aminopropyl group; acryloyloxymethyl group, methacryloyloxymethyl group, 2-(acryloyloxy)ethyl group, 2-(methacryloyloxy)ethyl group, 3-( Acryl groups such as acryloyloxy)propyl group and 3-(methacryloyloxy)propyl group; 2,3-epoxypropyl group, 2,3-epoxypropoxymethyl group, 2-(2,3-epoxypro group) Epoxy groups, such as epoxy) ethyl group, etc. are mentioned.

In addition, although the oligofluorene A2 of the present invention can be used as a raw material for a polymer having a divalent oligofluorene as a repeating unit, it is preferable that only two reactive functional groups are present, and for producing various resin compositions As polymerization conditions, it is preferable that a substituent acting as a polymerization-reactive group is not contained.

Among these, a preferable combination of the reactive functional group represented by the formula (A) and the other reactive functional group is that polyester can be produced from one type of oligofluorene compound, so that the formula (A) is an ester group, and the other A reactive functional group is a combination of a hydroxyl group, Formula (A) is a carboxyl group, the other reactive functional group is a combination of a hydroxyl group, and Formula (A) is an ester group, and the other reactive functional group is a combination of a hydroxyester group can be heard In addition, the ester group, hydroxyl group, carboxyl group, and hydroxyester group in this paragraph have the same meaning as the ester group, hydroxyl group, carboxyl group, and hydroxyester group which are specific structures of the reactive functional group illustrated in the previous paragraph. .

<2.2 Specific Structure>

As oligofluorene A2 of this invention, specifically, what is represented by the following general formula (2) can be used preferably.

[Formula 93]

In Formula (2), R<^3> is a C1-C4 alkylene group which may each independently have a direct bond or a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, a substituent a vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is a direct bond, optionally substituted alkylene group having 1 to 10 carbon atoms, optionally substituted arylene group having 4 to 10 carbon atoms, or optionally substituted aralkylene group having 6 to 10 carbon atoms;

or two or more groups selected from the group consisting of an optionally substituted C1-C10 alkylene group, an optionally substituted C4-C10 arylene group, and optionally substituted C6-C10 aralkylene group, an oxygen atom; It is an optionally substituted sulfur atom, an optionally substituted nitrogen atom, or a group linked to a carbonyl group.

R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms;

X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group.

A is a hydroxyl group, an amino group, an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group.

n represents the integer value of 1-5.

In the formula (2), R ³ a, there can be preferably used that exemplified as R ³ in the formula (1).

In addition, R ⁴ ~ roneun R ^9, it can be preferably used that exemplified as R ⁴ ~ R ⁹ in the formula (1).

The roneun R ~ ^a R ^c, and X, can be preferably used that exemplified as ^a R ~ R ^c and X in the formula (A).

As R ^{10 , those exemplified as the substituents α 1} and α ² in <4.1 divalent oligofluorene> described later can be preferably used.

As "ester group, amide group" in A, what was illustrated as "ester group, amide group" of X in said formula (A) can be used preferably.

In addition, the specific structure of the "amino group" in A is not particularly limited, for example, (i) a primary amino group having two hydrogen atoms in a nitrogen atom, (ii) a hydrogen atom and 1 to 10 carbon atoms in the nitrogen atom a secondary amino group having an organic substituent of (iii) a tertiary amino group each independently having two organic substituents having 1 to 10 carbon atoms on the nitrogen atom. As a C1-C10 organic substituent, what was illustrated as a C1-C10 organic substituent in the "ester group" of X of said formula (A) can be used preferably.

Among these, by using one type of oligofluorene A2 of the present invention, since polyester and polyamide can be produced, it is preferable that A is a hydroxyl group or an amino group, and from the viewpoint of easy production, it is a hydroxyl group more preferably.

<2.3 Specific examples of oligofluorene A2 having two different reactive functional groups>

Specific examples of the oligofluorene A2 of the present invention include structures as shown in the following group [F].

[Formula 94]

[Formula 95]

<2.4 Physical properties of oligofluorene A2 having two different reactive functional groups>

It is the same as that described in the section of <1.6 Physical properties of oligofluorene A1 having one reactive functional group>.

<2.5 Manufacturing method of oligofluorene A2 having two different reactive functional groups>

Although it does not specifically limit about the manufacturing method of the oligofluorene A2 of this invention, For example, by making the oligofluorene represented by said Formula (1), and the compound which has a spinneret react, the oligo represented by said Formula (2) The method of manufacturing fluorene A2 is mentioned.

[Formula 96]

Hereinafter, the manufacturing method of the oligofluorene A2 represented by the said Formula (2) is divided into manufacturing method A, manufacturing method B, manufacturing method C, and manufacturing method D for each kind of the compound which has electrophilicity, and is described.

<2.5.1 Manufacturing method A: Manufacturing method by addition of formaldehydes>

An oligofluorene represented by the following formula (2a) having a hydroxymethyl group as a reactive functional group is prepared from an oligofluorene A1 represented by the following formula (1) and formaldehyde in the presence of a base according to the reaction represented by the production method A can do.

[Formula 97]

In the formula (2a), R ³ to R ⁹ , R ^a to R ^c , X and n are the same as in the formula (1).

<2.5.1.1 Formaldehydes>

Formaldehydes used in Production Method A are not particularly limited as long as they are substances capable of supplying formaldehyde to the reaction system, and gaseous formaldehyde, aqueous formaldehyde solution, paraformaldehyde obtained by polymerization of formaldehyde, trioxane, etc. are mentioned. . Among these, it is industrially inexpensive to use paraformaldehyde, and since it is a powder form, operability is easy and it is especially preferable from the point which enables accurate weighing.

The amount of formaldehyde used is not particularly limited with respect to the raw material oligofluorene A1, but if the amount used is too large, the purification load after the reaction tends to increase, so usually 10 times moles relative to the oligofluorene A1. Below, Preferably it is 5 times mole or less, More preferably, it is 3 times mole or less. Since the lower limit is 1 mole by mole with respect to the raw material, it is usually 1 mole or more. In order to speed up the progress of the reaction and not to leave raw materials or intermediates, there is no problem in using formaldehydes somewhat excessively with respect to the raw material oligofluorene A1. In that case, the preferable usage-amount of formaldehyde is 1.1 times mole or more with respect to the oligofluorene A1 of a raw material, More preferably, it is 1.2 times mole or more.

<2.5.1.2 base>

Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide; carbonates of alkali metals such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate; magnesium carbonate; calcium carbonate; of alkaline earth metal carbonates, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate and potassium phosphate, organic lithium salts such as n-butyllithium and tert-butyllithium, sodium methoxide, sodium ethoxide, potassium tert-butoxy Alkoxide salts of alkali metals such as seed, alkali metal hydrides such as sodium hydride and potassium hydride, tertiary amines such as triethylamine and diazabicycloundecene, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, etc. quaternary ammonium hydroxide and the like are used. These may be used individually by 1 type, and may use 2 or more types together.

Among these, preferably, it is an alkali metal alkoxide which has sufficient basicity in this reaction, More preferably, they are industrially cheap sodium methoxide or sodium ethoxide. Here, a powdery thing may be used for the alkoxide of an alkali metal, and liquid things, such as an alcohol solution, may be used for it. Moreover, you may prepare it by making an alkali metal and alcohol react.

There is no upper limit to the amount of the base used, but if the amount used is too large, the purification load after the reaction tends to increase. The following is good. On the other hand, when there is too little usage-amount of a base, since advancing of reaction will become slow, as a lower limit, it is 0.01 times mole or more normally with respect to oligofluorene A1 of a raw material, Preferably it is 0.05 times mole or more.

<2.5.1.3 Solvent>

It is preferable to carry out manufacturing method A using a solvent.

Specifically, the usable solvent is acetonitrile, propionitrile, etc. as the alkylnitrile solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. as the ketone solvent, and methyl acetate and acetic acid as the ester solvent. Linear esters such as ethyl, propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, 3-methoxymethylpropionate, 3-ethoxymethylpropionate, methyl lactate, and ethyl lactate; γ- Cyclic esters such as butyrolactone and caprolactone; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol-1-monomethyl ether acetate, propylene glycol-1-mono Ether esters, such as ethyl ether acetate, etc. As an ether solvent, diethyl ether, tetrahydrofuran, 1, 4- dioxane, methylcyclopentyl ether, tert-butyl methyl ether, etc. As a halogen-type solvent, 1 ,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, etc., halogen-based aromatic hydrocarbons, such as chlorobenzene, 1,2-dichlorobenzene, and amide solvents, N, N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc., as a sulfoxide solvent, dimethyl sulfoxide, sulfolane, etc., as a cyclic aliphatic hydrocarbon, cyclopentane, cyclohexane, Monocyclic aliphatic hydrocarbons such as cycloheptane and cyclooctane; methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, and 1,4 derivatives thereof. -Dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethyl Cyclohexane and the like; Polycyclic aliphatic hydrocarbons such as decalin; n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Examples of acyclic aliphatic hydrocarbons and aromatic hydrocarbons include toluene, p-xylene, o-xylene, m-xylene, etc., as an alcoholic solvent, Methanol, ethanol, isopropanol, n-butanol, tert-butanol, hexanol, octanol, cyclohexanol, etc. are mentioned.

Among them, an amide solvent or a sulfoxide solvent of a polar solvent is preferable because the solubility of the anion generated from the oligofluorene A1 is high and the progress of the reaction tends to be good, and N,N-dimethylformamide is particularly preferred.

These solvents may be used individually by 1 type, and may mix and use 2 or more types. The amount of the solvent used is not particularly limited in the upper limit, but considering the production efficiency of the target product per reactor, it is usually 10 times the volume of the raw material oligofluorene A1, preferably 7 times the volume, more preferably 4 An amount equal to the volume of the vessel is used. On the other hand, when the amount of the solvent used is too small, stirring becomes difficult and the progress of the reaction tends to be slow, so the lower limit is usually one-fold, preferably two-fold, of the raw material oligofluorene A1 by volume. A volume amount, more preferably an amount that is three times the volume amount, is used.

<2.5.1.4 Reaction format>

When carrying out the production method A, the reaction format may be a batch reaction, a flow-through reaction, or a combination thereof, and the format in particular can be adopted without limitation.

Since it is known that the decomposition reaction tends to proceed when the base is added as a batch addition at the start of the reaction, the method of introducing the reaction reagent into the reactor in the case of a batch type, oligofluorene A1 as raw materials, formaldehydes, and A method of adding the base in small portions after adding the solvent is preferred.

<2.5.1.5 Reaction conditions>

In the production method A, when the temperature is too low, a sufficient reaction rate cannot be obtained, and when the temperature is too high, it turns out that the decomposition reaction tends to proceed, and it is preferable to control the temperature. Therefore, when N,N-dimethylformamide which is an optimal solvent and sodium ethoxide which is an optimal base are used, a minimum is normally implemented at -50 degreeC and an upper limit at 30 degreeC. Specifically, when R ³ is a methylene group, the upper limit of the reaction temperature is preferably 20°C, more preferably 10°C. On the other hand, the lower limit is preferably -20°C, more preferably 0°C or higher. When R ³ is an ethylene group, the upper limit of the reaction temperature is preferably 25°C, more preferably 20°C. The lower limit is preferably 0°C, more preferably 10°C or higher.

<2.5.1.6 Separation and purification of target substances>

After completion of the reaction, the target product, oligofluorene represented by formula (2a), can be isolated by adding the reaction solution to acidic water such as dilute hydrochloric acid, or adding acidic water such as dilute hydrochloric acid to the reaction solution for precipitation.

Moreover, after completion of the reaction, a solvent in which oligofluorene represented by the formula (2a) as the target product is soluble and water may be added to the reaction solution for extraction. The target substance extracted with the solvent can be isolated by a method of concentrating the solvent, a method of adding a poor solvent, or the like.

Although the oligofluorene represented by the obtained formula (2a) can be used for superposition|polymerization as it is as a polymer raw material, after refine|purifying, you may superpose|polymerize. As a purification method, a conventional purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be employ|adopted without limitation.

The presence of metal components is often a problem in polymerization reactions, and the content ratio in the monomers of metals of Groups 1 and 2 of the long-period periodic table is 500 mass ppm or less, more preferably 200 mass ppm or less, further Preferably it is 50 mass ppm or less, Especially preferably, it can be 10 mass ppm or less. In general, liquid separation operation is very effective to remove the metal component, but the oligofluorene represented by formula (2a) as the target product tends to dissolve only in highly polar solvents such as N,N-dimethylformamide and tetrahydrofuran. Therefore, the liquid separation operation performed in two steps is very difficult in many cases. On the other hand, it is difficult to sufficiently remove the mixed metal component even if the precipitate after the reaction has been stopped is subjected to a normal purification treatment such as washing with water or thermal sham washing with an optional solvent, and the precipitate contains several 100 masses. Metal components of the ppm order may remain. As a good purification method for removing the metal component, a reaction precipitate containing impurities is dissolved in a relatively highly soluble solvent such as N,N-dimethylformamide or tetrahydrofuran, and then added to water to precipitate. This is preferable as a simple and effective method for removing inorganic salts.

<2.5.2 Production method B: Production method by addition reaction of an olefin having an electron-withdrawing group>

Oligofluorene represented by the following formula (2b) is prepared from oligofluorene A1 represented by the following formula (1) and an olefin (4-2) having an electron withdrawing group different from the formula (4) in the presence of a base, It can manufacture according to the reaction represented by B.

[Formula 98]

In the formula (2b), R ³ to R ⁹ , R ^a to R ^c , X and n are the same as in the formula (1). Further, R ^a2 to R ^c2 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms; , Xa is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group. However, ^{at least any one of R a} to R ^c and X and R ^a2 to R ^c2 and Xa is not the same.

As R ^a2 to R ^c2 and Xa, those ^{exemplified as R a} to R ^c and X in the formula (A) can be preferably employed, but R ^a to R ^c and X and R ^a2 to R ^c2 and Xa , it is necessary to make at least one of them different. In particular, it is preferable that X and Xa are not the same in formula (2b) from the viewpoint of simply imparting specific physical properties derived from different reactive functional groups to the resin.

The oligofluorene represented by Formula (2b) can be manufactured according to the method of manufacturing the oligofluorene A1 represented by the said Formula (1). At this time, after producing the oligofluorene A1, after isolation and purification, it may be prepared, or after the oligofluorene represented by the formula (3) and the olefin having an electron withdrawing group represented by the formula (4) are reacted, then You may make the olefin which has an electron withdrawing group represented by Formula (4-2) react.

<2.5.3 Production method C: Production method of oligofluorene represented by Formula (2c) by alkylation and hydrolysis of oligofluorene A1)>

Oligofluorene represented by the following formula (2c) is synthesized by an alkylation reaction of oligofluorene A1 with an alkylating agent represented by formula (8) to synthesize an oligofluorene having a leaving group represented by formula (2c-1) ( It can be produced by a method passing through the step (ia)) and the subsequent hydrolysis reaction (step (iia)), and further, by the alkylation reaction of the oligofluorene A1 with the alkylating agent represented by the formula (9), the formula (2c- It can also be produced by a method such as a step of synthesizing an oligofluorene having a protecting group represented by 2) (step (ib)) and a subsequent hydrolysis reaction (step (iib)).

[Formula 99]

In the formula, R ³ to R ⁹ , R ^a to R ^c , X and n are the same as in the formula (1). R ¹⁰ is the same as ^{R 10 in} the formula (2).

In addition, Xb and Xc represent a leaving group. Examples of the leaving group include a halogen atom (excluding fluorine), a mesyl group, or a tosyl group.

T represents a protecting group. Examples of the protecting group include a methoxymethyl group, a 2-methoxyethoxymethyl group, a tetrahydropyranyl group, a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a trimethylsilyl group, or a tert-butyldimethylsilyl group.

The alkylation reaction of fluorenes is widely known, for example, 9,9-bis(haloalkyl) such as 9,9-bis(bromohexyl)fluorene or 9,9-bis(iodohexyl)fluorene Fluorene has been reported (J. Org. Chem., 2010, 75, 2714.). From these findings, by using oligofluorene A as a raw material, the synthesis|combination of the oligofluorene which has a leaving group is possible. Moreover, also regarding the hydrolysis of halogen, since many reported examples are known (Bull. Korean Chem. Soc., 2008, 29.2491.), the oligofluorene represented by Formula (2c) can be synthesize|combined by this route. .

Examples of the alkylating agent used in step (ia) include diiodomethane, 1,2-diiodoethane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,6 -diiodohexane, dibromomethane, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6- Dibromohexane, dichloromethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1-bromo-3- linear alkyldihalides such as chloropropane (excluding fluorine atoms), and branched alkyldihalides such as 2,2-dimethyl-1,3-dichloropropane (excluding fluorine atoms), 1 Aralkyl dihalides such as ,4-bis(bromomethyl)benzene and 1,3-bis(bromomethyl)benzene (excluding fluorine atoms), ethylene glycol dimesylate, ethylene glycol ditosylate, and propylene glycol Disulfonates of glycols, such as dimesylate and tetramethylene glycol dimesylate, etc. are mentioned.

Examples of the alkylating agent used in the step (ib) include protected products of haloalkyl alcohols such as 3-bromopropanol, 2-bromopropanol, and 3-chloro-2,2-dimethyl-1-propanol.

<2.5.4. Production method D: production method of oligofluorene represented by formula (2d) by alkylation of oligofluorene A1)>

The oligofluorene represented by Formula (2d) can be manufactured by the alkylation reaction of oligofluorene A1 and the alkylating agent represented by Formula (10).

[Formula 100]

In the formula (10), Xb and R ¹⁰ are the same as in the formula (8). R ²¹ is the same as ^{R g .}

In the formula (2d), R ³ to R ⁹ , R ^a to R ^c , X and n are the same as in the formula (1).

As the oligofluorene of the formula (2d), where R ¹⁰ is other than a direct bond, in the presence of a base, the oligofluorene A1 and the alkylating agent represented by the formula (10) are used in the step (ia) in <2.5.3 Production method C> Alternatively, it can be produced by carrying out an alkylation reaction in the same manner as described for (iib).

Examples of the alkylating agent used in Production Method D include methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, n-butyl chloroacetate, tert-butyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, tert-butyl bromoacetate, Methyl iodide acetate, ethyl iodide acetate, tert-butyl iodide acetate, methyl chloropropionate, ethyl chloropropionate, tert-butyl chloropropionate, methyl bromopropionate, ethyl bromopropionate, tert-butyl bromopropionate, methyl iodide propionate, iodine Alkyl haloalkanoates such as ethyl propionate and tert-butyl iodopropionate, methyl 4-chloromethylbenzoate, methyl 4-bromomethylbenzoate, ethyl 4-chloromethylbenzoate, ethyl 4-bromomethylbenzoate, and 3-chloromethylbenzoic acid Haloalkyl benzoate alkyl, such as methyl and 3-bromomethyl methyl benzoate, etc. are mentioned.

<3 Oligofluorene composition>

The oligofluorene composition of the present invention includes oligofluorene A1 (oligofluorene compound having one reactive functional group) and/or oligofluorene A2 (oligofluorene compound having two different reactive functional groups) (hereinafter, these are incorporated Therefore, it may be abbreviated as "oligofluorene A".) and the oligofluorene B mentioned later which has a different chemical structure from the oligofluorene A. In particular, from the viewpoint of controlling the polymerization rate and molecular weight of the resin, it is preferable to include oligofluorene A1, and on the other hand, from the viewpoint of easily obtaining resin properties resulting from two or more reactive functional groups, oligofluorene A2 is used. It is preferable to include

<3.1 Oligofluorene B>

In the oligofluorene B, the carbon atoms at the 9th position of two or more fluorene units b which may have a substituent are an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aral which may have a substituent. and an oligofluorene structural unit (hereinafter referred to as an oligofluorene structural unit b) bonded in a chain form via a cheylene group;

It has the same reactive functional group represented by a following formula (B) at the carbon atom of the 9th-position of the fluorene unit b of both terminals in this oligofluorene structural unit b.

[Formula 101]

In the formula (B), R ^d to R ^f are each independently a hydrogen atom, an optionally substituted C1-C10 alkyl group, an optionally substituted C4-C10 aryl group, or optionally substituted C6-C10 alkyl group. of an aralkyl group, and X ¹ is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group. * is a bond with the carbon atom at the 9th position of the fluorene unit b.

As the alkylene group, arylene group, and aralkylene group bonding the fluorene unit b, those exemplified in <1.1 alkylene group, arylene group, aralkylene group> can be preferably employed, respectively. Moreover, the group which couple|bonds the fluorene unit b may be the same as the group which couple|bonds the fluorene unit a in oligofluorene, and may differ. From a viewpoint of being able to manufacture simultaneously, the same thing is preferable.

Similarly, as the substituent which the fluorene unit a may have, those exemplified in <1.2 Substituents which the fluorene unit a may have> are preferably employable.

^{Similarly, as R d} to R ^f and X ¹ in the formula (B), those ^{exemplified as R a} to R ^c and X in <1.3 reactive functional group> can be preferably employed, respectively. In addition, R ^d to R ^f and X ¹ in the formula (B) may be the same as or different from ^{R a} to R ^{c and X in the formula (A) in the oligofluorene.} From a viewpoint of being able to manufacture simultaneously, the same thing is preferable.

<3.2 Specific structure of oligofluorene B>

As the oligofluorene B according to the present invention, specifically, those represented by the following general formula (7) can be preferably used.

[Formula 102]

In formula (7), R ¹³ is each independently a direct bond or an optionally substituted C1-C4 alkylene group;

R ¹⁴ to R ¹⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, a substituent A vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 14} to R ¹⁹ may be bonded to each other to form a ring.

R ^d to R ^f are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms;

X ¹ is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group.

n represents the integer value of 1-5.

^{As R 13} in Formula (7), what was illustrated as ^{R 3} in Formula (1) is preferably employable. ^{Similarly, as R 14} to R ¹⁹ in Formula (7), those ^{exemplified as R 4} to R ⁹ in Formula (1) can be preferably employed. The roneun R ~ ^d R ^f in the formula (7), can be preferably employed exemplified as R ~ ^a R ^c in the formula (1). In addition, as X<^1> in Formula (7), what was illustrated as X in Formula (1) is employable preferably. As n in Formula (7), what was illustrated as n in Formula (1) is employable preferably.

<3.3 Specific examples of oligofluorene B>

As a specific example of the oligofluorene B which concerns on this invention, a structure as shown to the following [G] group is mentioned.

[Formula 103]

[Formula 104]

[Formula 105]

<3.4 Content>

Although it does not specifically limit about the content of the said oligofluorene A in the oligofluorene composition of this invention, From a viewpoint of controlling the molecular weight of a polymer, it is preferable that it is 0.1 mass % or more, and it is more preferable that it is 0.5 mass % or more, It is still more preferably 1 mass % or more, and it is preferable that it is 60 mass % or less, It is more preferable that it is 50 mass % or less, It is still more preferable that it is 40 mass % or less.

Although it does not specifically limit about the content of the said oligofluorene B in the oligofluorene composition of this invention, From a viewpoint of raising the polymerization degree of a polymer, it is preferable that it is 5 mass % or more, and it is more preferable that it is 10 mass % or more, It is still more preferable that it is 15 mass % or more. Moreover, it is preferable that it is 60 mass % or less, It is more preferable that it is 50 mass % or less, It is still more preferable that it is 40 mass % or less.

Moreover, although it does not specifically limit about the content ratio of oligofluorene A and oligofluorene B contained in an oligofluorene composition, From a viewpoint of controlling the molecular weight of a polymer, oligofluorene A and oligofluorene contained in a composition The molar ratio of B (the number of moles of oligofluorene A/the number of moles of oligofluorene B) is preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.01 or more, and from the viewpoint of increasing the polymerization degree of the polymer, It is preferable that it is 0.05 or less, It is more preferable that it is 0.03 or less, It is still more preferable that it is 0.02 or less.

The number of moles of oligofluorene A or oligofluorene B contained in the oligofluorene composition can be estimated from, for example, area% of HPLC analysis using a calibration curve.

<4 resin composition>

By using the oligofluorene of the present invention, a resin composition can be prepared.

When oligofluorene A is used as oligofluorene, the resin composition which consists of a polymer which has a structure shown at the terminal by following formula (5), or contains this polymer, for example can be obtained.

[Formula 106]

In formula (5), R ³ is each independently a direct bond or an optionally substituted C1-C4 alkylene group,

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, a substituent a vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ^a to R ^c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms.

X is an ester group, an amide group, a carboxyl group, a cyano group, or a nitro group.

n represents the integer value of 1-5.

* is a bond with a linking group.

Equation ^{(5) R 3 ~ R 9} , R a ~ R c and n as are employed to fit the one exemplified as ^{R 3 ~ R 9, R a} ~ R c , and n in the formula (1) in the can do.

<4.1 Divalent Oligofluorene>

The polymer according to the resin composition of the present invention preferably has a divalent oligofluorene as a repeating unit.

In this case, the resin composition of this invention may contain the other polymer mentioned later other than the polymer which has a bivalent oligofluorene as a repeating unit, and may contain the additive etc.

Although it does not specifically limit about the method of obtaining the polymer which has a divalent oligofluorene as a repeating unit, For example, when the oligofluorene compound A2 is used as an oligofluorene, it has two or more types of coupling groups derived from a reactive functional group Furthermore, a polymer having a divalent oligofluorene as a repeating unit can be obtained. Moreover, also by using oligofluorene B, the polymer which has a bivalent oligofluorene as a repeating unit can be obtained.

The divalent oligofluorene contains two or more fluorene units which may have a substituent, and the carbon atoms at the 9th position of the fluorene unit are an alkylene group which may have a substituent, or an aryl which may have a substituent. They are linked in a chain form via a ren group or an aralkylene group which may have a substituent.

As the fluorene unit, those exemplified as the fluorene unit a of the oligofluorene A and those exemplified as the fluorene unit b of the oligofluorene B can be preferably used.

Similarly, as the alkylene group bonding the fluorene unit, those exemplified as the alkylene group bonding the fluorene unit a of oligofluorene A, and those exemplified as the alkylene group bonding the fluorene unit b of the oligofluorene B It can be used preferably.

Incidentally, as the arylene group bonding the fluorene unit, those exemplified as the arylene group bonding the fluorene unit a of the oligofluorene A, and those exemplified as the arylene group bonding the fluorene unit b of the oligofluorene B It can be used preferably.

Incidentally, the aralkylene group bonding the fluorene unit is exemplified as an aralkylene group bonding the fluorene unit a of oligofluorene A, and is illustrated as an aralkylene group bonding the fluorene unit b of the oligofluorene B One can preferably be used.

^{In the divalent oligofluorene, substituents α 1} and α ² are respectively bonded to carbon atoms at position 9 of the fluorene units positioned at both terminals among two or more fluorene units, and the substituents α ¹ and α ² are replaced with 2 It can also be used as a family flag. In this case, α ¹ and α ² may be the same or different. Further, the substituents α ¹ and α ² include a direct bond, that is, the carbon atom at the 9th position of the fluorene unit may be a divalent group.

The substituents α ¹ and α ² are not particularly limited, but a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted arral having 6 to 10 carbon atoms. At least two groups selected from the group consisting of a alkylene group or an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, and an optionally substituted aralkylene group having 6 to 10 carbon atoms; and an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom, or a group linked by a carbonyl group.

As "the optionally substituted C1-C10 alkylene group", what was illustrated as an alkylene group which couple|bonds the fluorene unit a can be used preferably. In this case, it is preferable to use the thing of carbon number 2 or more from a viewpoint of expressing reverse wavelength dispersion property. On the other hand, it is preferable to make the carbon number into 1 from a viewpoint of expressing flat dispersibility. In addition, in the case of expressing reverse wavelength dispersion, the number of carbon atoms is preferably 5 or less, and 4 or less from the viewpoint of making it easy to fix the orientation of the fluorene ring with respect to the main chain and efficiently obtaining reverse wavelength dispersion characteristics. It is more preferable, it is still more preferable that it is 3 or less, It is especially preferable that it is 2 or less. On the other hand, from the viewpoint of imparting flexibility to the resin composition, the carbon number is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more.

As "the optionally substituted arylene group having 4 to 10 carbon atoms", those exemplified as the arylene group to which the fluorene unit a is bonded can be preferably used. Similarly, as "the optionally substituted aralkylene group having 6 to 10 carbon atoms", those exemplified as the aralkylene group bonding the fluorene unit a can be preferably used.

"At least two groups selected from the group consisting of an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, and an aralkylene group having 6 to 10 carbon atoms which may be substituted are an oxygen atom; The specific structure of "the optionally substituted sulfur atom, the optionally substituted nitrogen atom, or the group linked by a carbonyl group" is given below, but is not limited thereto, but is a divalent group as shown in the following group [H].

[Formula 107]

can be heard Among these, preferably, two or more groups selected from an alkylene group, an arylene group, or an aralkylene group, which can impart flexibility while maintaining the transparency and stability of the resin composition, are linked by an oxygen atom, more preferably , which can increase the glass transition temperature of the resin composition while imparting flexibility, and is a group in which an alkylene group as shown in the following group [I] is linked by an oxygen atom.

[Formula 108]

Moreover, when setting it as these linked groups from a viewpoint of raising a fluorene ratio, it is preferable to set it as 2 or more, Moreover, it is preferable to set it as 6 or less, It is more preferable to set it as 4 or less.

Among these, ^{when at least one of the substituents α 1} and α ² is a direct bond, or when at least one of the substituents α ¹ and α ² has 2 or more carbon atoms, the fluorene ring (fluorene unit) is substantially perpendicular to the main chain In order to orientate, even if the ratio of the bivalent oligofluorene in a resin composition is small, there exists a tendency for reverse wavelength dispersion property to become easy to express. In the latter case, from the same viewpoint, ^{it is preferable that both of α 1} and α ² have 2 or more carbon atoms. On the other hand, when ^{both of the substituents α 1} and α ² are C1 (that is, a methylene group which may be substituted), the fluorene ring (fluorene unit) is not oriented substantially perpendicular to the main chain. , in order to orient with a large inclination, even if the ratio of the divalent oligofluorene in the resin composition is changed in a wide range, it tends to become flat dispersibility with a small difference in retardation in a broad band.

Among these, it is preferably a direct bond, optionally substituted alkylene group having 1 to 10 carbon atoms, optionally substituted arylene group having 4 to 10 carbon atoms, or optionally substituted alkylene group having 1 to 10 carbon atoms, which may be substituted. At least two groups selected from the group consisting of an arylene group having 4 to 10 carbon atoms and an optionally substituted aralkylene group having 6 to 10 carbon atoms are linked to an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group it's gi

More preferably, a direct bond, a linear alkylene group, an alkylene group containing a branched chain, or a linear or branched alkylene group at any two points of the alicyclic structure as shown in group [A] above An alicyclic alkylene group having a bond of Two or more groups selected from the group consisting of are groups connected by an oxygen atom.

More preferably, a direct bond, methylene group, ethylene group, n-propylene group, n-butylene group, methylmethylene group, which tends to achieve the low photoelastic modulus required for the optical film by not having an aromatic ring group, 1-methylethylene group, 2-methylethylene group, 2,2-dimethylpropylene group, 2-methoxymethyl-2-methylpropylene group, or alicyclic alkylene group as shown in the following group [J]

[Formula 109]

(The substitution positions of two bonds in each ring structure shown in the group [J] are arbitrary, and two bonds may be substituted on the same carbon.)

Even more preferably, they are a direct bond, a methylene group, an ethylene group, n-propylene group, n-butylene group, a methylmethylene group, 1-methylethylene group, 2-methylethylene group, or a 2,2-dimethylpropylene group. . Particularly preferably, they are a methylene group, an ethylene group, or an n-propylene group.

If the chain length is long, the glass transition temperature tends to be low, so a short-chain group, for example, a group having 2 or less carbon atoms is preferable. Further, since the molecular structure becomes small, the concentration (fluorene ratio) of the fluorene ring in the repeating unit tends to be high, so that desired optical properties can be efficiently expressed. Moreover, even if it is contained in an arbitrary mass with respect to the mass of the whole resin composition, it tends to be flat dispersion with small wavelength dispersion of retardation, and also has the advantage that it can be introduced in a single step and industrially inexpensively. It is preferable that there is a methylene group.

On the other hand, for the purpose of improving the mechanical strength and reliability at high temperature of the obtained film, an arylene group having 4 to 10 carbon atoms, which can increase the glass transition temperature of the resin composition, or an alkylene group having 1 to 10 carbon atoms which may be substituted and a group in which two or more groups selected from the group consisting of an arylene group having 4 to 10 carbon atoms which may be substituted are preferably linked by an oxygen atom, 1,4-phenylene group, 1,5-naphthylene group, 2,6-naph A tylene group or a divalent group as shown in the following group [H2] is more preferable.

[Formula 110]

Moreover, when applying to the retardation film which has reverse wavelength dispersion property, it is important to select ^{substituent (alpha)1} and (alpha) ^{2 suitably.} For example, a group having 1 carbon atom represented by a methylene base tends to have unexpectedly low reverse wavelength dispersion, so ^{it is preferable that α 1} and α ² are a direct bond, or that at least one of them is a group having 2 or more carbon atoms.

More preferably, a direct bond, optionally substituted C2-10 alkylene group, optionally substituted C4-C10 arylene group, or optionally substituted C1-C10 alkylene group, optionally substituted C4 At least two groups selected from the group consisting of an arylene group of to 10 and an optionally substituted aralkylene group having 6 to 10 carbon atoms are a group linked to an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom, or a carbonyl group .

More preferably, a direct bond, a linear alkylene group, an alkylene group including a branched chain, or a linear or branched alkylene group at any two points of the alicyclic structure as shown in group [A] above It consists of an alicyclic alkylene group having a bond, a phenylene group, or an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, and an optionally substituted aralkylene group having 6 to 10 carbon atoms. Two or more groups selected from the group are groups connected by an oxygen atom.

More preferably, a direct bond, ethylene group, n-propylene group, n-butylene group, methylmethylene group, 1-methylethylene group, which can achieve a low photoelastic modulus required for an optical film by not having an aromatic ring group, 2-methylethylene group, 2,2-dimethylpropylene group, 2-methoxymethyl-2-methylpropylene group, or an alicyclic alkylene group as shown in the group [J] above, or the glass transition temperature of the resin composition At least two groups selected from the group consisting of a 1,4-phenylene group, optionally substituted alkylene group having 1 to 10 carbon atoms, and optionally substituted arylene group having 4 to 10 carbon atoms, which can increase it's gi

Particularly preferably, they are a direct bond, an ethylene group, an n-propylene group, an n-butylene group, a methylmethylene group, a 1-methylethylene group, a 2-methylethylene group, or a 2,2-dimethylpropylene group.

Most preferably, it is an ethylene group or an n-propylene group. If the chain length is long, the glass transition temperature tends to be low, so a short-chain group, for example, a group having 3 or less carbon atoms is preferable. Moreover, since the molecular structure becomes small, the density|concentration (fluorene ratio) of the fluorene ring in a repeating unit can be made high, and desired optical properties can be expressed efficiently.

In addition, the substituents α ¹ and α ² are preferably the same for facilitating production.

Thus, the resin composition of this invention consists of a polymer which has a repeating unit which connected the carbon atoms at the 9th-position of two or more fluorene units b by a specific carbon-carbon bond, or by containing the polymer, fluorene There is a tendency that the optical properties derived from the ring can be obtained more effectively.

As said divalent oligofluorene, specifically, what is represented by the following general formula (11) can be used preferably.

[Formula 111]

In formula (11), R ¹ to R ³ are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, a substituent a vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

n represents the integer value of 1-5.

^{As R 1} and R ² in the formula (11), those exemplified as the substituents α ¹ and α ² can be preferably used, respectively.

In addition, the R ³ ~ R ⁹ and n in the formula (11), respectively, can be preferably used as an illustration of R ³ ~ R ⁹ and n in the formula (1).

<4.2 Polymer>

The polymer contained in the resin composition of this invention has a bivalent oligofluorene as a repeating unit. For example, the polymer in which bivalent oligofluorenes were connected by arbitrary coupling groups is mentioned. Moreover, the copolymer which has arbitrary repeating units other than bivalent oligofluorene may be sufficient as the polymer.

<4.3 Connector>

It is the same as described in the section of <3.4 coupling group> of <<Invention 2>>.

<4.4 Copolymer>

The polymer having a divalent oligofluorene as a repeating unit may be a copolymer further comprising any divalent organic group (however, except for a divalent oligofluorene) as a repeating unit. In this case, it is preferable that repeating units are what connected by the above-mentioned coupling group.

In the copolymer, the optional divalent organic group which may be used in combination with the divalent oligofluorene is the same as described in the section <3.5 copolymer> of the above <Invention 2>.

<4.5 Copolymer composition>

It is the same as described in the section of <3.7 Copolymerization composition> of <Invention 2> above.

<4.6 Composition of the resin composition>

It is the same as that described in the section of <3.9 Composition of the resin composition> of the above <Invention 2>.

≪Invention 4≫

Hereinafter, the oligofluorenediester of this invention 4 and the manufacturing method of the resin composition using the same are demonstrated in detail.

Further, (general) formulas (1), (1a), (1b), (1a-I), (1a-II), (10e), (I) to (V), (IIa) described below, (IIb) and (VI-1) describe each structure in the present invention 4;

<1 oligofluorene diester A>

The oligofluorenediester of the present invention (hereinafter, may be abbreviated as "oligofluorenediester A") contains two or more fluorene units which may have a substituent, and the 9-position of the fluorene unit is Carbon atoms are bonded to each other in a chain form via a direct bond or an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent, and the metal content is 500 mass ppm or less.

<1.1 Specific Structure>

As the oligofluorene diester of the present invention, specifically, those represented by the following general formula (1) can be preferably used.

[Formula 112]

In the formula, R ¹ to R ³ are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, a substituent a vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is an organic substituent having 1 to 10 carbon atoms.

n represents the integer value of 1-5.

In the formula (1), roneun R ¹ and R ^2, respectively, can be preferably used that exemplified in the art of the groups R ¹ and R ² of the above-described «1» invention.

Similarly, as R ³ , those exemplified in the group ^{of R 3 in} the aforementioned <Invention 1> can be preferably used.

As R ⁴ to R ⁹ , those exemplified in the group ^{of R 4} to R ^{9 in} the aforementioned <Invention 1> can be preferably used.

Moreover, as R< ¹⁰ >, what was illustrated as an organic substituent in <1.3 ester group> of <<Invention 2>> mentioned above can be used preferably.

<1.2 Metal content>

The content of the metal is preferably 400 mass ppm or less, more preferably 200 mass ppm or less, still more preferably from the viewpoint of reducing the thermal stability of the oligofluorene diester A and causing coloring. It is 100 mass ppm or less, More preferably, it is 50 mass ppm or less, Especially preferably, it is 10 mass ppm or less, Most preferably, it is 5 mass ppm or less.

The type of the metal is not particularly limited, but since the metal used as a catalyst may be mixed in the production of the oligofluorenediester, Group 1, Group 2, Group 12, and 14 of the long-period periodic table It is considered that it is at least 1 sort(s) of metal chosen from a group and a transition metal. Specifically, the Group 1 metal includes lithium, sodium, potassium, and cesium, the Group 2 metal includes magnesium, calcium, and barium, and the Group 12 metal includes zinc and cadmium. and aluminum as the group 13 metal, tin and lead as the group 14 metal, and iron, copper, titanium, zirconium, manganese, cobalt, and vanadium as the transition metal. The oligofluorenediester of this invention contains a metal normally, for example remaining the catalyst at the time of manufacture.

In the oligofluorenediester of the present invention, long-period periodic table metals such as sodium and potassium derived from a process of hydroxymethylation by reacting formaldehydes in the presence of a base, and second metals such as calcium There is a possibility that metals of the group may be contained. In addition, transition metals such as titanium, copper, iron, etc. resulting from the step of transesterification by reacting diaryl carbonates in the presence of a transesterification reaction catalyst, and long-period periodic table group 1 such as sodium and potassium; Group 2 metals, such as magnesium and calcium, Group 12 metals, such as zinc and cadmium, and Group 14 metals, such as tin, may be contained.

Among these, it is preferable that it is a transition metal from a reactive viewpoint of a transesterification reaction catalyst, It is more preferable that it is titanium or zirconium, It is more preferable that it is titanium.

As a measuring method of metal content, ICP-QMS method is mentioned, for example.

As a method of making the amount of metals within the above range, for example, conventional purification methods such as recrystallization, reprecipitation, extraction purification, filtration operations such as filter filtration, column chromatography, and the like are mentioned. Moreover, when manufacturing the oligofluorene diester A of this invention by the transesterification method, it is important to reduce the water|moisture content in a raw material, and the carboxylic acid component of an impurity.

<1.3 Manufacturing method of oligofluorene diester A>

Although it does not specifically limit about the manufacturing method of the oligofluorene of this invention, For example, it can manufacture by methods, such as manufacturing method A or manufacturing method B shown by a following formula.

[Formula 113]

Each of the structural formula wherein, R ¹ ~ R ³ are each independently, a bond, or may contain a substituent group the alkyl group of 1 to 4 carbon atoms are.

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted acyl group having 1 to 10 carbon atoms. , an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, a substituent a vinyl group having 1 to 10 carbon atoms which may have a substituent, an ethynyl group having 1 to 10 carbon atoms which may have a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring.

n represents the integer value of 1-5.

R ¹⁰ is an organic substituent having 1 to 10 carbon atoms.

<1.3.1 Recipe A>

Production method A uses fluorenes (I) as a raw material, converts it to 9-hydroxymethylfluorenes (IV), and then reacts the olefin compound (V) synthesized by dehydration with fluorenyl anion , A method for producing an oligofluorene compound (II) wherein ^{R 3 is a methylene group.} In addition, unsubstituted 9-hydroxymethylfluorene can be purchased as a reagent. From the oligofluorene compound (II) obtained here, according to the process (ii) mentioned later, an ester group can be introduce|transduced and it can be set as the oligofluorene diester (1).

For example, a method of synthesizing a mixture of oligofluorenes by anionic polymerization after converting 9-hydroxymethylfluorene into dibenzofulvene is known (J. Am. Chem. Soc., 123, 2001, 9182-9183.). With reference to these, the oligofluorene compound (II) can be produced.

<1.3.2 Recipe B>

Production method B synthesizes the oligofluorene compound (II) by carrying out a crosslinking reaction (step (i)) of fluorenes (I) as raw materials, and then introduces an ester group (step (ii)), This is a method for producing an oligofluorenediester (1).

[Formula 114]

Each of the above formula, R ¹ ~ R ¹⁰ is the same meaning as R ¹ ~ R ¹⁰ in the formula (1).

Hereinafter, the manufacturing method B is divided into the manufacturing method of the process (i) oligofluorene compound (II), and the manufacturing method of the process (ii) oligofluorene diester (1), and is described.

<1.3.3 Step (i): Manufacturing method of oligofluorene compound (II)>

[Formula 115]

In each of the above formulas, R ³ to R ⁹ and n have the same meanings as ^{R 3} to R ⁹ in the above formula (1).

Hereinafter, the manufacturing method of the oligofluorene compound (II) in the process (i) is divided into the case ^{of n and R<3> and is described.}

<1.3.3.1 When n=1, R ³ is a direct bond: 9,9': 9',9"-Method for producing terfluorenyl>

A plurality of methods for synthesizing 9,9'-bifluorenyl are known, and they can be synthesized from fluorenone or 9-bromofluorene (J. Chem. Res., 2004, 760; Tetrahedron Lett., 2007, 48, 6669.). Also, 9,9'-bifluorenyl is commercially available as a reagent.

<1.3.3.2 When n=2, R ³ is a direct bond: 9,9': 9',9"-Method for producing terfluorenyl>

The synthesis method of 9,9':9',9"-terfluorenyl is known and can be synthesized from fluorenone (Eur. J. Org. Chem. 1999, 1979-1984.).

<1.3.3.3 Step (ia): ^{Manufacturing method when R 3} is a methylene group>

The oligofluorene compound having a methylene bridge represented by the following general formula (IIa) can be produced from fluorenes (I) and formaldehydes in the presence of a base according to the reaction represented by the following formula.

[Formula 116]

Each of the above formula, R ~ ⁴ R ⁹ and n are the same meaning as R ⁴ ~ R ⁹ and n in the above formula (1).

<1.3.3.3.1 Formaldehydes>

The formaldehyde used in step (ia) is not particularly limited as long as it is a substance capable of supplying formaldehyde to the reaction system, and gaseous formaldehyde, aqueous formaldehyde solution, paraformaldehyde obtained by polymerization of formaldehyde, trioxane, etc. are mentioned. can Paraformaldehyde is more preferable from the point of view that it is industrially inexpensive, and since it is in powder form, operability is easy and accurate weighing is possible. On the other hand, since it is industrially cheap and it is liquid, from a viewpoint that there is little risk of exposure at the time of addition, formalin is more preferable.

(Definition of Theoretical Quantity)

When manufacturing the target oligofluorene compound (IIa), the theoretical amount (molar ratio) of formaldehydes with respect to the fluorenes (I) of a raw material is represented by n/(n+1).

(The reason why it is better not to exceed the theoretical amount)

With respect to the fluorenes (I), when more than the theoretical amount of formaldehyde is used, an oligofluorene compound in which fluorene is crosslinked more than the target oligofluorene compound (IIa) tends to be produced. Since solubility decreases as the number of fluorene rings in the oligofluorene compound increases, it can be seen that the purification load tends to increase when an oligofluorene compound having four or more fluorene rings crosslinked is present in the target product. Therefore, normally, it is preferable that the usage-amount of formaldehyde is n/(n+1) times mole or less of the theoretical amount made into the objective.

(The reason why it is better not to significantly lower the theoretical amount)

In addition, when the amount of formaldehyde used is significantly less than the theoretical amount of n/(n+1), an oligofluorene compound having fewer crosslinking numbers of fluorene rings than the target oligofluorene compound (IIa) is the main product, or , it turns out that since the fluorenes (I) of a raw material remain unreacted, there exists a tendency for a yield to fall largely.

Therefore, the optimal amount of formaldehyde to be used is, specifically, when n = 1, usually 0.1 times mole or more, preferably 0.3 times mole or more, more preferably 0.38 mole or more with respect to the fluorenes (I). More than twice moles, and usually 0.5 times moles or less, preferably 0.46 times moles or less, and more preferably 0.42 times moles or less.

Further, in the case of n = 2, usually 0.5 times mole or more, preferably 0.55 times mole or more, more preferably 0.6 times mole or more, and usually 0.66 times mole or less, preferably 0.65 times mole or less, further Preferably it is 0.63 times mole or less. As such, it can be seen that the structure of the main product and the ratio of the product change significantly depending on the amount of formaldehyde used, and by using the amount of formaldehyde under limited conditions, the target n number of oligofluorene compounds (IIa) can be obtained in high yield.

<1.3.3.3.2 base>

Examples of the base used in step (ia) include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide, and carbonates of alkali metals such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate. , alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate and potassium phosphate, organic lithium salts such as n-butyllithium and tert-butyllithium, sodium methoxide, sodium Alkoxide salts of alkali metals such as oxide and potassium tert-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; tertiary amines such as triethylamine and diazabicycloundecene; tetramethylammonium hydroxide; tetramethylammonium hydroxide; Quaternary ammonium hydroxides, such as butylammonium hydroxide, etc. are used. These may be used individually by 1 type, and may use 2 or more types together.

When the reaction is carried out in a homogeneous system, among them, alkali metal alkoxides having sufficient basicity in this reaction are preferable, and industrially inexpensive sodium methoxide and sodium ethoxide are more preferable. Here, a powdery thing may be used for the alkoxide of an alkali metal, and liquid things, such as an alcohol solution, may be used for it. Moreover, you may prepare it by making an alkali metal and alcohol react.

On the other hand, when the reaction is carried out in a two-layer system, an aqueous solution of an alkali metal hydroxide having sufficient basicity in this reaction is preferable among them, and more preferably an industrially inexpensive aqueous solution of sodium hydroxide or potassium hydroxide.

In addition, the concentration of the aqueous solution is usually 10 wt/wt% or more, preferably 25 wt/wt% or more, because when a particularly preferable aqueous sodium hydroxide solution is used, the reaction rate is significantly lowered when the concentration is softened; More preferably, it is particularly preferable to use an aqueous solution of 40 wt/wt% or more.

In the case of carrying out the reaction in a homogeneous system, the amount of the base used is not particularly upper limit with respect to the raw material fluorenes (I). However, if the amount used is too large, the purification load after stirring or reaction becomes large, so usually fluorenes It is 10 times mole or less, preferably 5 times mole or less, and more preferably 1 times mole or less of (I). On the other hand, when the amount of the base used is too small, the progress of the reaction becomes slow, so the lower limit is usually 0.01 times mole or more, preferably 0.1 times mole or more, more preferably, relative to the fluorenes (I) of the raw material. is 0.2 times mole or more.

On the other hand, when the reaction is carried out in a two-step system, the amount of the base used is not particularly upper limit with respect to the raw material fluorenes (I). It is 10 times mole or less, Preferably it is 5 times mole or less, More preferably, it is 2 times mole or less of the orene (I). On the other hand, if the amount of the base used is too small, the progress of the reaction will be slowed. Therefore, the lower limit is usually 0.1 times mole or more, preferably 0.3 times mole or more, more preferably, relative to the fluorenes (I) of the raw material. is more than 0.4 times mole.

<1.3.3.3.3 solvent>

It is preferable to carry out a process (ia) using a solvent. Specific examples of the solvent that can be used include acetonitrile, propionitrile, etc. as the alkylnitrile solvent, and diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, and the like as the ether solvent. Examples of the halogen-based solvent such as tert-butyl methyl ether include 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane, and examples of the halogen-based aromatic hydrocarbon include chlorobenzene, 1, Examples of the amide solvent, such as 2-dichlorobenzene, include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, and the sulfoxide solvent, dimethyl sulfoxide, sulfolane, etc. Examples of the cyclic aliphatic hydrocarbon include monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; Cyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2 ,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc.; Polycyclic aliphatic hydrocarbons such as decalin; n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n -Acyclic aliphatic hydrocarbons such as decane, n-dodecane, and n-tetradecane, aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, and alcohol solvents include methanol, Ethanol, isopropanol, n-butanol, tertiary butanol, hexanol, octanol, cyclohexanol, etc. are mentioned.

In a homogeneous reaction, the solubility of the anion generated from the fluorenes (I) is high, and since the progress of reaction tends to be favorable, the amide type solvent of a polar solvent, or a sulfoxide type solvent is preferable. Among them, N,N-dimethylformamide is particularly preferable. This is because the solubility of the oligofluorene compound (IIa) in N,N-dimethylformamide is low, and the target product precipitates rapidly after formation, and further reaction progress is suppressed, and the selectivity of the target product tends to increase. Because.

In a two-layer reaction, it forms two layers with a basic aqueous solution, the solubility of anions generated from fluorenes (I) is high, and the reaction tends to proceed favorably, so that the ether solvent of a polar solvent; Or a halogen-based solvent is preferable. Among them, tetrahydrofuran is particularly preferable. This is because the solubility of the oligofluorene compound (IIa) in tetrahydrofuran is low, and the target product is precipitated quickly after formation, the further reaction progress is suppressed, and the selectivity of the target product tends to increase.

These solvents may be used individually by 1 type, and may mix and use 2 or more types.

The amount of the solvent used is usually 10 times the volume of the raw material fluorenes (I), preferably 7 times the volume, more preferably 4 times the volume amount is used. On the other hand, when there is too little usage-amount of a solvent, since stirring becomes difficult and advancing of reaction becomes slow, as a lower limit, it is normally 1 time volume of the fluorenes (I) of a raw material, Preferably it is 2 times volume. amount, more preferably an amount that is three times the volume by volume.

<1.3.3.3.4 Reaction format>

When carrying out the step (ia), the reaction format may be a batch reaction, a flow-through reaction, or a combination thereof, and the format can be adopted without particular limitation.

<1.3.3.3.5 Reaction conditions>

In the process (ia), in order to suppress the formation of the compound in which the fluorene ring crosslinked rather than the oligofluorene compound (IIa), it is preferable to react at as low as possible. On the other hand, when the temperature is too low, there is a possibility that a sufficient reaction rate cannot be obtained.

Therefore, as a specific reaction temperature, an upper limit is 40 degreeC normally, Preferably it is 30 degreeC, More preferably, it implements at 20 degreeC. On the other hand, the lower limit is -50°C, preferably -20°C, more preferably 0°C.

As for the general reaction time in the step (ia), the lower limit is usually 30 minutes, preferably 60 minutes, more preferably 2 hours, and the upper limit is not particularly limited, but usually 20 hours, preferably 10 hours. hours, more preferably 5 hours.

<1.3.3.3.6 separation and purification of target material>

After completion of the reaction, the target oligofluorene compound (IIa) can be isolated by adding the reaction solution to acidic water such as dilute hydrochloric acid or adding acidic water such as dilute hydrochloric acid to the reaction solution for precipitation.

Moreover, after completion of the reaction, a solvent in which the oligofluorene compound (IIa) is soluble as the target product and water may be added to the reaction solution for extraction. The target substance extracted with the solvent can be isolated by a method of concentrating the solvent, a method of adding a poor solvent, or the like. However, since the solubility of the oligofluorene compound (IIa) with respect to a solvent tends to be very low at room temperature, the method of making it contact with acidic water and depositing is usually preferable.

Although it is also possible to use the obtained oligofluorene compound (IIa) as a raw material of a process (ii) as it is, after refine|purifying, you may use it for a process (ii). As a purification method, a conventional purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be employ|adopted without limitation.

<1.3.3.4 Step (ib): ^{Manufacturing method when R 3} is other than a direct bond>

The oligofluorene compound represented by the following general formula (IIb) is produced using fluorenes (I) as a raw material, in the presence of an alkylating agent (VIIIa) and a base, according to the reaction represented by the following formula (ib).

[Formula 117]

The oligofluorene compound in the above formula is represented by Structural Formula (IIb).

In the ^{formula, R 3, R 4 ~ R} 9 and n are the same meaning as R ^3, R ⁴ ~ R ⁹ and n in the above formula (1). X represents a leaving group. Examples of the leaving group include a halogen atom (excluding fluorine), a mesyl group, or a tosyl group.

For the preparation of the oligofluorene compound (IIb), a method of using n-butyllithium as a base, generating an anion of fluorenes (I), and then coupling with an alkylating agent (VIIIa) is known, wherein R ³ is In the case of an ethylene group, or a ^{production method in which R 3} is a propylene group, etc., is known (Organometallics, 2008, 27, 3924; J. Molec. Cat. A: Chem., 2004, 214, 187.). In addition to the alkylene group, there is a reported example of crosslinking with a xylylene group (J. Am. Chem. Soc., 2007, 129, 8458.). However, industrial production by the method using these n-butyllithium tends to be very difficult in terms of safety and cost.

Examples of the alkylating agent used in step (ib) include diiodomethane, 1,2-diiodoethane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,6 -diiodohexane, dibromomethane, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6- Dibromohexane, dichloromethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1-bromo-3- linear alkyldihalides such as chloropropane (excluding fluorine atoms), and branched alkyldihalides such as 2,2-dimethyl-1,3-dichloropropane (excluding fluorine atoms), 1 Aralkyl dihalides such as ,4-bis(bromomethyl)benzene and 1,3-bis(bromomethyl)benzene (excluding fluorine atoms), ethylene glycol dimesylate, ethylene glycol ditosylate, and propylene glycol Disulfonates of glycols, such as dimesylate and tetramethylene glycol dimesylate, etc. are mentioned.

<1.3.4 Production method of oligofluorenediester (1)>

Hereinafter, the manufacturing method of the oligofluorenediester (1) in the process (ii) shown by a following formula is divided for every kind ^{of R<1>} and R<^{2> and is described.}

[Formula 118]

Each of the above formula, R ¹ ~ R ⁹ and n is an R ¹ ~ R means ⁹ and is the same as n in the above formula (1). R _i , R _ii and R _iii represent a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms.

<1.3.4.1 Step (iia): Manufacturing method by Michael addition in General Formula (1)>

An oligofluorenediester represented by the following general formula (1a) is prepared from an oligofluorene compound (II) and an α,β-unsaturated ester (VI) in the presence of a base according to the reaction shown in the following step (iia) do.

[Formula 119]

In the formula, R ³ ~ R ¹⁰ and n are the same meaning as R ³ ~ R ¹⁰ and n in the above formula (1). R _i , R _ii and R _iii are each independently a hydrogen atom, an optionally substituted C1-C10 alkyl group, an optionally substituted C4-C10 aryl group, or optionally substituted C6-C10 Ar represents an alkyl group.

<1.3.4.1.1 α,β-unsaturated ester>

The α,β-unsaturated ester as the reaction reagent is represented by the general formula (VI) in the step (iia), in the general formula (VI), R _i , R _ii and R _iii are each independently a hydrogen atom , an alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclohexyl group (which may be straight or branched), such as an alkyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 2-thienyl group Aralkyl groups, such as an aryl group, such as a benzyl group, 2-phenylethyl group, and p-methoxybenzyl group, are mentioned.

As α,β-unsaturated ester (VI), methyl acrylate, ethyl acrylate, phenyl acrylate, allyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol Acrylic acid esters such as monoacrylate, methyl methacrylate, ethyl methacrylate, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, methacrylic acid ester such as 2-hydroxyethyl methacrylate and α-substituted unsaturated esters such as methyl 2-ethyl acrylate and methyl 2-phenyl acrylate, and β-substituted unsaturated esters such as methyl cinnamate, ethyl cinnamate, methyl crotonate, and ethyl crotonate. Among them, an unsaturated carboxylic acid ester represented by the following general formula (VI-1) into which a polymerization-reactive group can be introduced directly.

[Formula 120]

(In the formula, R ¹⁰ represents an organic substituent having 1 to 10 carbon atoms, R _iii is optionally an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydrogen atom, having 4 to 10 carbon atoms which may be optionally substituted aryl, or substituted which represents an aralkyl group having a carbon number of 6-10.) it is preferable, and there are, acrylic acid esters, methacrylic acid esters or substituted α- unsaturated esters are more preferably contained in, and R _iii is a hydrogen atom or a methyl group; Acrylic acid esters or methacrylic acid esters are more preferable from a viewpoint of reaction rate and reaction selectivity. As for R ¹⁰ , smaller ones are industrially inexpensive, distillation purification is easy, and reactivity is high. Therefore, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate, or phenyl methacrylate is preferable. more preferably. Among these, ethyl acrylate and ethyl methacrylate are particularly preferable because they are less likely to undergo hydrolysis and less likely to produce carboxylic acid as a by-product.

On the other hand, when the organic substituent of the ester group is an ester having a hydroxyalkyl group such as 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, or 1,4-cyclohexanedimethanol monoacrylate, in step 1 Since polyester carbonate and the raw material of polyester can be obtained, it is especially preferable.

Although two or more different types of α,β-unsaturated esters (VI) may be used, it is preferable to use one type of α,β-unsaturated esters (VI) from the viewpoint of simplicity of purification.

Since the α,β-unsaturated ester (VI) has high polymerization activity, when it exists at a high concentration, it tends to polymerize easily by external stimuli such as light, heat, and acid/base. In that case, since it accompanies large heat_generation|fever, it may become very dangerous. Therefore, the amount of the α,β-unsaturated ester (VI) to be used is preferably not excessively used from the viewpoint of safety. Usually, it is 10 times mole or less with respect to the oligofluorene compound (II) which is a raw material, Preferably it is 5 times mole or less, More preferably, it is 3 times mole or less. Since the lower limit is 2 times mole in the theoretical amount with respect to the raw material. Usually, it is 2 times mole or more. In order to speed up the reaction and not leave raw materials or intermediates, the amount of the α,β-unsaturated ester (VI) to be used is 2.2 times mole or more, more preferably 2.5 times the oligofluorene compound (II) of the raw material. It's more than a mole.

<1.3.4.1.2 base>

Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide; carbonates of alkali metals such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate; magnesium carbonate; calcium carbonate; of alkaline earth metal carbonates, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate and potassium phosphate, organic lithium salts such as n-butyllithium and tert-butyllithium, sodium methoxide, sodium ethoxide, potassium tert-butoxy Alkoxide salts of alkali metals such as seed, alkali metal hydrides such as sodium hydride and potassium hydride, tertiary amines such as triethylamine and diazabicycloundecene, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl Quaternary ammonium hydroxides, such as trimethylammonium hydroxide, are used. These may be used individually by 1 type, and may use 2 or more types together.

In the case where R ³ is a methylene group, and in the case where R 3 is a methylene group, there tends to be a large difference in the reactivity of the oligofluorene compound (II). Therefore, the case where R ³ is a methylene group and the case other than that are described separately.

When R ³ is a methylene group, the decomposition reaction of the oligofluorene compound (II) easily proceeds in a solvent and in the presence of a base. Therefore, since side reactions, such as a decomposition reaction, can be suppressed when reaction is performed in the two-layer system of an organic layer and an aqueous layer, it is preferable to use a water-soluble inorganic base. Among them, an aqueous solution of an alkali metal hydroxide is preferable from the viewpoint of cost and reactivity, and an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is particularly preferable.

In addition, the concentration of the aqueous solution is usually 10 wt/wt% or more, preferably 30 wt/wt% or more, since, when a particularly preferable aqueous sodium hydroxide solution is used, the reaction rate decreases significantly when the concentration is softened; More preferably, an aqueous solution of 40 wt/wt% or more is used.

When R ³ is other than a methylene group, the reaction proceeds even in a two-layer system of an organic layer and an aqueous layer, but when the reaction is carried out using an organic base dissolved in the organic layer, the reaction proceeds rapidly, so it is better to use an organic base desirable. Among these, preferably, it is an alkali metal alkoxide which has sufficient basicity in this reaction, More preferably, they are industrially cheap sodium methoxide or sodium ethoxide. Here, a powdery thing may be used for the alkoxide of an alkali metal, and liquid things, such as an alcohol solution, may be used for it. Moreover, you may prepare it by making an alkali metal and alcohol react.

When R ³ is a methylene group, the amount of the base used is not particularly limited with respect to the raw material oligofluorene compound (II), but if the amount used is too large, the purification load after stirring or reaction may increase, so it is particularly preferable When an aqueous solution of 40 wt/wt% or more sodium hydroxide as a base is used, usually 10 times or less by volume, preferably 5 times or less by volume, more preferably 2 times or less by volume with respect to oligofluorene (II). to be. When there is too little amount of a base, since reaction rate will fall remarkably, normally, a base is 0.1 times volume amount or more with respect to the oligofluorene compound (II) of a raw material. Preferably it is 0.2 times volume amount or more, More preferably, it is 0.5 times volume amount or more.

When R ³ is other than a methylene group, the amount of the base used is not particularly limited with respect to the raw material oligofluorene compound (II), but if the amount used is too large, the purification load after stirring or reaction may increase, When sodium methoxide or sodium ethoxide, which are particularly preferred bases, is used, usually 5 times mole or less, preferably 2 times mole or less, more preferably 1 times mole or less relative to the oligofluorene compound (II); Especially preferably, it is 0.5 times mole or less. Since the reaction rate will fall remarkably when there is too little amount of a base, normally, a base is 0.005 times mole or more with respect to oligofluorene (II) of a raw material. Preferably it is 0.01 times mole or more, More preferably, it is 0.05 times mole or more, Especially preferably, it is 0.1 times mole or more.

<1.3.4.1.3 Phase Transfer Catalyst>

In the step (iia), when the reaction is carried out in a two-layer system of an organic layer and an aqueous layer, in order to increase the reaction rate, it is preferable to use a phase transfer catalyst.

Examples of the phase transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, benzyltrimethylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium iodine, acetyltrimethylammonium bromide, benzyl Halides of quaternary ammonium salts such as triethylammonium chloride (excluding fluorine), N,N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodine, N-butyl-N-methylpyrrolidinium Halides of quaternary pyrrolidinium salts such as bromide, N-benzyl-N-methylpyrrolidinium chloride and N-ethyl-N-methylpyrrolidinium bromide (excluding fluorine), N-butyl-N-methylmorphol Halides of quaternary morpholinium salts such as nium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide (excluding fluorine), N-methyl-N-benzylpipe Lidinium chloride, N-methyl-N-benzylpiperidinium bromide, N,N-dimethylpiperidinium iodine, N-methyl-N-ethylpiperidinium acetate, N-methyl-N-ethylpiperidinium iodine, etc. halides of quaternary piperidinium salts (excluding fluorine), crown ethers, and the like. It is preferably a quaternary ammonium salt, more preferably tetrabutylammonium bromide, benzyltrimethylammonium chloride, or benzyltriethylammonium chloride.

These may be used individually by 1 type, and may use 2 or more types together.

When the amount of the phase transfer catalyst used is too large with respect to the raw material oligofluorene compound (II), the progress of side reactions such as hydrolysis of esters and successive Michael reaction tends to become remarkable, and also from the viewpoint of cost, it is usually As a result, it is 5 times mole or less, preferably 2 times mole or less, more preferably 1 times mole or less with respect to the oligofluorene compound (II). When there is too little usage-amount of a phase transfer catalyst, since the reaction rate tends to fall remarkably, normally, the usage-amount of a phase transfer catalyst is 0.01 times mole or more with respect to the oligofluorene compound (II) of a raw material. Preferably it is 0.1 times mole or more, More preferably, it is 0.5 times mole or more.

<1.3.4.1.4 Solvent>

It is preferable to carry out the process (iia) using a solvent.

Specifically, the usable solvent is acetonitrile, propionitrile, etc. as the alkylnitrile solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. as the ketone solvent, and methyl acetate and acetic acid as the ester solvent. Linear esters such as ethyl, propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, 3-methoxymethylpropionate, 3-ethoxymethylpropionate, methyl lactate, and ethyl lactate; γ- Cyclic esters such as butyrolactone and caprolactone; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol-1-monomethyl ether acetate, propylene glycol-1-mono Ether esters, such as ethyl ether acetate, etc. As an ether solvent, diethyl ether, tetrahydrofuran, 1, 4- dioxane, methylcyclopentyl ether, tert-butyl methyl ether, etc. As a halogen-type solvent, 1 ,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, etc., halogen-based aromatic hydrocarbons, such as chlorobenzene, 1,2-dichlorobenzene, and amide solvents, N, Examples of sulfoxide solvents such as N-dimethylformamide and N,N-dimethylacetamide include dimethyl sulfoxide and sulfolane, and examples of cyclic aliphatic hydrocarbons include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Monocyclic aliphatic hydrocarbons; Methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, and isopropyl derivatives thereof. Cyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc.; decalin, etc. Polycyclic aliphatic hydrocarbons; Acyclic aliphatic hydrocarbons and aromatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane Examples of the aromatic heterocyclic ring include toluene, p-xylene, o-xylene, m-xylene, and the like. Examples of the alcohol-based solvent include methanol, ethanol, isopropanol, n-butanol, tert-butanol, hexanol, octanol, and cyclohexanol.

It turns out that when R<^3> is a methylene group, there exists a tendency which can suppress side reactions, such as a decomposition reaction of oligofluorene compound (II), by using water and the solvent which phase-separates. In addition, when a solvent that dissolves the raw material oligofluorene compound (II) well is used, since the reaction tends to proceed favorably, a solvent having a solubility of the raw material oligofluorene compound (II) of 0.5 mass% or more is used. It is preferable to use, More preferably, 1.0 mass % or more, Especially preferably, 1.5 mass % or more of solvent is used. Specifically, a halogen-based aliphatic hydrocarbon, a halogen-based aromatic hydrocarbon, an aromatic hydrocarbon, or an ether-based solvent is preferable, and dichloromethane, chlorobenzene, chloroform, 1,2-dichlorobenzene, tetrahydrofuran, and 1,4-dioxane are preferable. , or methylcyclopentyl ether is particularly preferred.

These solvents may be used individually by 1 type, and may mix and use 2 or more types.

There is no particular upper limit on the amount of the solvent used, but considering the production efficiency of the target product per reactor, it is usually 20 times the volume of the raw material oligofluorene compound (II), preferably 15 times the volume, more preferably is used in an amount that is 10 times the volume. On the other hand, when the amount of the solvent used is too small, the solubility of the reagent deteriorates, stirring becomes difficult, and the progress of the reaction becomes slow. Preferably, an amount that is 2 times by volume, more preferably 4 times by volume is used.

When R ³ is other than a methylene group, it can be seen that the solubility of the organic base and the oligofluorene compound (II) tends to greatly affect the reaction rate, and in order to secure the solubility, a solvent having a dielectric constant greater than or equal to a certain value It is preferable to use As a solvent which readily dissolves the organic base and the oligofluorene compound (II), an aromatic heterocyclic ring, an alkylnitrile solvent, an amide solvent, or a sulfoxide solvent is preferable, and pyridine, acetonitrile, N,N-dimethylform Particular preference is given to amides, N,N-dimethylacetamide, dimethylsulfoxide and sulfolane.

These solvents may be used individually by 1 type, and may mix and use 2 or more types.

The amount of the solvent used is not particularly limited in the upper limit, but considering the production efficiency of the target product per reactor, it is usually 20 times the volume of the raw material oligofluorene (II), preferably 15 times the volume, more preferably is used in an amount that is 10 times the volume. On the other hand, when the amount of the solvent used is too small, the solubility of the reagent worsens, stirring becomes difficult, and the progress of the reaction tends to be slow. amount, preferably in an amount that is two times the volume, more preferably four times the volume.

<1.3.4.1.5 Reaction format>

When carrying out the step (iia), the reaction format may be a batch reaction, a flow-through reaction, or a combination thereof, and the format can be adopted without particular limitation.

In the case of batch type, when the reaction reagent is introduced into the reactor, α,β-unsaturated ester (VI) is present at a high concentration when the α,β-unsaturated ester (VI) is added as a batch at the start of the reaction. , the polymerization reaction of the side reaction tends to proceed. Therefore, it is preferable to sequentially add the ?,?-unsaturated ester (VI) in small portions after adding the raw material oligofluorene compound (II), a phase transfer catalyst, a solvent, and a base.

<1.3.4.1.6 Reaction conditions>

In the step (iia), when the temperature is too low, a sufficient reaction rate cannot be obtained, whereas when the temperature is too high, the polymerization reaction of the α,β-unsaturated ester (VI) proceeds or the following general formula (1a) is hydrolyzed. Since the oligofluorene monoester monocarboxylic acid represented by -I) and the oligofluorene dicarboxylic acid represented by (1a-II) tend to produce|generate easily, it is preferable to implement temperature control. Therefore, as a reaction temperature, specifically, normally, a minimum is 0 degreeC, Preferably it is 10 degreeC, More preferably, it implements at 15 degreeC. On the other hand, the upper limit is usually carried out at 40°C, preferably at 30°C, more preferably at 20°C.

[Formula 121]

In the formula, n, R ³ ~ ¹⁰ R, R _i, R _ii, and R _iii is, the above expression (1a) means the same as in the n, R ³ ~ ¹⁰ R, R _i, R _ii, and R _iii.

The general reaction time in the step (iia) is usually 30 minutes, preferably 1 hour, more preferably 2 hours, and if the reaction time is long, the resulting oligofluorenediester (1a) is hydrolyzed. And since there is a possibility that carboxylic acid is produced, it is usually 10 hours, preferably 5 hours, more preferably 2 hours.

<1.3.4.1.7 Separation and purification of target substance>

After completion of the reaction, the target oligofluorenediester (1a) is obtained by filtering the by-product metal halide and the remaining inorganic base from the reaction solution and then concentrating the solvent or adding a poor solvent of the target product. It can be isolated by employing a method or the like to precipitate the target oligofluorenediester (1a).

Moreover, after completion|finish of reaction, you may add acidic water and the solvent in which the oligofluorene diester (1a) which is the target object is soluble to the reaction liquid, and you may extract. The target substance extracted with the solvent can be isolated by a method of concentrating the solvent, a method of adding a poor solvent, or the like.

The solvent that can be used for extraction may be any solvent in which the target product, oligofluorenediester (1a), is dissolved, and there is no particular limitation, but aromatic hydrocarbon compounds such as toluene and xylene, dichloromethane and halogen-based solvents such as chloroform, etc. 1 type or 2 or more types are used suitably.

The oligofluorene diester (1a) obtained here can be used as it is as a polyester, or as a polyester carbonate raw material monomer, or as a precursor of a polycarbonate raw material monomer, but may be used after purification. In particular, when carboxylic acid components such as oligofluorene monoester monocarboxylic acid (1a-I) and oligofluorene dicarboxylic acid (1a-II) are contained as impurities, oligofluorenediaryl In the production of the ester (2), it is not only a catalyst poison of the transesterification reaction catalyst, but also increases the metal content contained in the oligofluorenediaryl ester (2), leading to a decrease in thermal stability, It is preferable to carry out a purification operation. As a purification method, a conventional purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be employ|adopted without limitation. Extraction purification is preferable because a carboxylic acid component can be removed to an aqueous layer as a carboxylate salt by using a basic aqueous solution. More preferably, an aqueous solution of an inorganic base such as sodium hydrogencarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, or potassium hydroxide is used, and still more preferably, sodium hydrogencarbonate, sodium carbonate, carbonate, which is hardly hydrolyzed, is used. It is an aqueous solution of a weak base such as potassium. It is also possible to dissolve the oligofluorenediester (1a) in a suitable solvent and treat it with activated carbon. The solvent usable in that case is the same as the solvent usable at the time of extraction.

The oligofluorene diester (1a) obtained here can be used as it is as a polyester, or as a polyester carbonate raw material monomer, or as a precursor of a polycarbonate raw material monomer, etc. are possible.

<1.3.4.2 Step (iib): Production method by alkylation reaction>

The oligofluorene diester (1b) can be produced by a method of subjecting the oligofluorene compound (II) to an alkylation reaction of the alkylating agents (VIIIb) and (VIIIc).

[Formula 122]

In the formula, R ¹ ~ R ¹⁰ and n have the above formula (1) is equal to the mean of the R ¹ ~ R ¹⁰ and n. X represents a leaving group. Examples of the leaving group include a halogen atom (excluding fluorine) mesyl group, tosyl group, and the like.

The alkylation reaction of fluorenes is widely known, for example, 9,9-bis(haloalkyl) such as 9,9-bis(bromohexyl)fluorene or 9,9-bis(iodohexyl)fluorene Fluorene has been reported (J. Org. Chem., 2010, 75, 2714.). From these findings, by using the oligofluorene compound (II) as a raw material, the synthesis|combination of oligofluorene diester (1b) is possible.

Examples of the alkylating agent used in the step (iib) include methyl chloroacetate, methyl bromoacetate, methyl iodide, ethyl chloroacetate, ethyl bromoacetate, ethyl iodide, propyl chloroacetate, n-butyl chloroacetate, and tert chloroacetate. -Butyl, tert-butyl bromoacetate, tert-butyl iodine acetate, methyl chloropropionate, methyl bromopropionate, methyl iodide propionate, ethyl chloropropionate, tert-butyl chloropropionate, tert-butyl bromopropionate, ethyl bromopropionate , ethyl iodopropionate, methyl chlorobutyrate, methyl bromobutyrate, methyl iodobutyrate, ethyl chlorobutyrate, ethyl chlorobutyrate, ethyl iodobutyrate, alkyl haloalkanoates such as tert-butyl iodopropionate, phenyl chloroacetate, phenyl bromoacetate , aryl haloalkanoate such as phenyl iodide acetate, 4-chloromethyl methyl benzoate, 4-bromomethyl methyl benzoate, 4-chloromethyl ethyl benzoate, 4-bromomethyl ethyl benzoate, 3-chloromethyl methyl benzoate, 3- Alkyl haloalkyl benzoate, such as methyl bromomethyl benzoate, etc. are mentioned.

Moreover, it is preferable to isolate and refine|purify the oligofluorenediester (1b) which is a target object after completion|finish of reaction in process (iib). As the method of isolation/purification, the method described in <1.3.4.1.7 separation/purification of the target substance> is preferably employable.

<1.3.4.3 Production method of oligofluorenediaryl ester of general formula (2) (Production method of oligofluorenediaryl ester compound (2) by transesterification)>

The oligofluorenediaryl ester compound (2) can be produced by a method in which an oligofluorenediester compound (1) and a diaryl carbonate (11a) are subjected to a transesterification reaction step (step (iic)).

[Formula 123]

In the formula, R ¹ ~ R ¹⁰ and n have the above formula (1) is equal to the mean of the R ¹ ~ R ¹⁰ and n. Ar ¹ represents an optionally substituted aryl group having 4 to 10 carbon atoms.

<1.3.4.3.1 Production method of oligofluorenediaryl ester of general formula (2) (Production method of oligofluorenediaryl ester compound (2) by transesterification)>

The ^{oligofluorenediaryl ester compound (2), wherein Ar 1} is an optionally substituted aryl group having 4 to 10 carbon atoms, is prepared from the oligofluorenediester compound (1) and diaryl carbonates (11a) in the presence of a transesterification catalyst. , prepared according to the reaction represented by step (iic).

<1.3.4.3.1.1 Oligofluorenediester compound (1)>

When there is much content of carboxylic acid of an oligofluorenediester compound (1), carboxylic acid becomes a catalyst poison of a transesterification reaction catalyst, and there exists a tendency for the need to use a transesterification reaction catalyst abundantly. Therefore, when there is much content of carboxylic acid, there exists a tendency for metal content contained in an oligofluorenediaryl ester compound (2) to increase. From the viewpoint of reducing the amount of metal contained in the oligofluorenediaryl ester (2), the content of the carboxylic acid in the oligofluorenediester compound (1) is preferably 5 mass% or less, more preferably It is 3 mass % or less, More preferably, it is 2 mass % or less, More preferably, it is 1 mass % or less. Moreover, although it is so preferable that there is little carboxylic acid content, when it is going to be set as 0 mass %, for prevention of impurity mixing, etc., there exists a possibility that it may be accompanied by a remarkable cost increase and a fall of production efficiency. Content of carboxylic acid which can maintain productivity and can reach is 0.1 mass % or more normally.

As carboxylic acid contained in the oligofluorene diester compound (1), oligofluorene monoester monocarboxylic acid and oligofluorene dicarboxylic acid are mentioned, for example.

The number of moles of the oligofluorene monoester monocarboxylic acid and oligofluorenedicarboxylic acid contained in the oligofluorene diester compound (1) is estimated using the analytical curve from the area% of HPLC analysis, for example. can do.

<1.3.4.3.1.2 Diaryl carbonates>

Diaryl carbonates as the reaction reagent include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-crezyl carbonate, dinaphthyl canate, bis (biphenyl) carbonate, and the like. Among them, diphenyl carbonate which is inexpensive and can be obtained industrially is preferable.

These diaryl carbonates may be used individually by 1 type, and may mix and use 2 or more types.

There is no upper limit in particular for the usage-amount of diaryl carbonates with respect to the raw material oligofluorenediester (1), but if the usage-amount is too large, since the purification load after reaction tends to become large, normally, 20 It is fold mole or less, Preferably it is 10 times mole or less, More preferably, it is 5 times mole or less.

On the other hand, if the amount of diaryl carbonates used is too small, oligofluorene diester (1) as a raw material and oligofluorene monoaryl ester (10e) as shown below as an intermediate may remain, so it is set to the lower limit. is usually 1 times mole or more, preferably 1.5 times mole or more, more preferably 2 times mole or more with respect to the oligofluorenediester (1) of the raw material.

[Formula 124]

In the formula, R ¹ ~ R ¹⁰ and n have the above formula (1) is equal to the mean of the R ¹ ~ R ¹⁰ and n. Ar ¹ represents an optionally substituted aryl group having 4 to 10 carbon atoms.

<1.3.4.3.1.3 Transesterification Catalyst>

Examples of the transesterification reaction catalyst include tetrabutoxy titanium, tetraisobutoxy titanium, tetramethoxy titanium, tetraisopropoxy titanium, tetraethoxy titanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxy titanium , tetraphenoxy titanium, titanium (IV) acetylacetonate, titanium (IV) diisopropoxide bis (acetylacetonato), and other titanium compounds; lithium carbonate, dibutylaminolithium, lithium acetylacetonate, sodium phenoxide , Alkali metal compounds such as potassium phenoxide; Cadmium compounds such as cadmium acetylacetonate and cadmium carbonate; Zirconium compounds such as zirconium acetylacetonate and zirconocene; Lead sulfide, lead hydroxide, lead acid salt, zincate, lead carbonate, Lead compounds, such as lead acetate, tetrabutyl lead, tetraphenyl lead, triphenyl lead, dimethoxy lead, and diphenoxy lead; Copper acetate, copper bisacetylacetonate, copper oleate, butyl copper, dimethoxy copper, copper chloride, etc. Copper compounds; Iron compounds such as iron hydroxide, iron carbonate, triacetoxy iron, trimethoxy iron and triphenoxy iron; zinc bisacetylacetonate, diacetoxy lead, dimethoxy zinc, diethoxy zinc, diphenoxy iron, etc. of zinc compounds; din-butyltin oxide, diphenyltin oxide, din-octyltin oxide, din-butyltin dimethoxide, din-butyltin diacrylate, din-butyltin dimethacrylate organic tin compounds such as , din-butyltin dilaurate, tetramethoxytin, tetraphenoxytin, tetrabutyl-1,3-diacetoxydistanoxane; aluminum acetate, aluminum methoxide, aluminum ethoxide; Aluminum compounds, such as aluminum phenoxide; Vanadium compounds, such as vanadium dichloride, vanadium trichloride, vanadium tetrachloride, and vanadium sulfate; Phosphonium salts, such as tetraphenylphosphonium phenoxide, etc. are mentioned. These may be used individually by 1 type, and may use 2 or more types together.

Among these, it is preferable to use a phosphonium salt, a lithium compound, a zirconium compound, an organotin compound, or a titanium compound, etc. from the viewpoint of being industrially inexpensive and having a superiority in reaction operation, and among them, an organotin compound or titanium Compounds are particularly preferred.

There is no upper limit in particular for the usage-amount of the transesterification catalyst with respect to the oligofluorenediester (1) used as a raw material, but if the usage-amount is too large, since the purification load after reaction becomes large, normally 20 mol% or less of fluorene is preferable. Preferably it is 10 mol% or less, More preferably, it is 5 mol% or less.

On the other hand, if the amount of the transesterification catalyst used is too small, the reaction time may become excessively long, so the lower limit is usually 0.1 mol% or more, preferably 0.5 mol%, based on the oligofluorenediester of the raw material. % or more, more preferably 1 mol% or more.

<1.3.4.3.1.4 Solvent>

In the step (iic), although a reaction solvent may be used, it is preferable to carry out the reaction only with the raw material oligofluorene diester (1), diaryl carbonates, and the transesterification catalyst without using the reaction solvent. However, when the raw material oligofluorene diester (1) and diaryl carbonates are solid at normal temperature and stirring is difficult, a reaction solvent may be used. When using a reaction solvent, the kind is arbitrary as long as it is a solvent which can melt|dissolve and/or disperse|distribute suitably the oligofluorenediester (1) of the above-mentioned raw material, diaryl carbonates, and the transesterification reaction catalyst. .

Specifically, the solvent that can be used is an alkylnitrile solvent, such as acetonitrile, propionitrile, a ketone solvent, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and an ether solvent, diethyl ether, As a halogen-based solvent such as tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, tert-butylmethyl ether, 1,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetra Chloroethane, etc., halogen-based aromatic hydrocarbons, such as chlorobenzene, 1,2-dichlorobenzene, etc., amide-based solvents, such as N,N-dimethylformamide, N,N-dimethylacetamide, etc., sulfoxide-based solvents Examples of cyclic aliphatic hydrocarbons such as dimethyl sulfoxide and sulfolane include monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and cyclooctane; derivatives thereof such as methylcyclopentane, ethylcyclopentane, methylcyclohexane; Ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane , isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc.; Polycyclic aliphatic hydrocarbons such as decalin; n-pentane, n-hexane, n-heptane, n- Examples of acyclic aliphatic hydrocarbons and aromatic hydrocarbons such as octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane include toluene, p-xylene, o-xylene, m-xylene, A pyridine etc. are mentioned as aromatic heterocyclic ring, such as 1,3,5-trimethylbenzene, 1,2,4- trimethylbenzene, 1,2,3,4- tetrahydronaphthalene.

Since this reaction is usually preferably carried out at a high temperature of 100°C or higher, among the above solvents, chlorobenzene, 1,2-dichlorobenzene, trichlorobenzene, toluene, p-xylene, o- Xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-tetrahydronaphthalene, decahydronaphthalene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, or sulfolane is preferable, the raw material oligofluorenediester (10b) can be suitably dissolved, the boiling point is 130° C. or higher, and the reaction at a higher temperature is 1,2-dichlorobenzene, xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, or 1,2,3,4-tetrahydronaphthalene, decahydronaphthalene Especially preferred.

These solvents may be used individually by 1 type, and may mix and use 2 or more types.

The amount of the solvent used is not particularly limited in the upper limit, but considering the production efficiency of the target product per reactor, it is usually 15 times the volume of the raw material oligofluorene diester (1), preferably 10 times the volume, more Preferably, an amount that is five times by volume is used. On the other hand, when there is too little usage-amount of a solvent, the solubility of a reagent worsens and stirring becomes difficult, and since advancing of reaction becomes slow, as a lower limit, it is normally 1 time as a density|concentration of the oligofluorenediester (1) of a raw material. An amount that is a volume amount, preferably a volume amount twice, more preferably a volume amount of 4 times is used.

<1.3.4.3.1.5 Reaction format>

When carrying out the step (iic), the reaction mode may be a batch reaction, a flow-through reaction, or a combination thereof, and the format can be adopted without particular limitation.

<1.3.4.3.1.6 Reaction conditions>

In the step (iic), if the temperature is too low, a sufficient reaction rate tends not to be obtained, so the lower limit is usually 50°C, preferably 70°C, more preferably 100°C. On the other hand, an upper limit is 250 degreeC normally, Preferably it is 200 degreeC, More preferably, it implements at 180 degreeC.

As for the general reaction time in the step (iic), the lower limit is usually 1 hour, preferably 2 hours, more preferably 3 hours, and the upper limit is not particularly limited, but usually 30 hours, preferably 20 hours. hours, more preferably 10 hours.

In the step (iic), the reaction may be carried out while distilling off the by-products under reduced pressure in order to shift the equilibrium to the product side. The pressure in the case of reducing the pressure is usually 20 kPa or less, preferably 10 kPa or less, and more preferably 5 kPa or less. On the other hand, if the pressure reduction degree is too high, there is a possibility of sublimation to the diaryl carbonates used as reagents, so it is usually 0.1 kPa or more, preferably 0.5 kPa or more, more preferably 1.0 kPa or more.

<1.3.4.3.1.7 Separation and purification of target substance>

After completion of the reaction, the target oligofluorenediaryl ester (2) can be isolated by adding a poor solvent to the reaction solution and precipitating it.

Moreover, after completion|finish of reaction, you may add and extract the solvent and water in which the oligofluorenediaryl ester (2) which is a target object is soluble to a reaction liquid. The target product extracted with the solvent can be isolated by a method using a solubility difference due to a temperature difference, a method of concentrating the solvent, a method of adding a poor solvent, or the like.

The obtained oligofluorenediaryl ester (2) is a polycarbonate raw material containing polyester carbonate, or a polyester raw material, and can also be used for superposition|polymerization as it is. As a purification method, a conventional purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be employ|adopted without limitation.

When refining by a purification method such as recrystallization or reprecipitation, the solvent specifically usable as a good solvent is an alkylnitrile-based solvent such as acetonitrile, propionitrile, and the ketone-based solvent is acetone, methylethylketone, As the ether solvent such as methyl isobutyl ketone, diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, tert-butyl methyl ether, etc., as the halogen solvent, 1,2-dichloro Ethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, etc., halogen-based aromatic hydrocarbons, such as chlorobenzene, 1,2-dichlorobenzene, and amide solvents, N,N-dimethylform Amide, N,N-dimethylacetamide, etc., as a sulfoxide solvent, dimethyl sulfoxide, sulfolane, etc., as an aromatic hydrocarbon, toluene, p-xylene, o-xylene, m-xylene, 1, A pyridine etc. are mentioned as aromatic heterocyclic rings, such as 3, 5- trimethylbenzene, 1,2, 4- trimethylbenzene, 1,2,3,4- tetrahydronaphthalene.

Since the oligofluorenediaryl ester (2) has a large solubility difference with respect to temperature, methyl isobutyl ketone, 1,4-dioxane, methylcyclopentyl ether, tert-butyl methyl ether, 1,1 having a boiling point of 100°C or higher ,2,2-tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, toluene, p-xylene, o -xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-tetrahydronaphthalene, and pyridine are preferable. Among these, toluene, p-xylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene of aromatic hydrocarbons that are stable at high temperatures even in the presence of a transesterification catalyst and have a small environmental load in a non-halogen system , 1,2,4-trimethylbenzene is more preferable.

These good solvents may be used individually by 1 type, and may mix and use 2 or more types.

The amount of the solvent used is not particularly limited in the upper limit, but in consideration of the purification efficiency of the target substance per reactor, usually 15 times the mass of the oligofluorenediaryl ester (2), preferably 10 times the mass, more preferably is used in an amount that is 5 times the mass. On the other hand, when there is too little usage-amount of a solvent, the solubility of a reagent worsens and stirring becomes difficult, and since advancing of reaction becomes slow, as a lower limit, normally 0.3 times mass as a density|concentration of oligofluorenediaryl ester (2). amount, preferably 0.5 times the mass, more preferably 1 times the mass amount is used.

When refining by a refining method such as recrystallization or reprecipitation, crystallization may be carried out only with a good solvent using the solubility difference depending on temperature, but in order to increase the recovery rate, it is preferable to use a poor solvent. . Specific examples of the poor solvent that can be used include monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and cyclooctane; methylcyclopentane, ethylcyclopentane, methylcyclohexane and its derivatives; Ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane , isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc.; Polycyclic aliphatic hydrocarbons such as decalin; n-pentane, n-hexane, n-heptane, n- Examples of acyclic aliphatic hydrocarbons such as octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane, and alcohol solvents include methanol, ethanol, isopropanol, n-butanol, tert-butanol, and hexanol. , octanol, cyclohexanol, and the like.

Since highly polar impurities can be removed, the poor solvent is preferably an alcohol-based solvent such as methanol, ethanol, isopropanol, n-butanol, tert-butanol, hexanol, octanol, or cyclohexanol. Shorter methanol and ethanol are more preferable.

In the oligofluorenediaryl ester (2), there exist a stable type and a metastable type crystal polymorph. When a good solvent is used and crystals are precipitated by a difference in solubility depending on temperature, the crystals precipitated in the metastable form are brittle and tend to be pulverized when the phase changes to the stable form. The pulverized crystals have poor fluidity when used industrially as a resin raw material, and may cause poor input. On the other hand, as a good solvent, toluene, p-xylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4- When an aromatic hydrocarbon such as tetrahydronaphthalene and an alcohol solvent such as methanol, ethanol, isopropanol, n-butanol, tert-butanol, hexanol, octanol or cyclohexanol are combined as a poor solvent, a stable form from the beginning crystals are obtained, which is preferable because pulverization does not occur.

When an aromatic hydrocarbon as a good solvent and an alcohol solvent as a poor solvent are combined, if the alcohol solvent is added at a low temperature, metastable crystals are precipitated before the alcohol solvent is added, and the ratio tends to increase. have. Therefore, the addition temperature of the alcohol solvent is usually 20°C or higher, preferably 30°C or higher, more preferably 40°C or higher, and particularly preferably 50°C or higher.

For metastable crystals of oligofluorenediaryl ester (2), when analyzed by powder X-ray diffraction measurement (XRD), 2θ = 5.6°, 8.5°, 11.0°, 12.5°, 12.9°, 14.9°, 16.3 A characteristic peak is observed at °, 19.1° (θ = ±0.2°). Since metastable crystals are brittle and tend to cause phase transition, they are pulverized by continuing stirring during crystallization, resulting in poor extraction from the reactor and deterioration of filterability. In addition, metastable crystals are weak to impact, but in order to avoid poor injection due to a decrease in powder fluidity, it is preferable not to include peaks of these incident angles in the crystals.

When the amount of the good solvent used for the crystallization of the oligofluorenediaryl ester (2) is too small, it becomes difficult to dissolve the oligofluorenediaryl ester (2) and the purification efficiency also decreases, so the amount of the good solvent The lower limit of is usually 0.3 times the mass of the oligofluorenediaryl ester (2), preferably 0.5 times the mass, more preferably 0.7 times the mass, still more preferably 0.9 times the mass. Moreover, when there is too much quantity of a good solvent, the loss with respect to the filtrate of oligofluorenediaryl ester (2) increases, and since a yield falls, the upper limit of the quantity of a good solvent is oligofluorenediaryl ester ( 2) is usually 5 times the mass, preferably 4 times the mass, more preferably 3 times the mass, still more preferably 2 times the mass.

When the amount of the poor solvent used for the crystallization of the oligofluorenediaryl ester (2) is too small, the loss of the oligofluorenediaryl ester (2) to the filtrate increases and the yield decreases, so the poor solvent The lower limit of the amount of is usually 2 times the mass of the oligofluorenediaryl ester (2), preferably 3 times the mass, more preferably 3.5 times the mass, still more preferably 4 times the mass. to be. When the amount of the poor solvent is too large, not only the purification efficiency decreases, but also the kiln efficiency decreases and the productivity decreases. 10 times the mass, preferably 9 times the mass, more preferably 8 times the mass, still more preferably 7 times the mass.

If a large amount of poor solvent is added at one time in order to obtain stable crystals from the beginning, solubility decreases rapidly, and crystals are precipitated at once, making it difficult to increase the size of the crystals. When a small amount of a specific poor solvent is added to a specific good solvent to oligofluorenediaryl ester (2), there exists a tendency for solubility to rise. There exists a tendency which can make a crystal size larger by making use of this property and adding a specific poor solvent in division|segmentation, or supplying a specific poor solvent intermittently. Specific good solvents include toluene, p-xylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-tetra Aromatic hydrocarbons, such as hydronaphthalene, are preferable, and toluene, p-xylene, o-xylene, and m-xylene which are industrially cheap and are easy to obtain are more preferable. As a specific poor solvent, alcohol solvents, such as methanol, ethanol, isopropanol, n-butanol, tert-butanol, hexanol, octanol, and cyclohexanol, are preferable, and isopropanol, methanol which is industrially cheap and easy to obtain; Ethanol is more preferable. Particularly preferred is a combination of o-xylene as a specific good solvent and methanol as a specific poor solvent.

When the specific poor solvent is added in two divided doses, if the ratio of the specific poor solvent to be added first is too high, the influence of the poor solvent is strong and the effect of improving the solubility is not seen, so usually 40 mass% or less, preferably is 30 mass% or less, more preferably 20 mass% or less. On the other hand, when the ratio of the specific poor solvent added at the beginning is too low, the effect of adding the poor solvent is not seen, so it is usually 5 mass% or more, preferably 10 mass% or more, more preferably 15 mass% or more. .

When adding a specific poor solvent in two divided doses, the optimum addition temperature needs to be adjusted depending on the combination of a specific good solvent and a specific poor solvent. , metastable crystals precipitate before addition of methanol, and the proportion tends to increase. Therefore, the temperature of methanol added initially is usually 45°C or higher, preferably 50°C or higher, more preferably 55°C or higher, and still more preferably 60°C or higher. Next, the lower limit of the temperature of methanol to be added is usually 0°C or higher, preferably 5°C or higher, and more preferably 10°C or higher. On the other hand, the upper limit of the temperature of methanol to be added next is usually 42°C or less, preferably 40°C or less, and more preferably 38°C or less.

In the oligofluorenediaryl ester (2), the particle size of the particles varies greatly depending on the crystallization conditions. When the particle diameter of the particles is too small, clogging of the filter cloth tends to occur in the crystal filtration step, the filtration time becomes long, the liquid content increases, and the purity of the oligofluorenediaryl ester (2) tends to decrease. . Moreover, when using it as a resin raw material, powder fluidity|liquidity deteriorates and there exists a possibility of raising the injection defect. Therefore, the lower limit of the average particle diameter of the particles of the oligofluorenediaryl ester (2) is usually 50 µm or more, preferably 70 µm or more, more preferably 90 µm or more, still more preferably 130 µm or more. or more, particularly preferably 170 µm or more. When the average particle diameter of the particle|grains of oligofluorenediaryl ester (2) is too large and it uses as a resin raw material, a filter may clog. Therefore, the upper limit of the average particle diameter of the particles of the oligofluorenediaryl ester (2) is usually 2 cm or less, preferably 1 cm or less, more preferably 0.5 cm or less, still more preferably 0.3 cm is below.

In the oligofluorenediaryl ester (2), the particle size of the particles varies greatly depending on the crystallization conditions. When the particle diameter of the particles is too small, clogging of the filter cloth tends to occur in the crystal filtration step, the filtration time becomes long, the liquid content increases, and the purity of the oligofluorenediaryl ester (2) tends to decrease. . Moreover, when using it as a resin raw material, powder fluidity|liquidity deteriorates and there exists a possibility of raising the injection defect. Therefore, the cumulative % of the particles of the oligofluorenediaryl ester (2) having a particle diameter of 50 µm or more is usually 50 µm or more, 50% or more, preferably 60% or more, more preferably 70% or more, More preferably, it is 80 % or more, Especially preferably, it is 90 % or more.

The particle diameter of the primary crystals obtained by crystallization or the aggregates in which the primary crystals are aggregated varies depending on various conditions such as the shape of the reactor or stirring blade, the stirring speed, and the material of the reactor. In general, when the scale becomes large, the shear force increases, so it tends to be pulverized, and the particle size tends to be small. However, by following the above-mentioned crystallization conditions, even if it uses a reactor of 1 m<3> or more, for example, the oligofluorenediaryl ester (2) of a preferable particle diameter can be obtained.

The content of the metal can be reduced by repeating the crystallization operation. At this time, although the recovery amount of the target oligofluorenediaryl ester (2) improves so that the crystallization temperature is low, there exists a tendency for the metal refining efficiency to fall.

When a Ti compound which is a particularly preferable transesterification catalyst is used as a catalyst, it is difficult to remove Ti in the oligofluorenediaryl ester (2), and the residual Ti may become a problem. In such a case, water is added to the reaction solution after the completion of the reaction or a solution in which the oligofluorenediaryl ester (2) isolated once again is dissolved in the above-mentioned solvent to inactivate the Ti compound, and insoluble titanium After conversion to a residue, it is desirable to remove the titanium residue in the filtration process. At this time, when water is added to the reaction solution after the completion of the reaction, the amount of titanium residue to be purified is large, and a large load is applied to the filtration step, so that the filterability tends to deteriorate. Therefore, it is preferable to add a poor solvent to the reaction completion liquid once and remove most of the Ti compound, then re-dissolve the isolated oligofluorenediaryl ester (2), deactivate it with water, and then proceed to the filtration step. do.

Since the particle diameter of the titanium residue is very fine, if the pore diameter is large, the titanium residue cannot be completely removed, and there is a risk of mixing in the product. Therefore, the pore diameter of the filter medium used for a filtration process is 10 micrometers or less normally, Preferably it is 5 micrometers or less, More preferably, it is 1 micrometer or less. On the other hand, when the pore diameter of a filter medium is too small, a filtration rate may fall and there exists a possibility of causing delay of process time. Therefore, as a pore diameter of the filter medium used for a filtration process, it is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, More preferably, it is 0.1 micrometer or more. Moreover, since a titanium residue deposits on a filter surface that the filtration surface of the filter medium used for a filtration process is flat, and it clogs, in order to shorten a filtration time, an excess filtration area is needed. On the other hand, if the shape of the filter medium used in the filtration step is a normal shape with the bottom surface closed, such as a filter bag, the titanium residue is deposited on the bottom surface, and since filtration can be performed also from the side surface, the risk of clogging is reduced. It can be reduced, and it is preferable. Moreover, the material of the filter medium used for a filtration process is cheap and from a viewpoint that it is industrially easy to obtain, polypropylene, cotton, and polyester are preferable, and from a viewpoint of high heat resistance, polyester, cotton and The product made from Teflon is preferable, More preferably, it is an inexpensive and high heat resistance cotton and polyester filter medium. Suction filtration, centre filtration, and pressure filtration are mentioned as a filtration process. Among them, pressure filtration has a high filtration rate and is preferable. The pressure of pressure filtration is 0.11 MPa or more normally in order to raise a filtration rate, Preferably it is 0.15 MPa or more, More preferably, it is 0.20 MPa or more. Although the upper limit of pressure filtration varies depending on facilities, in order to avoid a large load being applied to facilities, it is usually 5.0 MPa or less, Preferably it is 3.0 MPa or less, More preferably, it is 1.0 MPa or less.

In a filtration process, you may use a filter aid. Examples of the filter aid include diatomaceous earth, powdered cellulose, magnesium sulfate, sodium sulfate, silica gel, activated alumina, activated carbon, activated clay, perlite, glass fiber, glass beads, and the like.

Among these, diatomaceous earth, powdered cellulose, and perlite having a large filtration area and little loss due to adsorption are preferable.

<2 oligofluorene diester B>

The oligofluorenediester of the present invention (hereinafter, may be abbreviated as "oligofluorenediester B") contains two or more fluorene units which may have a substituent,

The carbon atoms at the 9th position of the fluorene unit are bonded in a chain form through a direct bond or an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent, , Also,

The content rate of carboxylic acid is 5 mass % or less.

As an alkylene group, an arylene group, and an aralkylene group, what was illustrated in <1.1 alkylene group, an arylene group, an aralkylene group> is employable preferably.

Similarly, as the fluorene unit, those exemplified in <1.2 Substituents which the fluorene unit may have> can be preferably employed.

^{In the oligofluorene diester B of the present invention, substituents α 1} and α ² are bonded to the carbon atom at position 9 of the fluorene unit located at both terminals, respectively, and the ester group is bonded to ^{the substituents α 1 and α 2 .} can In this case, α ¹ and α ² may be the same or different. Further, the substituents α ¹ and α ² include a direct bond, that is, an ester group may be directly bonded to the carbon atom at the 9th position of the fluorene unit.

As an ester group, what was illustrated in <1.3 ester group> of <<Invention 2>> mentioned above is employable preferably. It is preferable that it is a linear alkyl group from the point which especially the resistance with respect to hydrolysis tends to become high, and it is more preferable that it is a methyl group or an ethyl group.

As the substituents α ¹ and α ^{2 , those exemplified in <1.4 substituents α 1} and α ² > of the above-mentioned <Invention 2> can be preferably employed.

Moreover, as a specific structure of the oligofluorenediester B, what can be represented by the said General formula (1) can be used preferably. Moreover, as a specific example, the structure shown to the said [H] group is mentioned.

<2.1 Physical properties of oligofluorene diester B>

As mentioned above, in the oligofluorenediester of this invention, the content rate of carboxylic acid is 10 mass % or less. By making the content of carboxylic acid within a predetermined range in this way, when a diaryl ester is manufactured using the oligofluorenediester as a raw material, the tendency that the amount of metal contained in the diaryl ester can be reduced to a predetermined range There is this.

From the viewpoint of reducing the amount of metal contained in the diaryl ester, the content of the carboxylic acid is preferably 8 mass% or less, more preferably 5 mass% or less, still more preferably 4 mass% or less, and more More preferably, it is 3 mass % or less, Especially preferably, it is 2 mass % or less, Most preferably, it is 1 mass % or less. Moreover, although it is so preferable that there is little carboxylic acid content, when it is going to be set as 0 mass %, for prevention of impurity mixing, etc., there exists a possibility that it may be accompanied by a remarkable cost increase and a fall of production efficiency. Content of carboxylic acid which can maintain productivity and can reach is 0.1 mass % or more normally.

It is considered that the said carboxylic acid is a byproduct by hydrolysis at the time of oligofluorenediester manufacture. Although it does not specifically limit about the kind of said carboxylic acid, For example, oligofluorene monoester monocarboxylic acid (in oligofluorene diester, what substituted either ester group with carboxylic acid), oligo fluorenedicarboxylic acid (in oligofluorenediester, what substituted two ester groups with carboxylic acid) is mentioned.

As a measuring method of content of carboxylic acid, the method of quantifying the isolated carboxylic acid by high performance liquid chromatography is mentioned, for example.

As a method of making the amount of carboxylic acid within the above range, for example, a conventional purification method, for example, a filtration operation such as washing with basic water, recrystallization, reprecipitation, extraction purification, filter filtration, column chromatography, and column chromatography. and the like. Moreover, when manufacturing the oligofluorenediester B of this invention by reaction of a two-step system, it is important to suppress a hydrolysis reaction by lowering the reaction temperature, shortening of reaction time, etc.

In addition, the other physical property values of the oligofluorene diester B of the present invention are not particularly limited, but satisfy the physical property values exemplified in the section <1.6 Reactive functional group-containing oligofluorene A1> of <Invention 3> It is preferable to do

<2.2 Manufacturing method of oligofluorenediester B>

Although it does not specifically limit about the manufacturing method of the oligofluorene B of this invention, For example, it can manufacture by the method similar to the method described in <1.3.4 manufacturing method of oligofluorene diester (1)>.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by the following Examples unless the gist thereof is exceeded.

«Examples 1-1 to 1-6, Comparative Examples 1-1 to 1-17»

The quality evaluation of the oligofluorene monomer of the present invention and the evaluation of the properties of the resin and the transparent film were performed by the following method. In addition, the characteristic evaluation method is not limited to the following method, A person skilled in the art can select suitably.

<Evaluation of monomers and resins>

(1) Contents of aluminum and sodium in fluorene-based monomers

The content of aluminum and sodium in the monomer containing a fluorene ring (hereinafter, sometimes referred to as a fluorene-based monomer) was measured as follows. After the analysis sample was subjected to wet decomposition, the aluminum content and the sodium content were quantified using ICP-AES (ULTIMA 2C manufactured by HORIBA Jobin Yvon). Moreover, regarding the sodium content, the analysis by the atomic absorption method (SpectrAA-220P by VARIAN) was also used together depending on an analysis sample.

(2) Chlorine content in fluorene-based monomers

The chlorine content in the fluorene-based monomer was measured as follows. The analysis sample was combusted using Mitsubishi Chemical Co., Ltd. product combustion apparatus AQF-2100M, and the generated gas was made to absorb in pure water. Then, the pure water which absorbed the gas was introduce|transduced into the Nippon Dionex Co., Ltd. product ion chromatograph DX-500, and the chlorine content rate was quantified.

(3) Thermal decomposition temperature of fluorene-based monomers

The glass transition temperature of the fluorene-based monomer was measured using a differential thermogravimetric simultaneous analyzer TG-DTA6300 manufactured by SI Nanotechnology. About 4 mg of a fluorene-based monomer was put into an aluminum pan manufactured by the company and sealed, and the temperature was raised from room temperature (20 to 30°C) to 600°C at a temperature increase rate of 10°C/min under a nitrogen stream of 200 ml/min. . From the obtained TG data (thermogravimetric data), the temperature at which the sample weight decreased by 5 wt% was defined as the 5 wt% weight loss temperature. As for the monomer containing the solvent, the weight at the time when the ^{weight change ceases after the weight of the solvent estimated from 1} H-NMR decreases from the weight at the start of the measurement is taken as the initial weight, and the initial weight is 5 wt% The reduced temperature was set as the 5 wt% weight loss temperature. In addition, from the obtained TG data (thermogravimetric data), the peak top, in which no decrease in weight was observed and a steep endothermic peak was observed, was taken as the melting point of the sample.

(4) Absorption maximum wavelength in the ultraviolet visible region (UV-Vis) of the fluorene-based monomer

The absorption maximum wavelength in the ultraviolet visible region (UV-Vis: 280-800 nm) of a fluorene type monomer was measured using Shimadzu Corporation ultraviolet-visible absorption spectrophotometer UV-1650PC. The measurement solution was precisely prepared using tetrahydrofuran as a solvent so that the concentration was 10 µM as the fluorene ring. A quartz cell of 1 cm in width and length was used as the measurement cell, and measurement was performed in an environment with a temperature of 23±5°C. The absorption spectrum of the measurement solution was measured in the range of 280-800 nm, and the maximum value of absorption was made into absorption maximum wavelength ( _λmax ).

(5) Reduced viscosity of resin

The resin was dissolved in methylene chloride to prepare a resin solution having a concentration of 0.6 g/dL. It measured at the temperature of 20.0 degreeC +/-0.1 degreeC using the Moritomo Ewha Kogyo Co., Ltd. Uberode type viscosity tube, and the passage time t _{0 of a} solvent and the passage time t of a solution were measured. Using the obtained _{values of t 0 and t, the relative viscosity η rel} was determined by the following formula (I), and the specific viscosity _{η sp} was determined by the following formula (ii) using the _{obtained relative viscosity η rel} .

η _rel = t/t ₀ ... (I)

η _sp = (η - η ₀ )/η ₀ = η _rel - 1 ... (ii)

Then, by dividing the specific viscosity η _sp to a concentration c (g / ㎗) obtained it was calculated the reduced viscosity η _sp / c. The higher this value, the larger the molecular weight.

(6) melt viscosity of resin

Pellet-shaped resin was vacuum-dried at 90 degreeC for 5 hours or more. Using the dried pellets, it measured with the Toyo Seiki Co., Ltd. product capillary rheometer. The measurement temperature to 240 ℃, and a shear rate of ~ 9.12 was used as the value of the melt viscosity at 1824 sec ^-1 measured for melt viscosity, and 91.2 sec ^-1 between. In addition, for the orifice, a die having a diameter of phi 1 mm and a length of 10 mm was used.

(7) the glass transition temperature (Tg) of the resin

The glass transition temperature of the resin was measured using a differential scanning calorimeter DSC6220 manufactured by SI Nanotechnology. About 10 mg of resin was put into an aluminum pan manufactured by the company and sealed, and the temperature was raised from 30°C to 250°C at a temperature increase rate of 20°C/min under a nitrogen stream of 50 ml/min. After maintaining the temperature for 3 minutes, it was cooled to 30 °C at a rate of 20 °C/min. It was maintained at 30 degreeC for 3 minutes, and it heated up again at the rate of 20 degreeC/min to 200 degreeC. From the DSC data obtained at the second temperature increase, the temperature of the intersection of the straight line extending the baseline from the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the curve of the step-phase change portion of the glass transition is the maximum, extrapolated glass The transition initiation temperature was calculated|required, and it was made into the glass transition temperature. It evaluated that this glass transition temperature was 125 degreeC or more as being excellent in heat resistance.

<Evaluation of unstretched film>

(8) Forming of film

The unstretched film was manufactured by the following two methods.

In Example 1-1 and Comparative Examples 1-1 to 1-12 mentioned later, press molding was performed with the following procedure, and the unstretched film was manufactured. About 4 g of resin pellets vacuum-dried at 90°C for 5 hours or more, using a spacer having a length of 14 cm, a width of 14 cm, and a thickness of 0.1 mm, a polyimide film is spread on the upper and lower sides of the sample, and the temperature is 200 to 230. After preheating at °C for 3 minutes and pressurizing for 5 minutes under the conditions of a pressure of 40 MPa, the spacer was taken out and cooled to prepare a film. In this method, the thickness accuracy of the film could not be made 5% or less. In addition, in this specification, thickness precision is calculated by the following formula. That is, thickness precision measures the thickness of each position of a film, and shows the ratio with respect to the average value of the difference of the maximum or minimum value of a fluctuation range, and a set value.

Thickness precision [%] = ｜Maximum or minimum value of thickness - Set value｜ / Average value × 100

Moreover, in Examples 1-2-1-6 mentioned later, and Comparative Examples 1-13-1-17, the elongate unstretched film was manufactured by the melt-extrusion method. The melt extrusion method was performed as follows. The resin pellets vacuum-dried at 90 ° C. for 5 hours or more, using a single screw extruder manufactured by Isuzu Chemical Co., Ltd. (screw diameter 25 mm, cylinder set temperature: 220 ° C. to 240 ° C.), T-die (width 200 mm, set temperature: 200-240 degreeC). Cooling the extruded film with a chill roll (set temperature: 120-150 degreeC), it was made into roll shape with the winder, and the elongate unstretched film was manufactured. In addition, in the method described above, by adjusting the lip width of the T-die, the temperature of the chill roll, the distance between the T-die and the chill roll, and the like, it was possible to achieve a film thickness accuracy of 5% or less.

(9) Measurement of refractive index

A rectangular test piece having a length of 40 mm and a width of 8 mm was cut out from the unstretched film produced by the above-described hot press method or melt extrusion method to obtain a measurement sample. By using an interference filter of 589 ㎚ (D-line), (Note) The refractive index n _D was measured by Atago manufacturing the wavelength Abbe refractometer DR-M4 / 1550. The measurement was performed at 20 degreeC using monobromonaphthalene as an interface liquid.

(10) Measurement of total light transmittance

The unstretched film with a film thickness of about 100 micrometers was manufactured by the melt-extrusion method mentioned above, and the total light transmittance was measured using the Nippon Denshoku Industries Co., Ltd. product turbidimeter COH400.

(11) photoelastic modulus

Measurement was performed using a combination of a birefringence measuring device comprising a He-Ne laser, a polarizer, a compensating plate, an analyzer, and a photodetector, and a vibratory viscoelasticity measuring device (DVE-3 manufactured by Rheology). (For details, refer to the Journal of the Japanese Rheological Society Vol. 19, p 93-97 (1991).)

A sample having a width of 5 mm and a length of 20 mm was cut out from the unstretched film produced by any of the methods described above, fixed to a viscoelasticity measuring apparatus, and the storage modulus E' was measured at a room temperature of 25°C at a frequency of 96 Hz. Simultaneously, the emitted laser light is passed through a polarizer, a sample, a compensating plate, and an analyzer in this order, taken by a photodetector (photodiode), and through a lock-in amplifier, for a waveform of angular frequency ω or 2ω, The amplitude and the phase difference with respect to the distortion were calculated|required, and the distortion optical coefficient O' was calculated|required. At this time, the direction of a polarizer and an analyzer was orthogonal, and it adjusted so that it might make|form the angle of pi / 4 with respect to the extending|stretching direction of a sample, respectively. The photoelastic coefficient C was calculated|required from the following formula using the storage elastic modulus E' and the deformation|transformation optical coefficient O'.

C = O'/E'

That this photoelastic coefficient was 20 or less evaluated that it was excellent in a photoelastic characteristic.

(12) modulus of elasticity

A rectangular test piece having a width of 5 mm and a length of 50 mm was cut out from the film obtained by the method described above, and the storage elastic modulus (E') and the loss elastic modulus (E'') were measured. For the measurement, a rheometer RSA-III manufactured by TA Instruments was used in tension mode, the distance between chucks was 20 mm, the temperature was increased at a rate of 3°C/min, the frequency was 1 Hz, and the temperature was for each sample from 0°C under the conditions of 0.1% strain. The temperature was raised to above the glass transition temperature of The storage elastic modulus in 30 degreeC was used for the storage elastic modulus in this invention.

(13) Absorption rate

An unstretched film having a thickness of 100 to 300 µm was produced by any of the methods described above, and the sample was prepared by cutting out a square having a length of 100 mm and a width of 100 mm. Water absorption was measured using this sample in accordance with "Test method for water absorption and boiling water absorption of plastics" described in JIS K 7209.

(14) Toughness of the film (bending test)

An unstretched film having a thickness of 100 to 200 µm was produced by any of the methods described above, and a rectangular test piece having a length of 40 mm and a width of 10 mm was prepared from this film. The distance between the bonding surfaces on the left and right of the vise was widened to 40 mm, and both ends of the test piece were fixed in the bonding surface. Next, by narrowing the gap between the left and right bonding surfaces at a rate of 2 mm/sec or less, the entire film bent into a substantially U shape is compressed within the bonding surface while preventing the film from protruding out of the bonding surface of the vise. did it A case in which the test piece cracks in two pieces (or three or more pieces) at the bent part until the joint surfaces are in perfect contact with each other is "cracked". When it was done, it was called "no cracks". For the same type of film, the test is repeated 5 times, and among them, those with “cracking” 4 or more times are “x: brittle fracture”, and those with “cracking” 3 times or less are “○: brittle fracture” It was evaluated that it is excellent in toughness, saying "do not do not do it", and the thing which does not brittle fracture.

<Evaluation of retardation film>

(15) Stretching of the film

According to the manufacturing method of the above-mentioned unstretched film, the retardation film was manufactured by the following two methods.

About the unstretched film manufactured by the hot press method, it extended|stretched by the following method. A film piece having a width of 50 mm and a length of 125 mm is cut out from the unstretched film, and the glass transition temperature of the resin is +15°C using a batch-type biaxial stretching apparatus (Biaxial stretching apparatus BIX-277-AL manufactured by Ireland Kogyo Co., Ltd.) The free-end uniaxial stretching of the said film piece was performed by extending|stretching temperature, the extending|stretching speed of 300 %/min, and the draw ratio of 1.5 times, and the stretched film was obtained.

About the unstretched film produced by the melt-extrusion method, a stretch rate of 300%/min, a draw ratio of 2 times, and extending|stretching at the extending|stretching temperature of the glass transition temperature of resin +10 degreeC, a stretched film was obtained without breaking The paper and stretching temperature were lowered by 1°C, and it was carried out until the film broke during stretching. Evaluation mentioned later was performed using the stretched film acquired at the extending|stretching temperature one before the fracture|rupture temperature.

(16) Retardation, wavelength dispersion, and birefringence of stretched film

The central portion of the stretched film obtained by the above method was cut to a width of 4 cm and a length of 4 cm, and measuring wavelengths were 450, 500, 550, 590, and 630 nm using a retardation measuring apparatus KOBRA-WPR manufactured by Oji Instruments Co., Ltd. The phase difference was measured and the wavelength dispersion property was measured. The wavelength dispersion was expressed as the ratio (R450/R550) of the retardation R450 and R550 measured at 450 nm and 550 nm. When R450/R550 is greater than 1, the wavelength dispersion is positive, and when R450/R550 is less than 1, the wavelength dispersion is reversed. When used as a quarter wave plate, the ideal value of R450/R550 is 0.818 (450/550 = 0.818).

When the value obtained by subtracting the value of R450/R550 from 1 divided by the molar ratio of the fluorene-based monomer is taken as the expression property of the reverse wavelength dispersion, a value of 0.01 or more is evaluated as excellent in the expression property of the reverse wavelength dispersion did

In addition, as the value of B (R450/R550) in Formulas (1) to (3) of the present invention 1, the wavelength dispersion measured by evaluation using a stretched film obtained from an unstretched film produced by the above hot press method. value of is used.

Moreover, birefringence (DELTA)n was calculated|required from the following formula using the retardation R550 of 550 nm and the thickness of a stretched film.

Birefringence = R550 [nm] / (film thickness [mm] × 10 ⁶ )

It shows that the orientation degree of a polymer is so high that the value of birefringence is high. Moreover, the thickness of the film for obtaining a desired retardation value can be made thin, so that the value of birefringence is large.

＜Comprehensive evaluation＞

Among the above various evaluations, those having no items evaluated as inferior were evaluated as having excellent balance of various characteristics.

<Synthesis example of monomer>

Below, the synthesis method of the monomer used for manufacture of resin is demonstrated.

[Synthesis Example 1] Synthesis of bis(fluoren-9-yl)methane (Compound 1)

[Formula 125]

Fluorene (120 g, 722 mmol) and N,N-dimethylformamide (480 ml) were put in a 1 L 4-neck flask, and after nitrogen substitution, it cooled to 5 degrees C or less. Sodium ethoxide (24.6 g, 361 mmol) was added, and paraformaldehyde (8.7 g, 289 mmol) was added little by little so as not to exceed 10 degreeC, and it stirred. After 2 hours, 1N hydrochloric acid (440 ml) was added dropwise to stop the reaction. The resulting suspended solution was filtered with suction and washed with demineralized water (240 ml). Thereafter, the obtained crude product was dispersed in demineralized water (240 ml) and stirred for 1 hour. After suction filtration, this suspension was water washed with demineralized water (120 ml). After the obtained crude product was dispersed in toluene (480 ml), dehydration was performed under heating and reflux conditions using a Dean-Stark apparatus. After returning to room temperature (20 degreeC), it suction-filtered and dried under reduced pressure at 80 degreeC until it became a constant weight, to obtain 84.0 g of bis(fluoren-9-yl)methane (compound 1) as a white solid (yield: 84.5) %, HPLC purity: 94.0%) was obtained. The chemical shift in <^1> H-NMR spectrum of compound 1 was as follows.

[Synthesis Example 2] Synthesis of bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]methane (Compound 2)

[Formula 126]

Bis(fluoren-9-yl)methane (compound 1, 80 g, 232.3 mmol) obtained above, N-benzyl-N,N,N-triethylammonium chloride (10.6 g, 46.5) in a 1 liter 3-neck flask mmol) and methylene chloride (400 ml) were added, and after nitrogen substitution, the temperature was controlled at 15°C to 20°C in a water bath, and as a result of adding a 50% aqueous sodium hydroxide solution (64 ml), the color of the solution changed to pale red. did Then, ethyl acrylate (50.5 ml, 465 mmol) was dripped over 5 minutes. After 1 hour, ethyl acrylate (25.3 ml, 232 mmol) was further added, and the mixture was stirred for 9 hours while tracking the progress of the reaction by HPLC. After confirming that the mono-adduct was 5% or less by HPLC, the mixture was cooled in an ice bath, and 3N hydrochloric acid (293 ml) was added dropwise in balance with the temperature, followed by quenching. The organic layer was washed with water until the liquid became neutral, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was dispersed in methanol (400 ml) and heated to reflux for 30 minutes, followed by heat washing. Then, it returned to room temperature (20 degreeC), and dried under reduced pressure until it became a constant weight at 80 degreeC after suction filtration, and bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl] as a white solid 96.1 g of methane (compound 2) (yield: 75.9%, HPLC purity: 96.0%) was obtained. The chemical shift in <^1> H-NMR spectrum of compound 2 was as follows.

Moreover, the 5 wt% weight loss temperature (in nitrogen atmosphere) of compound 2 was 295 degreeC, and melting|fusing point was 141 degreeC.

[Synthesis Example 3] Synthesis of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 3)

[Formula 127]

Bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]methane (compound 2, 50.0 g, 91.80 mmol), diphenyl carbonate (98.3 g, 459) obtained above in a 1 liter 4-neck flask mmol) and tetraisopropyl orthotitanate (1.3 ml, 4.59 mmol) were added, the pressure reduction degree was adjusted to 3 kPa, and the temperature range was 145°C to 150°C, followed by stirring for 6 hours while distilling off by-products. . It cooled to 90 degreeC, and after confirming completion|finish of reaction by HPLC, toluene (100 ml) was added and it cooled to 50 degreeC. Methanol (250 ml) was added there, and suction filtration was performed after cooling to 5 degreeC. The obtained white solid was dispersed in toluene (100 ml) and heated to reflux for 30 minutes. After cooling to 50°C, methanol (200 mL) was added. After cooling to room temperature (20 degreeC), suction filtration was performed, and it dried under reduced pressure at 100 degreeC until it became a constant weight, and bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl] as a white solid Methane (compound 3) was obtained in 50 g (yield: 85%, HPLC purity: 98.1%). The chemical shift in <^1> H-NMR spectrum of compound 3 was as follows.

Moreover, the 5 wt% weight loss temperature (in nitrogen atmosphere) of compound 3 was 336 degreeC, and melting|fusing point was 176 degreeC.

[Synthesis Example 4] Synthesis of 1,2-bis(fluoren-9-yl)ethane (Compound 4)

[Formula 128]

Fluorene (2.0 g, 12 mmol) and tetrahydrofuran (35 mL) were placed in a 100 mL four-necked flask, and after nitrogen substitution, the mixture was cooled to -50°C or lower in an ethanol-dry ice bath. 1.6 mol/L n-butyllithium (7.8 ml, 12.5 mmol) was added little by little so as not to exceed -40 degreeC, and it stirred. Then, after heating up to 10 degreeC and stirring for 1 hour, 1,2-dibromoethane (0.55 mL, 6.4 mL) was added, and it stirred for further 2 hours. Thereafter, 1N hydrochloric acid (0.5 ml) was added dropwise, the resulting suspended solution was suction filtered, washed with water, and dried under reduced pressure at 80°C until it became a constant weight, whereby 1,2-bis(fluorene-9) as a white solid. -yl) ethane (compound 4) 0.63 g (yield: 29.2%, HPLC purity: 98.0%) was obtained. Moreover, the solvent of the filtrate was distilled off under reduced pressure, ethanol (25 ml) was added, and it stirred for 30 minutes. The suspension was filtered by suction and dried under reduced pressure at 80°C until it became a constant weight to obtain 0.44 g of 1,2-bis(fluoren-9-yl)ethane (compound 4) as a white solid (yield: 20.5%, HPLC purity). : 84.0%) was obtained. When the obtained white solid was put together, it was 1.07 g (yield: 49.7%). The chemical shift in <^1> H-NMR spectrum of compound 4 was as follows.

[Synthesis Example 5] Synthesis of 1,2-bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]ethane (Compound 5)

[Formula 129]

1,2-bis(fluoren-9-yl)ethane (compound 4, 85 g, 237 mmol) obtained above, tetrahydrofuran (725 ml), N,N-dimethylformamide in a 1 liter 4-neck flask (85 mL) was added, and sodium ethoxide (3.23 g, 47.5 mmol) was added after nitrogen substitution, and the temperature was raised to room temperature (20°C), followed by stirring for 30 minutes. Ethyl acrylate (59.3 ml, 545 mmol) was added dropwise over 2.5 hours. After confirming disappearance of the raw material by HPLC, 0.1 N hydrochloric acid (55 ml) was added dropwise to the reaction solution to stop the reaction. After tetrahydrofuran was distilled off under reduced pressure, toluene (425 ml) was added, and the organic layer was washed with purified water until the liquid became neutral, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was disperse|distributed in methanol (400 ml), and it heat-washed by heating and refluxing for 1 hour. Then, it returned to room temperature (20 degreeC) and dried under reduced pressure until it became a constant weight at 80 degreeC after suction filtration, and, as a white solid, 1,2-bis[9-(2-ethoxycarbonylethyl)fluorene- 101 g (yield: 76.1%, HPLC purity: 98.6%) of 9-yl]ethane (compound 5) was obtained. The chemical shift in <^1> H-NMR spectrum of compound 5 was as follows.

Moreover, the 5 wt% weight loss temperature (in nitrogen atmosphere) of compound 5 was 306 degreeC, and melting|fusing point was 150 degreeC.

[Synthesis Example 6] Synthesis of 1,2-bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]ethane (Compound 6)

[Formula 130]

1,2-bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]ethane (Compound 5, 100.0 g, 179 mmol) obtained by the above method in a 1 liter 4-neck flask, diphenyl carbonate (115 g, 537 mmol) and tetraisopropyl orthotitanate (2.62 ml, 8.95 mmol) were added, and after nitrogen substitution, the temperature was raised to 135°C, followed by stirring for 24 hours. In the middle, at the time of 12 hours and at the time of 20 hours, diphenyl carbonate (38.3 g, 179 mmol) was further added. After confirming the completion of the reaction by HPLC, toluene (400 ml) was added and the mixture was heated to reflux for 1 hour. Suction filtration was performed after cooling to room temperature (20 degreeC). The obtained white solid was dispersed in toluene (300 ml) and heated to reflux for 1 hour. 1,2-bis[9-(2-phenoxycarbonylethyl)fluorene- as a white solid by performing suction filtration after cooling to room temperature (20 degreeC) and drying under reduced pressure until it becomes a constant weight at 80 degreeC 82 g (yield: 70.0%, HPLC purity: 98.0%) of 9-yl]ethane (compound 6) was obtained. The chemical shift in <^1> H-NMR spectrum of compound 6 was as follows.

Moreover, the 5 wt% weight loss temperature (in nitrogen atmosphere) of compound 6 was 337 degreeC, and melting|fusing point was 232 degreeC.

[Synthesis Example 7] Synthesis of bis[9-(3-hydroxypropyl)-fluoren-9-yl]methane (Compound 7)

[Formula 131]

Bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]methane (Compound 2, 50 g, 91.8 mmol) and toluene (250 mL) obtained in Synthesis Example 2 were placed in a 500 mL four-neck flask After nitrogen substitution, the mixture was cooled to 5 ° C. or less in an ice bath, and a 65 wt% toluene solution (82.7 ml, 275 mmol) of sodium bis(2-methoxyethoxy) aluminum hydride (82.7 ml, 275 mmol) was added dropwise while maintaining 10 ° C or less. , and stirred for 1 hour. After confirming disappearance of the raw material by HPLC, ethyl acetate (9.9 ml) was added dropwise, followed by stirring for 30 minutes, and further, 3.1 N aqueous sodium hydroxide solution was added dropwise thereto, followed by stirring for 2 hours. The resulting suspended solution was filtered by suction and washed with demineralized water (100 ml). Thereafter, the obtained crude product was dispersed in demineralized water (150 ml) and stirred for 30 minutes. After suction filtration, water spray washing was performed until the liquid became neutral, and water spray washing was performed with toluene (50 ml). The obtained crude product was dispersed in tetrahydrofuran (150 ml) and dissolved by warming. After returning the tetrahydrofuran solution to room temperature (20°C), it was passed through a silica gel short pass (50 g), washed with tetrahydrofuran (350 ml), and the resulting solution was evaporated under reduced pressure using an evaporator. . The obtained crude product was dispersed in toluene (250 ml), and heated to reflux for 30 minutes, followed by heat washing. After returning to room temperature (20°C), suction filtration, followed by drying under reduced pressure at 80°C until constant weight, as a white solid, bis[9-(3-hydroxypropyl)-fluoren-9-yl]methane ( Compound 7) was obtained in 35.5 g (yield: 83.9%, HPLC purity: 99.8%). Both the sodium content in the solid and the aluminum content were less than 1 ppm. The chemical shift in <^1> H-NMR spectrum of compound 7 was as follows.

Moreover, the 5 wt% weight loss temperature (in nitrogen atmosphere) of compound 7 was 301 degreeC, and melting|fusing point was 214 degreeC.

[Synthesis Example 8] Synthesis of 1,2-bis[9-(3-hydroxypropyl)-fluoren-9-yl]ethane (Compound 8)

[Formula 132]

1,2-bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]ethane (compound 5, 100 g, 179 mmol) obtained in Synthesis Example 5 in a 1 liter 4-neck flask, tetrahydro Furan (500 ml) was added, and after nitrogen substitution, cooled to 5° C. or lower in an ice bath, and maintained at 15° C. or lower, 65 wt% toluene solution of sodium bis(2-methoxyethoxy)aluminum hydride (161 mL, 537) mmol) was added dropwise and stirred for 1 hour. After confirming disappearance of the raw material by HPLC, ethyl acetate (32 mL) was added dropwise, followed by stirring for 45 minutes, and further, 3.1 N aqueous sodium hydroxide solution (257 mL) was added dropwise, followed by stirring for 1 hour. After distilling off tetrahydrofuran under reduced pressure, the obtained suspension solution was suction-filtered, and water washing|cleaning was carried out with demineralized water (100 ml). Then, the obtained crude product was dissolved in ethyl acetate (700 ml), and washed 3 times with demineralized water (100 ml). The organic layer was dried over magnesium sulfate, passed through a silica gel short pass (50 g), washed with tetrahydrofuran (800 ml), and the solvent was evaporated under reduced pressure for the resulting solution with an evaporator. The obtained crude product was dispersed in toluene (400 ml), and heat-washed by heating to reflux for 30 minutes. After returning to room temperature (20 degreeC), 1,2-bis[9-(3-hydroxypropyl)-fluorene-9- as a white solid by drying under reduced pressure at 100 degreeC after suction filtration until it becomes constant weight. 75.6 g of ethyl]ethane (compound 8) (yield: 89.0%, HPLC purity: 98.7%) was obtained. The sodium content in the solid was 2 ppm and the aluminum content was less than 2 ppm. The chemical shift in <^1> H-NMR spectrum of compound 8 was as follows.

Moreover, the 5 wt% weight loss temperature (in nitrogen atmosphere) of compound 8 was 312 degreeC, and melting|fusing point was 253 degreeC.

[Synthesis Example 9] Synthesis of bis(9-hydroxymethylfluoren-9-yl)methane (Compound 9)

[Formula 133]

Bis(fluoren-9-yl)methane (compound 1, 100 g, 290 mmol) and N,N-dimethylformamide (400 ml) obtained in Synthesis Example 1 were placed in a 500 ml four-necked flask, and after nitrogen substitution , paraformaldehyde (18.3 g, 610 mmol) was added. Sodium ethoxide (0.698 g, 13 mmol) was added after cooling to 5 degrees C or less, and it stirred so that it might not exceed 10 degreeC. After 1 hour and a half, 1N hydrochloric acid (32 ml) was added so that the temperature did not exceed 25°C, and the reaction was stopped. Furthermore, water (300 ml) was added and stirred, and the obtained suspension solution was suction-filtered, and it water-washed with demineralized water (100 ml). The obtained crude product was dispersed in tetrahydrofuran (400 ml), and then heated to reflux for 1 hour. After returning to room temperature (20 degreeC), it dried under reduced pressure at 80 degreeC after suction filtration until it became a constant weight, and obtained 108 g (yield: 91%, HPLC purity: 99.1%) of a white solid. The sodium content in the obtained white solid was 620 ppm. Thereafter, the white solid was dispersed in a mixed solution of toluene (800 ml) and water (200 ml), heated to reflux for 1 hour, filtered and dried, and the sodium content in the obtained solid was measured. As a result, it was 390 ppm. . Further, the obtained white solid was dispersed in N,N-dimethylformamide (500 ml), heated to make a uniform solution, cooled to 40° C. or lower, and slowly added dropwise into 0.03 N hydrochloric acid (1500 ml). The resulting suspended solution was filtered with suction, dispersed in demineralized water (200 ml), and stirred for 1 hour. After suction filtration of this suspension, it water-washed with demineralized water (100 ml). After the obtained product was dispersed in toluene (800 ml), azeotropic dehydration was performed under heating and reflux. After returning to room temperature (20°C), suction filtration, followed by drying under reduced pressure at 100°C until constant weight, bis(9-hydroxymethylfluoren-9-yl)methane (compound 9) was obtained as a white solid 104 g (yield) 87%, HPLC purity: 99.8%) was obtained. The content of sodium and chlorine in the solid was less than 10 ppm, respectively. The chemical shift in <^1> H-NMR spectrum of compound 9 was as follows.

_{In addition, the absorption maximum wavelength λ max} in the UV-Vis spectrum (solvent: THF) of Compound 9 existed at 263 nm, 292 nm, and 304 nm. Moreover, the 5 wt% weight loss temperature (in nitrogen atmosphere) of compound 9 was 289 degreeC, and melting|fusing point was 226 degreeC.

[Synthesis Example 10] Synthesis of 1,2-bis(9-hydroxymethylfluoren-9-yl)ethane (Compound 10)

[Formula 134]

1,2-bis(fluoren-9-yl)ethane (compound 4, 100 g, 278.9 mmol) obtained in Synthesis Example 4, paraformaldehyde (17.6 g, 585.8 mmol), N in a 1 liter 4-neck flask ,N-Dimethylformamide (400 ml) was added, and after nitrogen substitution, the mixture was cooled to 10°C or less. Sodium ethoxide (1.80 g, 27.9 mmol) was added, and it heated up to room temperature (20 degreeC), and stirred for 1 hour. After confirming disappearance of the raw material by HPLC, the reaction solution was added dropwise in 0.1 N hydrochloric acid (440 ml) to stop the reaction. The resulting suspended solution was filtered by suction and washed with demineralized water (100 ml). Thereafter, the obtained crude product was dispersed in N,N-dimethylformamide (300 ml) and stirred for 1 hour. This suspension was added dropwise into 0.005 N hydrochloric acid (1000 ml), stirred for 30 minutes, and then filtered with suction. The obtained crude product was dispersed in demineralized water (500 ml) and stirred for 1 hour. After suction filtration of this suspension, it water-washed with demineralized water (200 ml). After the obtained crude product was dispersed in toluene (500 ml), dehydration was performed under heating and reflux conditions using a Dean-Stark apparatus. After returning to room temperature (20 degreeC), it suction-filtered, and dried under reduced pressure at 100 degreeC until it became constant weight, and 1,2-bis(9-hydroxymethylfluoren-9-yl)ethane (compound) as a white solid 10) was obtained (yield: 96.3%, HPLC purity: 99.1%) of 112.4 g. The sodium content in the solid was less than 1 ppm. The chemical shift in <^1> H-NMR spectrum of compound 10 was as follows.

_{In addition, the absorption maximum wavelength λ max} in the UV-Vis spectrum (solvent: THF) of Compound 10 existed at 264 nm, 291 nm, and 302 nm. Moreover, the 5 wt% weight loss temperature (in nitrogen atmosphere) of compound 10 was 301 degreeC, and melting|fusing point was 278 degreeC.

[Synthesis Example 11] Synthesis of 1,2-bis(fluoren-9-yl)butane (Compound 11)

[Formula 135]

Fluorene (3.5 g, 21 mmol), 1,4-butanediol (4.9 g, 54 mmol), 85% KOH (1.52 g, 23 mmol), tetraethylene glycol dimethyl in a 70 ml SUS316 autoclave Ether (4.9 g) was added, and it was made to react at 250 degreeC in nitrogen atmosphere for 8 hours. After cooling, the contents were dispersed in tetrahydrofuran and water, and neutralized with dilute hydrochloric acid. From the obtained suspension solution, the precipitated powder was collected by filtration and washed with water to obtain 1.7 g (yield: 41.9%, HPLC purity: 97.4%) of 1,4-bis(fluoren-9-yl)butane (compound 11) as a white solid. . The chemical shift in <^1> H-NMR spectrum of compound 11 was as follows.

[Synthesis Example 12] Synthesis of 1,2-bis(9-hydroxymethylfluoren-9-yl)butane (Compound 12)

[Formula 136]

1,2-bis(fluoren-9-yl)butane (compound 11, 37.0 g, 95.7 mmol) obtained above, paraformaldehyde (6.03 g, 201 mmol), N,N in a 500 ml four-necked flask -Dimethylformamide (148 ml) was added, and after nitrogen substitution, it cooled to 10 degrees C or less. Sodium ethoxide (0.65 g, 9.6 mmol) was added, and it heated up to room temperature (20 degreeC), and stirred for 1 hour. After confirming disappearance of the raw material by HPLC, the reaction solution was added dropwise into 0.1 N hydrochloric acid (162 ml) to stop the reaction. The resulting suspended solution was filtered by suction and washed with demineralized water (37 ml). After the obtained crude product was dispersed in toluene (185 ml), dehydration was performed under heating and reflux conditions using a Dean-Stark apparatus. 1,2-bis(9-hydroxymethylfluoren-9-yl)butane (compound) as a white solid by returning to room temperature (20°C), filtering with suction, and drying under reduced pressure at 80°C until constant weight 12) was obtained in 39.8 g (yield: 93.1%, HPLC purity: 99.1%). The chemical shift in <^1> H-NMR spectrum of compound 12 was as follows.

_{Moreover, the absorption maximum wavelength λmax} in the UV-Vis spectrum (solvent: THF) of Compound 12 existed at 291 nm and 302 nm. Moreover, the 5 wt% weight loss temperature (in nitrogen atmosphere) of compound 12 was 314 degreeC, and melting|fusing point was 212 degreeC.

[Synthesis Example 13] Synthesis of α,α'-bis-(9-hydroxymethylfluoren-9-yl)-1,4-xylene (Compound 13)

[Formula 137]

α,α'-bis-(fluoren-9-yl)-1,4-xylene (130 g, 0.3 mol), paraformaldehyde (18.9 g, 0.63 mol), N in a 1 liter 4-necked eggplant flask ,N-dimethylformamide (520 ml) was put, and after nitrogen substitution, sodium ethoxide (2.04 g, 0.03 mol) was added, and the mixture was stirred at room temperature (20°C) for 1 hour. 520 ml of demineralized water and 1 N hydrochloric acid (45 ml) were placed in a 1 L beaker, and the reaction solution was added to the stirred place to quench the reaction. The obtained crystal|crystallization was suction-filtered, and it water-washed with demineralized water (100 ml). After dispersing the obtained crude product in demineralized water (500 ml), it was filtered by suction and washed with water with demineralized water (100 ml). After the obtained crude product was dispersed in toluene (500 ml), dehydration was performed under heating and reflux conditions using a Dean-Stark apparatus. After returning to room temperature (20 degreeC), it filtered with suction and dried under reduced pressure at 70 degreeC until it became a constant weight, 130 g (yield: 87%, HPLC purity: 97.6%) of a white solid (compound 13) was obtained. The chemical shift in <^1> H-NMR spectrum of compound 13 was as follows.

Moreover, the 5 wt% weight loss temperature (in nitrogen atmosphere) of compound 13 was 327 degreeC, and melting|fusing point was 198 degreeC.

[Synthesis Example 14] Synthesis of 1,2-bis(9-hydroxyfluoren-9-yl)ethane (Compound 14)

[Formula 138]

1,2-bis(fluoren-9-yl)ethane (compound 4, 20 g, 59 mmol) obtained by the method of Synthesis Example 4 in a 1 liter 4-neck flask, N,N-dimethylformamide (200 ml) was added, tributyl phosphite (37.9 ml, 140 mmol) was added, and after nitrogen substitution, benzyltrimethylammonium hydroxide (40% methanol solution) (25 ml) was added, and air (100 ml/min) and A mixed gas of nitrogen (300 ml/min) was passed through the reaction system. After stirring for 3 hours, benzyltrimethylammonium hydroxide (40% methanol solution) (10 ml) was added and stirred for 5 hours. Furthermore, benzyltrimethylammonium hydroxide (40% MeOH solution) (10 mL) was added, and it stirred for further 1 hour. 1N hydrochloric acid (200 mL) was added to stop the reaction, and ethyl acetate (400 mL) was added to carry out liquid separation operation. Furthermore, the organic layer was washed 3 times with saturated brine (100 ml). The organic layer was dried over magnesium sulfate, filtered, and the organic solvent was distilled off under reduced pressure. Toluene (100 ml) and hexane (200 ml) were added to the resulting suspension solution, stirred for 30 minutes, filtered with suction, and dried under reduced pressure at 80 ° C. until a constant weight was obtained. As a white solid, 1,2-bis ( 13.9 g (yield: 63.8%, HPLC purity: 92.5%) of 9-hydroxyfluoren-9-yl)ethane (Compound 14) was obtained. The chemical shift in <^1> H-NMR spectrum of compound 14 was as follows.

[Synthesis Example 15] Synthesis of bis-{[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl}ethane (Compound 15)

[Formula 139]

1,2-bis(fluoren-9-yl)ethane (compound 14, 17 g, 45 mmol) and phenoxyethanol (37 g, 267 mmol) obtained by the above method were placed in a 300 ml four-necked flask, After nitrogen substitution, it was cooled to 10 °C or less. A boron trifluoride-diethyl ether complex (5.6 ml, 45 mmol) was added, and after stirring at room temperature (20° C.) for 3 hours, further boron trifluoride-diethyl ether complex (5.6 ml, 45 mmol) was added. ), chloroform (35 ml) was added, and the mixture was stirred at 40°C for 4 hours and at 60°C for 2 hours. Further, boron trifluoride-diethyl ether complex (5.6 ml, 45 mmol) was added, and the mixture was refluxed under superheat for 2 hours. After cooling to room temperature (20 DEG C), neutralization was performed using a saturated aqueous sodium hydrogen carbonate solution, and then insoluble matter was removed by suction filtration. Ethyl acetate (120 ml) was added, and the organic layer was washed twice with saturated brine and once with demineralized water, dried over magnesium sulfate, filtered, and the organic solvent was distilled off under reduced pressure. Again, it was dissolved in ethyl acetate (150 ml), activated carbon (Nippon Norrit Co., Ltd., SXPLUS, pH = 7, 2.5 g) was added, stirred for 1 hour, filtered through Celite, and the organic solvent was distilled off under reduced pressure. . Methanol (100 ml) was added, stirred for 1 hour, filtered with suction, and dried under reduced pressure at 80°C until constant weight, thereby forming bis-{[4-(2-hydroxyethoxy)phenyl]flu as a white solid. Oren-9-yl}ethane (Compound 15) was obtained in 15.8 g (yield: 56.1%, HPLC purity: 86%). The chemical shift in <^1> H-NMR spectrum of compound 15 was as follows.

[Synthesis Example 16] Synthesis of fluorene-9,9-diethanol (Compound 16)

[Formula 140]

It was synthesized according to the method described in Japanese Patent Application Laid-Open No. 2010-261008.

<Synthesis example and characteristic evaluation of resin>

The abbreviations of the compounds used in the following Examples and Comparative Examples are as follows.

BHEPF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]-fluorene (manufactured by Osaka Gas Chemical Co., Ltd.)

BCF: 9,9-bis(4-hydroxy-3-methylphenyl)-fluorene (manufactured by Osaka Gas Chemical Co., Ltd.)

・DPC: diphenyl carbonate (manufactured by Mitsubishi Chemical Co., Ltd.)

・ISB: Isosorbide (manufactured by Rocket Frere, trade name: POLYSORB)

CHDM: 1,4-cyclohexanedimethanol (cis, trans mixture, manufactured by SK Chemicals)

・TCDDM: tricyclodecane dimethanol (manufactured by Oxea)

・SPG: Spiroglycol (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

・BPA: 2,2-bis[4-hydroxyphenyl]propane (manufactured by Mitsubishi Chemical Co., Ltd.)

・PEG: Polyethylene glycol number average molecular weight: 1000 (manufactured by Sanyo Chemical Co., Ltd.)

·CHDA: 1,4-cyclohexanedicarboxylic acid (cis, trans mixture, manufactured by Eastman Chemicals)

・DMT: Dimethyl terephthalate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Example 1-1]

Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 3) 38.06 parts by mass (0.059 mol), 53.73 parts by mass (0.368 mol) of ISB, 9.64 parts by mass (0.067 mol) of CHDM , DPC 81.28 parts by mass (0.379 mol), and 3.83 x 10 ^-4 parts by mass (2.17 x 10 ^-6 mol) of calcium acetate monohydrate as a catalyst were charged into the reaction vessel, and the inside of the reaction apparatus was purged with reduced pressure nitrogen. In a nitrogen atmosphere, the raw material was dissolved at 150°C for about 10 minutes while stirring. As the first step of the reaction, the temperature was raised to 220°C over 30 minutes, and the reaction was carried out at normal pressure for 60 minutes. Next, the pressure was reduced from the normal pressure to 13.3 kPa over 90 minutes, maintained at 13.3 kPa for 30 minutes, and generated phenol was taken out of the reaction system. Subsequently, the pressure was reduced to 0.10 kPa or less over 15 minutes while raising the heat medium temperature to 240°C over 15 minutes as a step of the second stage of the reaction, and the generated phenol was taken out of the reaction system. After reaching a predetermined stirring torque, the reaction was stopped by returning the pressure to normal pressure with nitrogen, and the resulting polyester carbonate was extruded into water, and the strands were cut to obtain pellets. Various evaluations mentioned above were performed using the obtained polyester carbonate pellet. Table 1 shows the evaluation results.

In the polyester carbonate of Example 1-1, the content of the oligofluorene structural unit derived from compound 3 is 27.0 mass %, which is a small amount, but the wavelength dispersion (R450/R550) of the retardation film is 0.835, and the reverse wavelength dispersion is It can be understood that the expression property is as high as 0.025. Moreover, the polyester carbonate of Example 1-1 had a low photoelastic coefficient, and the glass transition temperature became the value excellent in the balance of melt processability and heat resistance at 143 degreeC.

[Comparative Example 1-1]

1,2-bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]ethane (Compound 6) 45.69 parts by mass (0.070 mol), ISB 43.13 parts by mass (0.295 mol), CHDM 15.64 parts by mass (0.108 mol), 72.36 parts by mass of DPC (0.338 mol), and 3.55 x 10 ^-4 parts by mass of ^{calcium acetate monohydrate (2.02 x 10 -6} mol) were synthesized in the same manner as in Example 1-1, Polyester carbonate pellets were obtained. Various evaluations mentioned above were performed using the obtained polyester carbonate pellet. Table 1 shows the evaluation results.

Although the polyester carbonate of Comparative Example 1-1 also had high reverse wavelength dispersion and excellent mechanical properties, the photoelastic properties were inferior.

[Comparative Example 1-2]

Bis[9-(3-hydroxypropyl)-fluoren-9-yl]methane (Compound 7) 35.02 parts by mass (0.076 mol), ISB 40.75 parts by mass (0.279 mol), CHDM 12.71 parts by mass (0.088 mol), Synthesis was carried out in the same manner as in Example 1-1 except that 95.85 parts by mass (0.447 mol) of DPC and 3.90 x 10 ^-4 parts by mass (2.22 x 10 ^{-6 mol) of calcium acetate monohydrate were used, and polycarbonate pellets were prepared} got it The various evaluations mentioned above were performed using the obtained polycarbonate pellet. Table 1 shows the evaluation results.

Although the polycarbonate of Comparative Example 1-2 also had comparatively excellent characteristics, it was inferior to the developability of reverse wavelength dispersion|distribution.

[Comparative Example 1-3]

1,2-bis[9-(3-hydroxypropyl)-fluoren-9-yl]ethane (Compound 8) 37.92 parts by mass (0.080 mol), 42.45 parts by mass (0.290 mol) of ISB, 8.47 parts by mass of CHDM ( 0.059 mol), DPC 92.84 parts by mass (0.433 mol), and 3.78 x 10 ^-4 parts by mass (2.15 x 10 ^-6 mol) of calcium acetate monohydrate were synthesized in the same manner as in Example 1-1, and poly A pellet of carbonate was obtained. The various evaluations mentioned above were performed using the obtained polycarbonate pellet. Table 1 shows the evaluation results.

The polycarbonate of Comparative Example 1-3 was inferior in the developability of reverse wavelength dispersion|distribution and the photoelastic property.

[Comparative Example 1-4]

Bis(9-hydroxymethylfluoren-9-yl)methane (Compound 9) 28.19 parts by mass (0.070 mol), ISB 42.45 parts by mass (0.290 mol), CHDM 16.95 parts by mass (0.118 mol), DPC 103.35 parts by mass ( 0.482 mol) and 1.68 x 10 ^-3 mass parts (9.55 x 10 ^-6 mol) of calcium acetate monohydrate were synthesized in the same manner as in Example 1-1 to obtain polycarbonate pellets. The various evaluations mentioned above were performed using the obtained polycarbonate pellet. Table 1 shows the evaluation results.

Compound 9 is a compound capable of introducing the same oligofluorene structural unit as the fluorene-based monomer used in Example 1-1 or Comparative Examples 1-1 to 1-3, but the polycarbonate using Compound 9 has unexpectedly reverse wavelength dispersion. did not show This is presumed to be due to the fact that the fluorene ring of compound 9 is not oriented in a direction perpendicular to the stretching direction.

[Comparative Example 1-5]

1,2-bis(9-hydroxymethylfluoren-9-yl)ethane (Compound 10) 47.08 parts by mass (0.112 mol), ISB 29.71 parts by mass (0.203 mol), CHDM 12.71 parts by mass (0.088 mol), DPC Except having used 87.40 mass parts (0.408 mol) and 7.12 x 10 ^-4 mass parts (4.04 x 10 ^-6 mol) of calcium acetate monohydrate, it synthesize|combined similarly to Example 1-1, and the polycarbonate pellet was obtained. . The various evaluations mentioned above were performed using the obtained polycarbonate pellet. Table 1 shows the evaluation results.

The resin of this example did not show reverse wavelength dispersion property similarly to Comparative Example 1-4.

[Comparative Example 1-6]

1,2-bis(9-hydroxymethylfluoren-9-yl)butane (Compound 12) 32.13 parts by mass (0.072 mol), ISB 43.30 parts by mass (0.296 mol), CHDM 12.71 parts by mass (0.088 mol), DPC Except having used 98.74 mass parts (0.461 mol) and 8.04 x 10 ^-4 mass parts (4.56 x 10 ^-6 mol) of calcium acetate monohydrate, it synthesize|combined similarly to Example 1-1, and the polycarbonate pellet was obtained. . The various evaluations mentioned above were performed using the obtained polycarbonate pellet. Table 1 shows the evaluation results.

The resin of this example did not show reverse wavelength dispersion property similarly to Comparative Example 1-4.

[Comparative Example 1-7]

Bis(9-hydroxymethylfluoren-9-yl)methane (Compound 9) 33.85 parts by mass (0.084 mol), 28.97 parts by mass (0.201 mol) of CHDM, 48.03 parts by mass (0.279 mol) of CHDA, and tetra- as a catalyst ^{Except having used 9.49 x 10 -3} mass parts (2.79 x 10 ^-5 mol) of n-butyl titanate, it synthesize|combined similarly to Example 1-6, and obtained the polyester pellet. The various evaluations mentioned above were performed using the obtained polyester pellet. Table 1 shows the evaluation results.

In this example, although polyester was synthesize|combined from the compound 9 used with the polycarbonate of Comparative Example 1-4, reverse wavelength dispersion property was not shown also in polyester.

[Comparative Example 1-8]

α,α'-bis-(9-hydroxymethylfluoren-9-yl)-1,4-xylene (Compound 13) 38.00 parts by mass (0.077 mol), ISB 33.96 parts by mass (0.232 mol), CHDM 16.95 Synthesis was carried out in the same manner as in Example 1-1 except that parts by mass (0.118 mol), 92.32 parts by mass (0.431 mol) of DPC, and 7.52 x 10 ^-4 parts by mass (4.27 x 10 ^{-6 mol) of calcium acetate monohydrate were used.} and polycarbonate pellets were obtained. The various evaluations mentioned above were performed using the obtained polycarbonate pellet. Table 1 shows the evaluation results.

The resin of this example did not show reverse wavelength dispersion property similarly to Comparative Example 1-4. From the results of Comparative Examples 1-4 to 1-8, it is considered that the distance between the carbonyl group and the fluorene ring contained in the carbonate group or the ester group affects the presence or absence of reverse wavelength dispersion. When the distance between the carbonyl group and the fluorene ring is too close, it is presumed that the fluorene ring cannot be oriented in a preferred direction due to steric hindrance of the carbonyl group, and reverse wavelength dispersion is not exhibited.

[Comparative Example 1-9]

Bis-{[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl}ethane (Compound 15) 37.46 parts by mass (0.059 mol), ISB 39.05 parts by mass (0.267 mol), CHDM 12.71 parts by mass ( 0.088 mol), DPC 89.73 mass parts (0.419 mol), and calcium acetate monohydrate 7.31 x 10 ^-4 mass parts (4.15 x 10 ^-6 mol) were synthesized in the same manner as in Example 1-1, and poly A pellet of carbonate was obtained. The various evaluations mentioned above were performed using the obtained polycarbonate pellet. Table 1 shows the evaluation results.

The resin of this example had a wavelength dispersion (R450/R550) value close to 1, and had flat wavelength dispersion. In the resin of this example, when the amount of the structural unit derived from compound 15 is increased, it is estimated that reverse wavelength dispersion property is exhibited, but it is judged that the expression property of reverse wavelength dispersion is low.

[Comparative Example 1-10]

Fluorene-9,9-diethanol (Compound 16) 32.66 parts by mass (0.128 mol), 54.34 parts by mass (0.372 mol) of ISB, 109.30 parts by mass (0.510 mol) of DPC, 1.32×10 ^-3 parts by mass of calcium acetate monohydrate Except having used (7.50 x 10 ^-6 mol), it synthesize|combined similarly to Example 1-1, and obtained the pellet of polycarbonate. The various evaluations mentioned above were performed using the obtained polycarbonate pellet. Table 1 shows the evaluation results.

Although the resin of this example showed reverse wavelength dispersion property, the expression property of reverse wavelength dispersion property was inferior, and the photoelastic coefficient was also high. In addition, in this example, the foaming of the resin at the time of polymerization or melt film forming was slightly much, and it was a mode that thermal stability was inferior.

[Comparative Example 1-11]

BHEPF 68.07 parts by mass (0.155 mol), ISB 22.84 parts by mass (0.156 mol), PEG 0.97 parts by mass (9.75×10 ^-4 mol), DPC 67.60 parts by mass (0.316 mol), magnesium acetate tetrahydrate 5.36×10 ^-4 mass Except having used part (2.50 x 10 ^-6 mol), it synthesize|combined similarly to Example 1-1, and obtained the pellet of polycarbonate. The various evaluations mentioned above were performed using the obtained polycarbonate pellet. Table 1 shows the evaluation results.

It can be understood that the resin of this example has a very large content of the structural unit derived from BHEPF of 67.8 mass %, and is poor in the expression property of the reverse wavelength dispersion of this structural unit. Moreover, the photoelastic coefficient also became a high value.

[Comparative Example 1-12]

BCF 41.17 parts by mass (0.109 mol), SPG 51.59 parts by mass (0.170 mol), DPC 63.19 parts by mass (0.295 mol), and 4.90 x 10 ^-3 parts by mass (2.78 x 10 ^-5 mol) of calcium acetate monohydrate were used, Except having set the final polymerization temperature to 260 degreeC, it synthesize|combined similarly to Example 1-1, and obtained the pellet of polycarbonate. The various evaluations mentioned above were performed using the obtained polycarbonate pellet. Table 1 shows the evaluation results.

Although the resin of this example showed comparatively excellent optical properties, the obtained film was very brittle and had poor toughness to be prone to cracking.

In Examples 1-2 to 6 and Comparative Examples 1-13 to 1-17 below, resins were synthesized using larger polymerization equipment, and elongated films were produced by melt extrusion method to evaluate various properties. carried out. In particular, stretching was performed under conditions near the fracture limit, and the birefringence (orientation property) of the stretched film was evaluated.

[Example 1-2]

Polymerization was carried out using a batch polymerization apparatus comprising two vertical reactors equipped with stirring blades and a reflux condenser controlled at 100°C. Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 3) 36.94 parts by mass (0.058 mol), ISB 64.02 parts by mass (0.438 mol), DPC 82.43 parts by mass (0.385 mol) ^{and 3.86 x 10 -4} parts by mass (2.19 x 10 ^-6 mol) of calcium acetate monohydrate as a catalyst. After replacing the inside of the reactor with reduced pressure nitrogen, heating was performed with a heat medium, and stirring was started when the internal temperature reached 100°C. The internal temperature was made to reach 220 degreeC 40 minutes after the start of temperature increase, and while controlling so that this temperature might be maintained, pressure reduction was started and it was set to 13.3 kPa in 90 minutes after reaching 220 degreeC. The phenol vapor produced by the polymerization reaction was guided to a reflux condenser at 100° C., the monomer component contained in a small amount in the phenol vapor was returned to the reactor, and the phenol vapor that was not condensed was recovered by inducing it to a condenser at 45° C. After nitrogen was introduced into the first reactor and the pressure was returned to atmospheric pressure, the oligomerized reaction solution in the first reactor was transferred to the second reactor. Next, the temperature increase and pressure reduction in the 2nd reactor were started, and it was set as the internal temperature of 240 degreeC and the pressure of 0.2 kPa in 50 minutes. Thereafter, polymerization was allowed to proceed until a predetermined stirring power was reached. When a predetermined power was reached, nitrogen was introduced into the reactor and the pressure was restored, the resulting polyester carbonate was extruded into water, and the strands were cut to obtain pellets.

From the obtained polyester carbonate, a long unstretched film having a length of 3 m, a width of 200 mm, and a thickness of 72 μm was prepared using the melt extrusion method described above. Then, longitudinal uniaxial stretching was performed by the method described above, and a retardation film was prepared under conditions near the fracture limit. Table 2 shows the results of various evaluations.

The retardation film of this example exhibited reverse wavelength dispersion and was excellent in all characteristics, such as orientation degree, photoelastic coefficient, heat resistance, and toughness.

[Example 1-3]

Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 3) 38.06 parts by mass (0.059 mol), ISB 43.06 parts by mass (0.295 mol), CHDM 20.28 parts by mass (0.141 mol) , DPC 81.46 parts by mass (0.380 mol), calcium acetate monohydrate 3.83 × 10 ^-4 mass parts (2.18 × 10 ^-6 mol) was used, Example 1-2 except that the thickness of the unstretched film was 66 μm In the same manner as to prepare a retardation film. Table 2 shows the results of various evaluations.

Since the retardation film of this example has a larger value of birefringence than Example 1-2, it can be understood that the orientation degree of a polymer is high.

[Example 1-4]

Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 3) 31.02 parts by mass (0.048 mol), ISB 43.08 parts by mass (0.295 mol), TCDDM 25.26 parts by mass (0.129 mol) Example 1-2 except that 81.26 parts by mass of DPC (0.379 mol), 3.73 × 10 ^-4 parts by mass of ^{calcium acetate monohydrate (2.12 × 10 -6} mol) were used, and the thickness of the unstretched film was 73 μm. In the same manner as to prepare a retardation film. Table 2 shows the results of various evaluations.

The retardation film of this example had comparatively high orientation and the photoelastic coefficient became low.

[Example 1-5]

Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 3) 29.60 parts by mass (0.046 mol), ISB 29.21 parts by mass (0.200 mol), SPG 42.28 parts by mass (0.139 mol) Example 1-2 except that 63.77 parts by mass (0.298 mol) of DPC, 1.19 × 10 ^-2 parts by mass (6.78 × 10 ^-5 mol) of calcium acetate monohydrate, and the thickness of the unstretched film was 62 µm In the same manner as to prepare a retardation film. Table 2 shows the results of various evaluations.

The retardation film of this example was excellent in birefringence and photoelastic coefficient than Example 1-2.

[Example 1-6]

Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 3) 29.18 parts by mass (0.046 mol), ISB 30.38 parts by mass (0.208 mol), SPG 41.27 parts by mass (0.136 mol) Example 1-2 except that 64.55 parts by mass (0.298 mol) of DPC, 1.21 x 10 ^-2 parts by mass (6.86 x 10 ^-5 mol) of calcium acetate monohydrate, and the thickness of the unstretched film were 58 µm. In the same manner as to prepare a retardation film. Table 2 shows the results of various evaluations.

In the retardation film of this example, by weakening the reverse wavelength dispersion compared to Example 1-2, the value of birefringence could be made larger than Example 1-2, and the orientation degree of a polymer was able to be improved. The retardation film of this example is farther from the ideal value of R450/R550 than in Example 1-2, but when thinning of the film is important due to the use, the retardation film of Example 1-6 can be suitably used.

[Comparative Example 1-13]

BHEPF 63.72 parts by mass (0.145 mol), ISB 26.74 parts by mass (0.183 mol), PEG 0.97 parts by mass (9.75 x 10 ^-4 mol), DPC 71.24 parts by mass (0.333 mol), magnesium acetate tetrahydrate 7.06 x 10 ^-4 mass A retardation film was manufactured in the same manner as in Example 1-2 except that part (3.29 × 10 ^-6 mol) was used and the thickness of the unstretched film was 76 µm. Table 2 shows the results of various evaluations.

It can be understood that the retardation film of the present example is inferior in orientation and reverse wavelength dispersion and photoelastic coefficient compared with Examples.

[Comparative Example 1-14]

BHEPF 68.07 parts by mass (0.155 mol), ISB 22.84 parts by mass (0.156 mol), PEG 0.97 parts by mass (9.75×10 ^-4 mol), DPC 67.60 parts by mass (0.316 mol), magnesium acetate tetrahydrate 5.36×10 ^-4 mass A retardation film was manufactured in the same manner as in Example 1-2 except that part (2.50 × 10 ^-6 mol) was used and the thickness of the unstretched film was 87 µm. Table 2 shows the results of various evaluations.

The retardation film of this example made the wavelength dispersion property of Comparative Example 1-13 close to the ideal value of R450/R550, but by strengthening the reverse wavelength dispersion, the orientation fell and the expressivity of the reverse wavelength dispersion was also inferior.

[Comparative Example 1-15]

32.20 parts by mass of BCF (0.085 mol), 60.43 parts by mass of SPG (0.199 mol), 64.40 parts by mass of DPC (0.301 mol), and 5.00 x 10 ^-3 parts by mass of ^{calcium acetate monohydrate (2.84 x 10 -5} mol) were used, A retardation film was prepared in the same manner as in Example 1-2 except that the final polymerization temperature was 260°C and the thickness of the unstretched film was 76 µm. Table 2 shows the results of various evaluations.

The retardation film of this example was inferior in orientation and the expressivity of reverse wavelength dispersion|distribution, and had the fault that a film was soft.

[Comparative Example 1-16]

BHEPF 80.49 parts by mass (0.184 mol), BPA 13.23 parts by mass (0.058 mol), DPC 53.29 parts by mass (0.249 mol), and 2.13 x 10 ^-3 parts by mass of ^{calcium acetate monohydrate (1.21 x 10 -5} mol) were used, A retardation film was prepared in the same manner as in Example 1-2 except that the final polymerization temperature was 260°C and the thickness of the unstretched film was 98 µm. Table 2 shows the results of various evaluations.

In the retardation film of this example, the birefringence fell significantly compared with the Example. Moreover, the photoelastic coefficient also became large. Since there was much quantity of the aromatic structure on a principal chain, and since the quantity of the aromatic component for expressing reverse dispersibility was also required large, it is thought that the fall of the optical characteristic was brought about.

[Comparative Example 1-17]

BHEPF 86.84 parts by mass (0.198 mol), DMT 14.95 parts by mass (0.077 mol), DPC 28.90 parts by mass (0.135 mol), tetra-n-butyl titanate 1.35 x 10 ^-2 parts by mass (3.96 x 10 ^-5 mol) A retardation film was prepared in the same manner as in Example 1-2 except that the final polymerization temperature was 260°C and the thickness of the unstretched film was 148 µm. Table 2 shows the results of various evaluations.

Also in the retardation film of this example, compared with an Example, birefringence fell large and the photoelastic coefficient also became large.

«Examples 2-1 to 2-2, Reference Examples 2-1 to 2-2»

The quality evaluation of the trifluorenediester of this invention, and the characteristic evaluation of the resin composition and a transparent film were implemented by the following method. In addition, the characteristic evaluation method is not limited to the following method, A person skilled in the art can select suitably.

In addition, the abbreviation of the compound used in the following synthesis example and an Example, etc. are as follows.

ISB: Isosorbide (manufactured by Rocket Frere, trade name: POLYSORB)

DPC: Diphenyl carbonate (manufactured by Mitsubishi Chemical Co., Ltd.)

CHDM: 1,4-cyclohexanedimethanol (cis, trans mixture, manufactured by SK Chemicals)

SPG: Spiroglycol (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

BHEPF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]-fluorene (manufactured by Osaka Gas Chemical Co., Ltd.)

THF: tetrahydrofuran (without stabilizer, manufactured by WAKO)

(1) Thermal decomposition temperature of oligofluorene monomer (TG-DTA)

The decomposition initiation temperature and melting point of the oligofluorene monomer were measured using a differential thermogravimetric simultaneous analyzer (TG-DTA6300 manufactured by SI Nanotechnology). About 4 mg of the analysis sample was put into an aluminum pan manufactured by the company, sealed, and the temperature was raised from room temperature (20 to 30°C) to 600°C at a temperature increase rate of 10°C/min under a nitrogen stream of 200 ml/min. From the obtained TG data (thermogravimetric data), the temperature of the intersection of the low-temperature side baseline extrapolated baseline of the weight loss behavior and the tangent to the weight loss maximum inclination point was set as the decomposition start temperature. Further, from the obtained TG data (thermogravimetric data), the peak top in which a decrease in sample weight was not confirmed and a steep endothermic peak was observed was set as the melting point of the sample.

(2) Content ratio of Na, K, Cs, Fe in the resin composition

About 0.5 g of a resin composition sample was precisely weighed in a microwave decomposition vessel manufactured by Perkin Elmer, and 2 ml of 97% sulfuric acid (ultra-high purity sulfuric acid manufactured by Tama Chemical) was added thereto, sealed and microwave-heated at 230°C for 10 minutes. . After cooling to room temperature (30°C or less), 1.5 ml of 68% nitric acid (ultra-high-purity nitric acid manufactured by Tama Chemical) is added, sealed and microwave-heated at 150°C for 10 minutes, and then again to room temperature (30°C or less) It cooled, 2.5 ml of 68% nitric acid was added, it was made into a sealed state again, and it microwave-heated at 230 degreeC for 10 minute(s), and the content was completely decomposed|disassembled. The microwave heater used Multiwave3000 manufactured by Perkin Elmer, Inc., and adjusted the temperature by adjusting the output between 300 W and 1000 W. After cooling to room temperature (30°C or lower), the obtained solution was diluted with pure water and quantified by ICP-MS manufactured by Thermoquest.

(3) Residual monohydroxy compound in resin composition

About 1 g of the resin composition sample was precisely weighed and dissolved in 5 ml of methylene chloride, and then acetone was added so that the total amount was 25 ml. The solution was filtered with a 0.2 µm disk filter and phenol was quantified by liquid chromatography, and then the content was calculated.

(4) Toughness of the film (bending test)

A film having a thickness of 100 to 200 µm was molded by the method using the hot press described above, and a rectangular test piece having a length of 40 mm and a width of 10 mm was prepared from this film. The distance between the bonding surfaces on the left and right of the vise was widened to 40 mm, and both ends of the test piece were fixed in the bonding surface. Next, the gap between the left and right bonding surfaces was narrowed at a speed of 2 mm/sec or less, and the entire film bent in the letter "K" was compressed within the bonding surface while preventing the film from protruding out of the bonding surface of the vise. . If the test piece cracks in two pieces (or more than three pieces) at the bent part until the joint surfaces are in perfect contact, "There is a crack"; ' he said. The test is repeated 5 times for the same type of film, and among them, "x: brittle fracture" for 4 or more times "with cracks", and 3 or less times for "with cracks", "○: brittle fracture" I don't do it,' he said.

(5) Measurement of refractive index and Abbe number

A rectangular test piece having a length of 40 mm and a width of 8 mm was cut out from the film obtained by the method by the hot press described above to obtain a measurement sample. With a multi-wavelength Abbe refractometer (DR-M4/1550 manufactured by Atago Co., Ltd.), the refractive index of each wavelength using an interference filter of wavelengths 656 nm (C line), 589 nm (D line), and 486 nm (F line); nC, nD, and nF were measured. The measurement was performed at 20 degreeC using monobromonaphthalene as an interface liquid. The Abbe number νd was calculated by the following equation.

νd = (1 - nD) / (nC - nF)

The larger the Abbe number, the smaller the wavelength dependence of the refractive index.

Measurements of the reduced viscosity, glass transition temperature, melt viscosity, and photoelastic coefficient of the resin composition are the same as in Example 1-1 described above.

<Example 2-1>

Bis{[9-(2-ethoxycarbonylethyl)fluoren-9-yl]-methyl}fluorene (Compound 3) and bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl ]Synthesis of methane (compound 2)

[Formula 141]

35.0 g (102 mmol) of bis(fluoren-9-yl)methane (Compound 1) and 175 ml of THF were added to a 1-L separable flask, and it stirred at 15 degreeC in nitrogen atmosphere. After adding 28.68 g of 50 wt% sodium hydroxide aqueous solution and 4.61 g (20.2 ml) of benzyl triethylammonium chloride, it stirred for 15 minutes. After adding 22.4 ml (224 mmol) of ethyl acrylate over 60 minutes, it aged at 16 degreeC for 2 hours. As a result of performing HPLC analysis at the time of completion|finish of reaction, compound 2 (13.5 min) was 75.3 area%, and compound 3 (15.2 min) was 8.4 area%. After neutralization with 3 N hydrochloric acid, the liquid was separated to remove the aqueous layer. 70 ml of toluene was added here, and the organic layer was wash|cleaned 5 times with 105 ml of water. After adding 35 ml of toluene and 35 ml of THF to the organic layer, the mixture was concentrated under heating and reduced pressure to 70 ml while maintaining the internal temperature of 60° C. or higher. After adding 35 ml of toluene, it stood to cool to 45 degreeC, methanol 210 ml was added, and bis [9-(2-ethoxycarbonylethyl) fluoren-9-yl] methane (compound 2) was crystallized. did White crystals of bis{[9-(2-ethoxycarbonylethyl)fluoren-9-yl]-methyl}fluorene (Compound 3) generated by filtering the crystallized product and allowing the filtrate to stand at room temperature for several days was recovered by filtration.

Bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]methane (Compound 2): 37.47 g (68.7 mmol, Yield: 67.6%), white powder

HPLC analysis result Compound 2 (13.5 min): 91.7 area%, Compound 3 (15.2 min): 5.2 area%

Decomposition initiation temperature (in nitrogen atmosphere): 295 °C

m.p.: 141 °C

Bis{[9-(2-ethoxycarbonylethyl)fluoren-9-yl]-methyl}fluorene (Compound 3): 0.20 g (0.3 mmol, Yield: 0.3%), white crystals

HPLC analysis result Compound 2 (13.5 min): 3.5 area%, Compound 3 (15.2 min): 92.6 area%

Decomposition initiation temperature (under nitrogen atmosphere): 364 °C

m.p.：166 ℃

In addition, after completion|finish of reaction, HPLC after crystallization and filtration were all implemented on condition of the following.

Column: Inertsil ODS-3V 150 mm x 4.8 mm φ

Temperature: 40 degrees Celsius

Eluent conditions: 0-5 min: tetrahydrofuran/water = 50/50, 20 min: tetrahydrofuran/water = 100/0

Flow rate: 1.0 ml/min

Injection amount: 2 μl

<Example 2-2>

Bis{[9-(2-phenoxycarbonylethyl)fluoren-9-yl]-methyl}fluorene (compound 5) and bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl ]Synthesis of methane (compound 4)

[Formula 142]

Bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]methane (compound 2, 84.1 g, 154.5 mmol) and bis{[9-(2-ethoxy In a tetrahydrofuran/o-xylene mixed solution containing carbonylethyl)fluoren-9-yl]-methyl}fluorene (Compound 3, 3.3 g, 6.9 mmol), diphenyl carbonate (147.5 g, 5685.5 After the mmol) addition, the internal temperature was gradually raised to 104°C, and then the pressure was reduced to 3 kPa, and the solvent was distilled off. The pressure was restored, and tetraisopropyl orthotitanate (2.45 g, 8.61 mmol) was added thereto, the pressure was reduced to 3 kPa again, and the reaction effluent was distilled off while gradually raising the temperature to 184°C. After reaching 184°C, the reaction was carried out for 3 hr, the temperature was lowered to 90°C and the pressure was restored, and the progress of the reaction was confirmed by HPLC analysis. o-xylene (144 ml) was added, and when the temperature was lowered to 41°C, precipitation of crystals was confirmed. Methanol (356 ml) was added after cooling to 40 degreeC, and suction filtration was performed after cooling to 5 degreeC. The obtained crude crystals were dispersed in o-xylene (272 ml), and after addition of water (0.32 g), the temperature was raised to 80° C. and dissolved. After washing the organic layer twice with water (240 ml), it was filtered under pressure (0.25 MPa) with a PTFE membrane filter (0.5 µm). Then, after 110 g of solvents were distilled off with an evaporator, when it cooled to 50 degreeC, precipitation of a crystal|crystallization was seen. Further, after cooling to 40°C, methanol (336 ml) is added, and after cooling to room temperature (20°C), suction filtration is performed, and the bis[9-(2-) Phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 4) 59.9 g (yield: 55.6%, 46.8 mmol) and bis{[9-(2-phenoxycarbonylethyl)fluorene-9 A white solid was obtained as a mixture of -yl]-methyl} fluorene (compound 5) 0.2 g (yield: 2.2%, 0.15 mmol).

HPLC analysis result Compound 4 (15.3 min): 98.17 area%, Compound 5 (16.5 min): 0.15 area%

In addition, after completion|finish of reaction, HPLC after crystallization and filtration were all implemented on condition of the following.

Column: Inertsil ODS-3V 150 mm x 4.8 mm φ

Temperature: 40 degrees Celsius

Eluent conditions: 0-5 min: tetrahydrofuran/water = 50/50, 20 min: tetrahydrofuran/water = 100/0

Flow rate: 1.0 ml/min

Injection amount: 2 μl

¹ H-NMR measurement result Compound 4

m.p. (Compound 4): 176°C

LC/MS measurement result

Compound 4 (13.1 min): (Exact Mass) 640

(Positive) 663[M+Na] ⁺ , 679[M+K] ⁺ , (Negative) 639[MH] ^-

Compound 5 (14.2 min): (Exact Mass) 818

(Positive) 841[M+Na] ⁺ , 875[M+K] ⁺ , (Negative) 817[MH] ^-

In addition, LC-MS measurement conditions were implemented under the following conditions.

LC system: Agilent 1200

Column: Inertsil ODS-3 5 μm 4.6 × 150 mm No. 2EI85047

Temperature: 40 degrees Celsius

Eluent conditions: 0-5 min: tetrahydrofuran/water = 50/50, 20 min: tetrahydrofuran/water = 100/0

Flow rate: 1.0 ml/min

Injection amount: 0.2 μl

Mass spectrometer: Agilent LC/MS 6130

Ion mode: AJS (Positive/Negative)

Capillary Voltage: 4500 V (P/N)

Fragment Voltage: 100V

Mass Range: m/z = 100-1500

Driving gas：N ₂ , DG = 12 ℓ/min, NP = 60 psi, DGT = 300 ℃

Other conditions: SG = 12 ℓ/min, ST = 300 °C, NV = 1000

[Synthesis Example of Polymer]

<Synthesis Example 2-1>

Bis[9-(2-ethoxycarboxyl) containing 0.05 parts by mass (0.0001 mole) of bis{[9-(2-ethoxycarbonylethyl)fluoren-9-yl]-methyl}fluorene (Compound 3) Bornylethyl)fluoren-9-yl]methane (Compound 2) 26.44 parts by mass (0.0489 mol), 10.37 parts by mass (0.072 mol) of CHDM, and 14.65×10 ^-3 parts by mass of tetra-n-butyl titanate (4.30) as a catalyst x 10 ^-5 mol) was put into a reaction vessel, and reacted at 220°C for 120 minutes under normal pressure in a nitrogen atmosphere. Next, the pressure was reduced to 13.3 kPa over 30 minutes, maintained at 13.3 kPa for 30 minutes, and generated ethanol was taken out of the reaction vessel. Thereafter, the reaction solution was once cooled to room temperature (20° C.), and 31.43 parts by mass (0.215 mol) of ISB and 51.66 parts by mass (0.241 mol) of DPC were put into the same reaction vessel, and the heating bath temperature was set to 150 in a nitrogen atmosphere. The raw material was dissolved while stirring as needed (about 10 minutes). After dissolution, the temperature was raised to 220°C over 30 minutes as a step in the first stage of the reaction, and the reaction was performed at normal pressure for 60 minutes. Next, the pressure was reduced from the normal pressure to 13.3 kPa over 90 minutes, maintained at 13.3 kPa for 30 minutes, and the generated phenol was taken out of the reaction vessel.

Subsequently, as a step of the second stage of the reaction, the pressure was reduced to 0.10 kPa or less over 15 minutes while the temperature of the heating tank was raised to 240°C over 15 minutes, and the generated phenol was taken out of the reaction vessel. After reaching a predetermined torque, the reaction was terminated, and the produced polymer was extruded into water to obtain polycarbonate resin pellets.

Table 3 shows the measurement results such as the glass transition temperature of the obtained resin composition, the refractive index anisotropy of the stretched film when the film is formed and stretched, the retardation ratio (Re450/Re550), and the toughness of the film.

<Synthesis Example 2-2>

Bis[9-(2-phenoxycarbonyl) containing 0.1 parts by mass (0.0001 mole) of bis{[9-(2-phenoxycarbonylethyl)fluoren-9-yl]-methyl}fluorene (Compound 5) nylethyl)fluoren-9-yl]methane (Compound 4) 29.5 parts by mass (0.0458 mol), 30.20 parts by mass SPG (0.099 mol), 40.34 parts by mass (0.276 mol) DPC, 70.49 parts by mass (0.329 mol) and As a catalyst, 9.91 x 10 ^-4 parts by mass (5.63 x 10 ^-6 mol) of calcium acetate monohydrate was put into a reaction vessel, and the raw material was dissolved while stirring as needed at a heating bath temperature of 150° C. under a nitrogen atmosphere. (about 10 minutes). After dissolution, the temperature was raised to 220°C over 30 minutes as a step in the first stage of the reaction, and the reaction was performed at normal pressure for 60 minutes. Next, the pressure was reduced from the normal pressure to 13.3 kPa over 90 minutes, maintained at 13.3 kPa for 15 minutes, and generated phenol was taken out of the reaction vessel.

Subsequently, as a step of the second stage of the reaction, the pressure was reduced to 0.10 kPa or less over 15 minutes while the temperature of the heating tank was raised to 245° C. over 15 minutes, and the generated phenol was taken out of the reaction vessel. After reaching a predetermined torque, the reaction was terminated, and the produced polymer was extruded into water to obtain polyester carbonate pellets.

Table 3 shows the measurement results such as the glass transition temperature of the obtained resin composition, the refractive index anisotropy of the stretched film when the film is formed and stretched, the retardation ratio (Re450/Re550), and the toughness of the film.

<Reference Example 2-1>

Bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]methane (Compound 2) 22.65 parts by mass (0.042 mol), 10.77 parts by mass (0.075 mol) of CHDM and tetra-n-butyltita as a catalyst 15.54×10 ⁻³ parts by mass (4.57×10 ⁻⁵ mol) of the nate was put into a reaction vessel, and it was reacted at 220° C. for 120 minutes at normal pressure in a nitrogen atmosphere. Next, the pressure was reduced to 13.3 kPa over 30 minutes, maintained at 13.3 kPa for 30 minutes, and generated ethanol was taken out of the reaction vessel. Thereafter, the reaction solution is once cooled to room temperature, and 33.58 parts by mass (0.230 mol) of ISB and 56.96 parts by mass (0.266 mol) of DPC are put into the same reaction vessel, and under a nitrogen atmosphere, the temperature of the heating bath is set to 150° C. While stirring according to the method, the raw material was dissolved (about 10 minutes). After dissolution, as a step of the first stage of the reaction, the temperature was raised to 220°C over 30 minutes, and the reaction was carried out at normal pressure for 60 minutes. Next, the pressure was reduced from the normal pressure to 13.3 kPa over 90 minutes, maintained at 13.3 kPa for 30 minutes, and the generated phenol was taken out of the reaction vessel.

Subsequently, as a step of the second stage of the reaction, the pressure was reduced to 0.10 kPa or less over 15 minutes while the temperature of the heating tank was raised to 240°C over 15 minutes, and the generated phenol was taken out of the reaction vessel. After reaching a predetermined torque, the reaction was terminated, and the produced polymer was extruded into water to obtain polyester carbonate resin pellets.

Table 3 shows the measurement results such as the glass transition temperature of the obtained resin composition, the refractive index anisotropy of the stretched film when the film is formed and stretched, the retardation ratio (Re450/Re550), and the toughness of the film.

<Reference Example 2-2>

9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BHEPF) 62.40 parts by mass (0.142 mol), ISB 28.78 parts by mass (0.197 mol), DPC 73.40 parts by mass (0.343 mol), and As a catalyst, 7.28 × 10 ^-4 parts by mass (3.39 × 10 ^-6 mol) of magnesium acetate tetrahydrate was put into a reaction vessel, and the raw material was dissolved while stirring as needed while setting the heating bath temperature to 150° C. under a nitrogen atmosphere. (about 10 minutes). After dissolution, the temperature was raised to 220°C over 30 minutes as a step in the first stage of the reaction, and the reaction was performed at normal pressure for 60 minutes. Next, the pressure was reduced from the normal pressure to 13.3 kPa over 90 minutes, maintained at 13.3 kPa for 30 minutes, and the generated phenol was taken out of the reaction vessel.

Subsequently, as a step of the second stage of the reaction, the pressure was reduced to 0.10 kPa or less over 15 minutes while the temperature of the heating tank was raised to 240°C over 15 minutes, and the generated phenol was taken out of the reaction vessel. After reaching a predetermined torque, the reaction was terminated, and the produced polymer was extruded into water to obtain polycarbonate pellets.

Table 3 shows the measurement results such as the glass transition temperature of the obtained resin composition, the refractive index anisotropy of the stretched film when the film is formed and stretched, the retardation ratio (Re450/Re550), and the toughness of the film.

<Calculation of energy and angle of conformation>

In order to examine the relationship between the chemical structure and optical properties of oligofluorene, the energy calculation of the specific configuration (conformation) of the repeating unit derived from the oligofluorene monomer and the angle between the fluorene ring and the main chain in the configuration was calculated as follows.

For the AM1 method, PC Spartan Pro 1.0.5 (Windows (registered trademark) 32 bit version) manufactured by Wavefunction Co., USA was used for the AM1 method. In addition, all input values related to calculation precision, such as a procedure determination value, used the default value of the said software.

Calculation was performed about the structure derived from compound 3 and compound 2 shown below. Here, with respect to compound 3 and compound 2, which are diester monomers, assuming a resin polymerized by transesterification, calculations were made for a structure in which both ester groups were used as methyl esters.

As shown below, the bond A between the carbon atom at the 9th position of fluorene and the carbon atom couple|bonded with fluorene on the adjacent fluorene side, the atom of the side chain couple|bonded with fluorene, and this atom, and bond The dihedral angle formed by the bond B between the atoms of the main chain is 180° (that is, the side chain is in a trans configuration), and 60° and -60° (that is, the side chain has two types of Goshu conformation) as the initial structure Thus, the equilibrium structure and its energy (heat of formation) were calculated by the AM1 method. Here, in each compound, the substituent which has the methyl ester couple|bonded with the carbon atom of the fluorene 9th position is called a side chain. Here, in order to guess the three-dimensional structure in the polymer of each repeating unit, both of the side chains which each compound has are changed. That is, in Table 4, with the trans conformation, both of the two side chains which exist in each monomer are the structures of the trans configuration, and, with the Goshu conformation, both of the two side chains which exist in each monomer are the structures of the Goshu conformation. Moreover, although there exist two types of 60 degree and -60 degree of Goshu conformation, both of two side chains are calculating about two types of 60 degree and -60 degree.

At this time, the energy difference between the two side chains present in each monomer is the trans conformation and the two types of Goshu conformation conformers are calculated, and the most stable of these three conformations is set to 0 (kJ/mol). Table 4 shows the energy difference (kJ/mol) at the time. Moreover, when the energy difference was 4 kJ/mol or more, the conformation with low energy (heat of formation) (the conformation set to 0 (kJ/mol)) was made into the stable conformation. Regarding the validity of the results of the AM1 method in this calculation, in Japanese Patent Application No. 2013-214986, it was confirmed that the same tendency as the ^{B3LYP/6-31G* method, which is a more advanced calculation, was exhibited.}

Incidentally, the angle between the main chain and the fluorene ring was calculated and described for the trans conformation and the two types of Goshu conformations.

In addition, the angle which a main chain and a fluorene ring make was determined as follows. First, let the straight line connecting the carbon atoms of the methyl groups at both terminals be the main chain direction, and the plane passing through the carbon atoms at the 3rd, 6th, and 9th positions of fluorene is the fluorene plane. At this time, although the straight line on the fluorene plane intersecting the main chain direction exists infinitely, the straight line on the fluorene plane whose angle with the main chain direction becomes the minimum is uniquely determined. The angle was made into the angle which a main chain and a fluorene ring make. Here, since compound 3 has three fluorene groups in the molecule, the angle between the main chain and the fluorene ring was calculated using the central fluorene ring.

[Formula 143]

Comparing Compound 3 and Compound 2 in Table 4, the difference between the energy (heat of formation) of the trans conformation and the energy (heat of formation) of the two types of Goshu conformation is the same, or the trans form is slightly stable.

In the comparison of compound 3 and compound 2, with respect to the angle between the main chain of the trans configuration and the fluorene ring, compound 3 having three fluorene groups is 84.2°, and compound 2 having two fluorene groups is 74.6°. 3 indicates a value close to 90°.

The present inventors discovered that a fluorene ring expresses the optical characteristic by being orthogonal to a principal chain in a resin composition. Further, in Japanese Patent Application No. 2013-214986, there is a correlation between the angle between the main chain and the fluorene ring in the stable conformation determined by calculation, the difference spectrum of polarization ATR analysis, and the reverse wavelength dispersion characteristic, and the calculation The difference spectrum of the polarized light ATR analysis is observed to be larger as the angle obtained by is closer to 90°, and it is confirmed that a strong reverse wavelength dispersion characteristic is obtained. When the angle of the trans conformation is 50° or more, preferably 60° or more, more preferably 70° or more, and particularly preferably 80° or more, reverse wavelength dispersion is expressed, and the repeating structures used are all in reverse wavelength. It can be expected that acidity is expressed.

From the comparison of Reference Example 2-1 and Reference Example 2-2, when a retardation film use showing reverse wavelength dispersion is assumed, difluorenediester is used to express the same retardation ratio (Re450/Re550) 0.90 Since the reference example 2-1 (polyester carbonate) used has much less fluorene ring-containing monomer than the reference example 2-2 (polycarbonate) using BHEPF, the one using the compound 2 uses BHEPF. It can be said that the effect of expressing reverse wavelength dispersion is higher than that. This is because compound 2 of difluorenediester has a higher fluorene ratio than BHEPF, and compound 2 has a lower ratio of flexible alkylene chains than BHEPF and is rigid, so the fluorene ring with respect to the main chain It is thought to be due to the fact that it is easy to take the state of going straight.

From the simulation results, it is considered that compound 2 has the same stability of the trans conformation and the Goshu conformation, or that the trans conformation is slightly stable, whereas compound 3 is stable in the trans conformation and has a high abundance ratio. In addition, in the trans configuration of each of Compound 3 and Compound 2, the angle between the main chain and the fluorene ring is 70° or more, and it can be expected that high reverse wavelength dispersion is expressed. In addition, in compound 3, the angle formed between the main chain and the fluorene ring exceeds 80°, and since it is considered that the reverse wavelength dispersion of compound 2 or higher is expressed, the amount used in compound 2 is less than that of compound 2, and the reverse is equivalent to that of compound 2. It is thought that wavelength dispersion property can be expressed.

In addition, since compound 3 has a melting point of 20° C. or more higher than compound 2 and has a higher decomposition initiation temperature, the glass transition temperature in the case of a resin is assumed to be higher than that of the resin using compound 2, and thermal stability is also high. do.

<Fluorene Ratio>

In Table 5, the chemical structural formula of the repeating unit derived from the fluorene ring containing monomer synthesize|combined in Synthesis Example 2-1, and the fluorene ratio are collectively shown. In addition, the fluorene ratio was computed from the following formula. However, the molecular weight of the fluorene skeleton in the following formula is calculated as 13 carbon atoms (hydrogen atom not included).

Fluorene ratio (%) = molecular weight of fluorene skeleton / molecular weight of repeating unit x 100

As described above, it is thought that desired optical properties can be efficiently expressed by increasing the ratio of fluorene in the repeating unit, but the fluorene ratios of Compound 2, Compound 3, Compound 4 and Compound 5 are all 70 % or more, it is thought that the resin composition of this invention using them is suitable for expressing a desired optical characteristic efficiently. On the other hand, in BHEPF, the fluorene ratio in the repeating unit derived therefrom is less than 50%, so it is not efficient to express the desired optical properties. In order to express the desired optical properties, the use of a monomer having fluorene I think the ratio needs to be increased.

From the above, when the use of retardation film showing reverse wavelength dispersion is assumed, the resin composition containing the polymer having a trifluorene repeating unit of the present invention can reduce heat resistance and the like even with a small amount of trifluorene diester. It has shown that various physical properties, positive intrinsic birefringence, and retardation ratio can be achieved.

«Example 3-1»

The abbreviations of the compounds used in the following examples are as follows.

ISB; Isosorbide (manufactured by Rocket Frere, trade name: POLYSORB)

DPC; diphenyl carbonate (manufactured by Mitsubishi Chemical Co., Ltd.)

CHDM; 1,4-cyclohexanedimethanol (cis, trans mixture, manufactured by SK Chemicals)

THF: tetrahydrofuran (without stabilizer, manufactured by WAKO)

[Example of Monomer]

<Example 3-1> Synthesis of 9-{[(2-ethoxycarbonylethyl)fluoren-9-yl]-methyl}fluorene (Compound 2)

[Formula 144]

<Synthesis Example 3-1A> Synthesis of bis(fluoren-9-yl)methane (Compound 1)

Fluorene (120 g, 722 mmol) and N,N-dimethylformamide (480 ml) were put in a 1 L 4-neck flask, and after nitrogen substitution, it cooled to 5 degrees C or less. Sodium ethoxide (24.6 g, 361 mmol) was added, and paraformaldehyde (8.7 g, 289 mmol) was added little by little so as not to exceed 10 degreeC, and it stirred. After 2 hours, 1N hydrochloric acid (440 ml) was added dropwise to stop the reaction. The resulting suspended solution was filtered with suction and washed with demineralized water (240 ml). Thereafter, the obtained crude product was dispersed in demineralized water (240 ml) and stirred for 1 hour. After suction filtration, this suspension was water washed with demineralized water (120 ml). After the obtained crude product was dispersed in toluene (480 ml), dehydration was performed under heating and reflux conditions using a Dean-Stark apparatus. After returning to room temperature (20 degreeC), it suction-filtered and dried under reduced pressure at 80 degreeC until it became a constant weight, to obtain 84.0 g of bis(fluoren-9-yl)methane (compound 1) as a white solid (yield: 84.5) %, HPLC purity: 94.0%) was obtained.

<Synthesis Example 3-1B-1> Synthesis of 9-{[(2-ethoxycarbonylethyl)fluoren-9-yl]-methyl}fluorene (Compound 2)

Bis(fluoren-9-yl)methane (Compound 1, 34.0 g, 98.7 mmol) obtained in Synthesis Example 3-1A in a 1 liter separable flask, N-benzyl-N,N,N-triethylammonium chloride ( 4.47 g, 19.6 mmol) and tetrahydrofuran (170 ml) were added, and after nitrogen substitution, the internal temperature was controlled to 15°C to 18°C, and as a result of adding a 50 wt/wt% aqueous sodium hydroxide solution (25.93 g), The color of the solution changed to pale yellow. Then, after ethyl acrylate (10.7 ml, 103 mmol) was dripped over 30 minutes, it analyzed by HPLC.

(HPLC conditions)

Column: Inertsil ODS-3V 150 mm x 4.8 mm φ

Temperature: 40 degrees Celsius

Eluent conditions: 0 to 5 min: tetrahydrofuran/water = 50/50, 20 min: tetrahydrofuran/water = 100/0

Flow rate: 1.0 ml/min

Injection amount: 2 μl

(HPLC analysis result)

Compound 1 (13.9 min): 15 area%, Compound 2 (13.1 min): 61 area%, Compound 3 (13.5 min): 15 area%

<Synthesis Example 3-1B-2> 9-{[(2-ethoxycarbonylethyl)fluoren-9-yl]-methyl}fluorene (Compound 2)

Compound 1 (1.0 g, 2.9 mmol), benzyltriethylammonium chloride (132 mg, 0.58 mmol), and THF (5 mL) were added to a 50 mL three neck flask, followed by stirring at room temperature under a nitrogen atmosphere. Ethyl acrylate (290 mg, 2.9 mmol) was added over 30 minutes, and then aged at room temperature for 3 hours. After aging at 16° C. for 1 hour, it was neutralized with 3 N hydrochloric acid. Toluene (5 mL) was added thereto, and the toluene phase was washed once with a saturated aqueous sodium hydrogencarbonate solution (5 mL) and three times with water (5 mL). After distilling toluene off with an evaporator, the residue was purified by silica gel chromatography to obtain compound 2 (0.63 g, 1.4 mmol, yield: 49%, white crystals).

From Synthesis Example 3-1B-1, when 1 equivalent of ethyl acrylate was added using compound 1 as a raw material, when the rate of the addition reaction of ethyl acrylate was the same in the first addition and the second addition, in theory, compound 1 and compound 2 and compound 3 will be produced such that the ratio is 1:2:1. However, surprisingly, in this reaction, it can be seen that the area ratio of HPLC is 1:4:1, and that Compound 2 as a mono-adduct is selectively produced. This is because the structure in which two fluorene rings are stacked in Compound 3 is the most stable structure, whereas in Compound 1 and Compound 2, the structure in which the two fluorene rings are inverted is the most stable structure, so the second acrylic acid in Compound 2 is When ethyl is added, it is considered that it is necessary to add one fluorene ring inverted. The protons derived from the fluorene ring of Compound 1 and Compound 2 ^{are observed as a whole at δ6.60-7.80 ppm by 1} H-NMR on the low field side, whereas the protons derived from the fluorene ring of Compound 3 are δ6.77 It is observed at -7.03 ppm on the high magnetic field side, and also from the fact that the influence of the strong shielding effect is seen, that the fluorene ring takes a stacking structure is supported.

In general, in the case of having a substituent introduction site at two points, it may be difficult to selectively introduce a reactive functional group at only one point, but in the case of a specific oligofluorene compound, due to a difference in steric reactivity, etc. It tends to be easy to selectively introduce only at one point, and it is considered that it can be industrially manufactured.

In addition, when a reactive substituent is introduced by an addition reaction or a substitution reaction with respect to an oligofluorene compound such as Compound 1, it is thought that there is a tendency that oligofluorene having one reactive functional group can be selectively produced in the same way. , is considered to be widely applicable other than ethyl acrylate.

<Use of oligofluorene having one reactive substituent as a resin raw material>

For example, a monoester such as compound 2 is considered to act as a terminator by using it as a raw material of polyester or polyester carbonate, so it is considered useful as a molecular weight regulator of polyester or polycarbonate. .

<Use as a resin raw material of an oligofluorene compound having two different reactive functional groups>

For example, a monoester such as compound 2 can also synthesize an oligofluorene compound having two different reactive functional groups by introducing a hydroxyl group as a reactive substituent. Because it can be obtained, it is considered useful.

«Examples 4-1 to 4-4, Comparative Examples 4-1 to 4-2»

The quality evaluation of the oligofluorene monomer of the present invention and the evaluation of the properties of the resin composition and the transparent film were performed by the following method. In addition, the characteristic evaluation method is not limited to the following method, A person skilled in the art can select suitably.

In addition, the abbreviation of the compound used in the following synthesis example and an Example, etc. are as follows.

ISB; Isosorbide (manufactured by Rocket Frere, trade name: POLYSORB)

DPC; diphenyl carbonate (manufactured by Mitsubishi Chemical Co., Ltd.)

CHDM; 1,4-cyclohexanedimethanol (cis, trans mixture, manufactured by SK Chemicals)

BHEPF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]-fluorene (manufactured by Osaka Gas Chemical Co., Ltd.)

(1) Powder X-ray diffraction of oligofluorene diester

The powder X-ray diffraction pattern of the oligofluorenediester was measured using a powder X-ray diffraction measuring device (X-Pert'Pro, Spectris PANalitical Division).

(2) Measurement of particle size distribution of oligofluorene diester

The particle size distribution of the oligofluorenediester was measured by dispersing it in methanol as a solvent using a laser diffraction/scattering particle size distribution analyzer (MT3300EX manufactured by Microtrac Bell).

(3) Rotational angle of repose of oligofluorene diester

The rotational angle of repose of the oligofluorene diester was measured by the cylindrical rotation method using a three-wheeled angle-of-repose measuring device (manufactured by Tsutsui Chemical Machinery Co., Ltd.).

(4) Evaluation of thermal stability of oligofluorene diester

500 mg of oligofluorene diester was added to the 30 mL flask, and it stirred at 185 degreeC in nitrogen atmosphere for 7 hours. The color tone before and after heating was visually confirmed. Moreover, the 1 wt% THF solution of the oligofluorene diester before and behind a heating was prepared, and the absorbance of 400 nm wavelength was measured using the ultraviolet-visible absorption spectrophotometer (UV-1650PC by Shimadzu Corporation).

<Example 4-1>

[Formula 145]

<Example 4-1A> Synthesis of bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]methane (Compound 2)

Bis(fluoren-9-yl)methane (50 g, 145.2 mmol), benzyltriethylammonium chloride (6.6 g, 29.0 mmol), tetrahydrofuran (250 ml) were placed in a 1 liter separable flask, and nitrogen After substitution, the temperature was controlled at 17°C to 19°C in a water bath, and a 50 wt/vol% aqueous sodium hydroxide solution (26.5 ml) was added. As a result, the color of the solution changed to pale red. Then, ethyl acrylate (15.1 ml, 145.2 mmol) was dripped over 30 minutes. Then, benzyltriethylammonium chloride (6.6 g, 29.0 mmol) was added, and ethyl acrylate (30.2 ml, 290.2 mmol) was added, and the mixture was stirred for 2 hours while tracking the progress of the reaction by HPLC. After confirming that the mono-adduct was 2% or less by HPLC, the mixture was cooled in an ice bath, and 3N hydrochloric acid (166.4 ml) was added dropwise in balance with the temperature, followed by quenching. After discarding the aqueous layer, 100 ml of toluene was added, the organic layer was washed with a saturated aqueous sodium hydrogencarbonate solution (150 ml), and the organic layer was further washed with demineralized water (150 ml). Then, after distilling off tetrahydrofuran under reduced pressure, methanol (200 mL) was added and crystallization was performed. After suction filtration, 61.9 g (yield: 78.0%, HPLC purity: 87.4 area%) was obtained.

<HPLC conditions>

Column: Inertsil ODS-3V 150 mm x 4.8 mm φ

Temperature: 40 degrees Celsius

Eluent conditions: 0-5 min: tetrahydrofuran/water = 50/50, 20 min: tetrahydrofuran/water = 100/0

Flow rate: 1.0 ml/min

Injection amount: 2 μl

HPLC analysis result compound 4 (5.9 min): 0.0 area% (0.0 mass%), compound 5 (10.4 min): 3.0 area% (2.9 mass%), compound 3 (13.5 min): 87.4 area% (89.0 mass%)

( ) indicates the quantitative value calculated from the calibration curve.

<Example 4-1B> Synthesis of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2)

Bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]methane (Compound 1, 49.7 g, 91.2 mmol), diphenyl carbonate (98.3 g, 459 mmol) in a 1 liter 4-necked flask , tetraisopropyl orthotitanate (1.3 ml, 4.59 mmol) was added, the pressure reduction degree was adjusted to 3 to 2 kPa, and the temperature range was 140° C. to 150° C., and the mixture was stirred for 10 hours while distilling off by-products. It cooled to 90 degreeC, and after confirming completion|finish of reaction by HPLC, toluene (100 ml) was added and it cooled to 50 degreeC. Methanol (250 ml) was added there, and suction filtration was performed after cooling to room temperature. The obtained white solid was dispersed in toluene (100 ml) and heated to reflux for 30 minutes. After cooling to 50°C, methanol (250 mL) was added. After cooling to room temperature (20 degreeC), suction filtration was performed, and it dried under reduced pressure at 100 degreeC until it became a constant weight, and bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl] as a white solid 35.2 g (yield: 60%, HPLC purity: 98.4 area%) of methane (compound 2) was obtained.

Ti content: 330 mass ppm

<Example 4-2> Synthesis of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2)

Diphenyl carbonate (74.9 parts by mass) was added to a 250 L GL reactor and dissolved at 120°C. Bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]methane (Compound 1, 38.1 parts by mass) and tetraisopropyl orthotitanate (1.0 parts by mass) were added thereto, and the pressure reduction degree was set to 3.0. It stirred for 7 hours until internal temperature reached 185 degreeC, adjusting to kPa and distilling off a by-product. After returning to normal pressure with nitrogen, it was cooled to 90°C, and after completion of the reaction was confirmed by HPLC, toluene (66 parts by mass) was added, transferred to a 400 L GL reactor, and cooled to 50°C. There, methanol (151 mass parts) was added, and centri filtration was performed after cooling to 5 degreeC. The obtained crude product was dispersed in toluene (66 parts by mass) and heated to reflux for 30 minutes. After cooling to 50°C, methanol (151 parts by mass) was added, and centri filtration was performed after cooling to 22°C. Furthermore, the obtained crude product was disperse|distributed in toluene (66 mass parts), and it heated and refluxed for 30 minutes. After cooling to 50°C, methanol (151 parts by mass) was added, and centri filtration was performed after cooling to 22°C. By drying under reduced pressure at 80°C until constant weight, 27.2 g of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (compound 2) as a white solid (yield: 61%, HPLC) Purity: 99.5 area%) was obtained.

Ti content: 40 mass ppm

<Example 4-3> Synthesis of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2)

Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2, 60 g) and toluene (120 ml) obtained in Example 4-2 were added to a 1 L separable flask, and , After heating up to 80 degreeC and dissolving, demineralized water (180 ml) was added, and after stirring for 30 minutes, the aqueous layer was discarded by liquid separation operation. Again, demineralized water (180 ml) was added, stirred for 30 minutes, the aqueous layer was discarded by liquid separation operation, the organic layer was filtered under pressure (0.2 MPa, ADVANTEC PTFE membrane filter, pore diameter 0.5 µm: H050A47A), and the organic layer was was added to a 1 L separable flask, stirred, and cooled to 40°C. Methanol (300 ml) was added there, and suction filtration was performed after cooling to 22 degreeC. By drying under reduced pressure at 80°C until constant weight, 54.1 g (yield: 90%) of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (compound 2) was obtained as a white solid. .

Ti content: < 0.1 ppm by mass

<Example 4-4>

Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2, 61.7 g) obtained in Example 4-2 was dissolved in chloroform, followed by silica gel column chromatography (eluent: chloroform) ) was purified. Chloroform was distilled off under reduced pressure for the obtained chloroform solution with an evaporator, and MeOH (300 mL) was added. After cooling to room temperature (20°C), suction filtration was performed, followed by drying under reduced pressure at 80°C until it became a constant weight, whereby bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl] as a white solid Methane (compound 2) was obtained in 59.8 g (yield: 97%, HPLC purity: 99.5 area%).

Ti content: < 0.1 ppm by mass

<Comparative Example 4-1> Synthesis of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2)

Bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]methane (compound 1, 35.0 g, 64.3 mmol), diphenyl carbonate (68.8 g, 321 mmol) in a 500 ml four-necked flask , tetraisopropyl orthotitanate (0.95 ml, 3.24 mmol) was added, the degree of reduced pressure was adjusted to 2.8 to 3.2 kPa, and the temperature range was 135°C to 150°C, and the mixture was stirred for 6 hours while distilling off by-products. It cooled to 90 degreeC, and after confirming completion|finish of reaction by HPLC, toluene (70 mL) was added and it cooled to 50 degreeC. Methanol (175 ml) was added there, and suction filtration was performed after cooling to 5 degreeC. The obtained white solid was dispersed in toluene (70 ml) and heated to reflux for 30 minutes. After cooling to 50°C, methanol (175 mL) was added. After cooling to room temperature (20°C), suction filtration was performed, followed by drying under reduced pressure at 80°C until it became a constant weight, whereby bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl] as a white solid Methane (compound 2) was obtained in 32.2 g (yield: 78%, HPLC purity: 99.0 area%).

Ti content: 770 mass ppm

<Comparative Example 4-2>

[Formula 146]

<Comparative Example 4-2A> Synthesis of bis[9-(2-methoxycarbonylethyl)fluoren-9-yl]methane (Compound 3)

Bis(fluoren-9-yl)methane (10.01 g, 29.06 mmol), N-benzyl-N,N,N-triethylammonium chloride (1.32 g, 5.78 mmol), tetrahydro in a 200 ml four-necked flask Furan (50 ml) was added, and after nitrogen substitution, the temperature was controlled to 15 to 20° C. in a water bath, and a 50% aqueous sodium hydroxide solution (8 ml) was added. As a result, the color of the solution changed to light red. Then, the internal temperature was controlled to 17-18 degreeC using the ice bath, and methyl acrylate (7.8 ml, 86 mmol) was dripped over 3 hours. After stirring for 3 hours while tracking the progress of the reaction by HPLC, it was cooled in an ice bath, and quenched by dropping 3N hydrochloric acid (22 ml) while controlling the internal temperature not to exceed 18°C. Toluene (20 ml) was added to the organic layer obtained by liquid separation, washed with demineralized water, and the solvent was distilled off under reduced pressure and concentrated. The concentrate was returned to room temperature (20 degreeC), methanol (40 mL) was added and it crystallized. After suction filtration, 7.05 g (yield: 47.0%, HPLC purity: 80.0 area%) was obtained.

<HPLC conditions>

Column: Inertsil ODS-3V 150 mm x 4.8 mm φ

Temperature: 40 degrees Celsius

Eluent conditions: 0-5 min: tetrahydrofuran/water = 50/50, 20 min: tetrahydrofuran/water = 100/0

Flow rate: 1.0 ml/min

Injection amount: 2 μl

HPLC analysis result compound 4 (5.9 min): 12.8 area% (12.8 mass%), compound 6 (not detected): not detected, compound 3 (11.8 min): 80.0 area% (84.6 mass%)

( ) indicates the quantitative value calculated from the calibration curve.

<Comparative Example 4-2B> Synthesis of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2)

Bis[9-(2-methoxycarbonylethyl)fluoren-9-yl]methane (compound 3, 6.0 g, 11.6 mmol), diphenyl carbonate (12.1 g, 56.6 mmol) in a 50 ml three neck flask , tetraisopropyl orthotitanate (0.16 mL, 0.55 mmol) was added, the temperature was raised to 145°C, and the mixture was stirred for 1 hour. Since it was confirmed by HPLC that reaction was not advancing, tetraisopropyl orthotitanate (0.32 ml, 1.1 mmol) was further added, and HPLC analysis was performed again 1 hour later, As a result, the disappearance and reaction of the peak of compound 4 Since progress was confirmed, the mixture was further stirred at 145 °C for 1 hour. After confirming completion of the reaction by HPLC, toluene (15 ml) was added, and the mixture was heated to reflux for 1 hour. After cooling to 50°C, methanol (18 mL) was added. Suction filtration was performed after cooling to room temperature (20 degreeC). The obtained white solid was dispersed in toluene (12 ml) and heated to reflux for 1 hour. After cooling to 50°C, methanol (18 mL) was added. After cooling to room temperature (20 degreeC), suction filtration was performed, and it dried under reduced pressure at 100 degreeC until it became a constant weight, and bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl] as a white solid Methane (Compound 2) was obtained in 5.39 g (yield: 64%, HPLC purity: 98.1 area%).

Ti content: 3300 ppm by mass

<Reference Example 4-1>

A 32.7 wt% o-xylene solution of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2, 1201 parts by mass) was slowly introduced into a glass-lined 12 m3 reactor from 86°C. It temperature-falled, when it reached 60 degreeC, methanol (551 mass parts) was added, and when it reached 55 degreeC, the seed crystal was added, and the crystal|crystallization was deposited. Then, it cooled to 40 degreeC over 5 hr, methanol (3548 mass parts) was added over 1 hr, and it cooled to 21 degreeC over 5 hr further. Divide into 10 batches by centrifugal filtration to obtain crystals, divide into 2 batches with a conical dryer and dry at 80°C until constant weight, thereby forming bis[9-(2-phenoxycarbonylethyl)fluorene- as a white solid 9-yl]methane (compound 2) was obtained in 1125 parts by mass (recovery: 94%, HPLC purity: 99.8 area%).

Average particle diameter: 178 μm, 50 μm or more particle diameter cumulative %: 99%

Rotational angle of repose: 55°

Powder X-ray diffraction pattern: 2θ = 6.9°, 9.8°, 10.3°, 11.7°, 12.0°, 12.7°, 13.3°, 13.8°, 15.0°, 15.8°, 17.3°, 17.9°, 18.9°, 19.6°

<Reference Example 4-2>

A 32.0 wt% o-xylene solution of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2, 1224 parts by mass) was slowly introduced into a glass-lined 12 m3 reactor from 81°C. It temperature-fallen, and when it reached 68 degreeC, the seed crystal was added. Then, it cooled to 49 degreeC, methanol (4579 mass parts) was added over 1 hr, and it cooled to 21 degreeC over 5 hours further. Divide into 6 batches by centrifugal filtration to obtain crystals, divide into 2 batches with a conical dryer and dry at 80°C until constant weight, thereby forming bis[9-(2-phenoxycarbonylethyl)fluorene- as a white solid 9-yl]methane (compound 2) was obtained in 1043 parts by mass (recovery: 85%, HPLC purity: 99.8 area%).

Average particle diameter: 44 μm, 50 μm or more particle diameter cumulative %: 30%

Rotational angle of repose: 62°

<Reference Example 4-3>

After nitrogen substitution in a glass-lined 1 m3 reactor, bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2, 250 parts by mass), o-xylene (450 parts by mass) was added, and the temperature was raised to 100 °C or higher to dissolve. Then, it cooled to 80 degreeC, and after adding a seed crystal, it cooled to 20 degreeC at the cooling rate of 10 degreeC in 1 hour, and centri filtration was started.

Although filtration was possible in the first centimeter, gradually the crystals in the reactor were finely pulverized, resulting in a dramatic deterioration in the slurry properties, and filtration was possible up to the third centimeter, but after that, extraction became difficult and centri filtration was stopped. 63.2 parts by mass of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2) as a white solid by drying the obtained 3 centimeters at 80°C until a constant weight was obtained ( Recovery: 25%) was obtained.

1st cent

Powder X-ray diffraction pattern: 2θ = 5.6°, 6.9°, 8.5°, 9.8°, 10.3°, 11.0°, 11.7°, 12.0°, 12.5°, 12.7°, 12.9°, 13.3°, 13.8°, 14.9°, 15.0°, 15.8°, 17.3°, 17.9°, 16.3°, 18.9°, 19.1°, 19.6°

Average particle diameter: 220 μm, 50 μm or more particle diameter cumulative %: 88%

3rd cent

Powder X-ray diffraction pattern: 2θ = 6.9°, 9.8°, 10.3°, 11.7°, 12.0°, 12.7°, 13.3°, 13.8°, 15.0°, 15.8°, 17.3°, 17.9°, 18.9°, 19.6°

Average particle diameter: 25 μm, 50 μm or more particle diameter cumulative %: 5%

Comparing Example 4-1 and Example 4-2, the Ti content of the target oligofluorenediaryl ester (Compound 2) decreases from 330 ppm to 40 ppm by increasing the number of crystallization of toluene/methanol. it can be seen that Further, comparing Example 4-1 with Comparative Example 4-1, in Comparative Example 4-1, the yield was improved from 60% to 78% by lowering the toluene/methanol crystallization temperature from room temperature to 5°C. However, it can be seen that the residual amount of Ti is significantly deteriorated from 330 ppm to 770 ppm. Moreover, in Comparative Example 4-2, when a raw material containing oligofluorenedicarboxylic acid in a ratio exceeding 10 mass% is used, the reaction does not proceed with a predetermined amount of the transesterification catalyst and the transesterification reaction It was necessary to add a catalyst. This is considered to be the cause of oligofluorenedicarboxylic acid forming a complex with the Ti compound of a transesterification reaction catalyst, and making it deactivate. For this reason, it turns out that Ti content of the obtained oligofluorenediaryl ester (compound 2) is increasing significantly. In Example 4-3, the compound 2 obtained in Example 4-2 was subjected to a water washing step and pressure filtration. In Example 4-4, the compound obtained in Example 4-2 was purified by silica gel column chromatography. , the Ti content can be reduced to below the detection limit. In particular, the purification method by a water washing process and pressure filtration is comparatively low-cost, and since it can implement industrially, it can be said that it is an excellent purification method.

In Table 6, Ti content in the oligofluorenediester of each Example and a comparative example, and the result of thermal stability evaluation are collectively shown.

Next, based on Table 6, the change in color tone of the crystal in the molten state due to heating is discussed. The color tone before heating was pale yellow with a slightly yellowish taste in Example 4-1, but Example 4-2, Example 4-3, and Example 4-4 were white. On the other hand, Comparative Example 4-1 and Comparative Example 4-2 were colored yellow before heating. Moreover, as a result of heating at 185 degreeC for 7 hours, in Example 4-3 and Example 4-4, coloring was not seen and colorless transparent crystal|crystallization was obtained. In Example 4-2, Example 4-1, Comparative Example 4-1, and Comparative Example 4-2, as the Ti content increased, the color clearly showed a tendency to deepen, and in particular, Comparative Example 4-1 and Comparative Example Crystals after heating at 4-2 were brown.

Although the details of coloring are not clear, it is thought that chelation of a metal component is one of the causes.

Next, based on FIG. 1, the change in color tone before and after heating is discussed according to the change in absorbance at 400 nm of a 1 wt% THF solution. 1, Example 4-2 (40 ppm), Example 4-3 (<0.1 ppm), and Example 4-4 (<0.1 ppm) showed almost no change in the absorbance of the THF solution before and after heating didn't In Example 4-1 (330 ppm) and Comparative Example 4-1 (770 ppm), the Ti content was about 2 times, but the difference in absorbance was close to 4 times. From this, it was confirmed that there exists a large dispersion|variation in the influence which Ti content has on color tone between 330 ppm of Example 4-1 and 770 ppm of Comparative Example 4-1. Moreover, regarding the comparative example 4-2 (3300 ppm), color tone deterioration and precipitation of an insoluble component were severe, and it was difficult to measure the absorbance at 400 nm.

From the above, by using the oligofluorene diester of this invention, since there is little change of color tone even in a molten state, it has shown that suppression of coloring of the resin composition which may generate|occur|produce when it goes through a melting process is possible.

As shown in FIG. 2 , comparing Reference Example 4-1 and Reference Example 4-2 in which crystallization is carried out in a 12 m 3 glass-lined reactor, in Reference Example 4-2, the average particle diameter of the obtained crystal is 44 μm. It was small and exhibited a high value with a rotational angle of repose of 62°, which is an index of powder fluidity. On the other hand, in Reference Example 4-1, by adding methanol in portions, the average particle diameter of the crystals increased to 178 mu m, and the rotation angle of repose was improved to 55 DEG . From the above, by using the crystal|crystallization with a large average particle diameter of this invention, even if it uses as a resin raw material, it has shown that there is no problem in injectability.

In Reference Example 4-3, crystallization was carried out using only o-xylene, which is a good solvent, and as a result, good crystals with an average particle diameter of 220 µm after drying in the first centimeter were obtained. It was changed to a potage-shaped suspension, and it became clear that the average particle diameter after drying in the third centimeter was pulverized to 25 µm. Moreover, since the fluidity deteriorated further after the 3rd centimeter, extraction from the reaction solution became difficult, centri filtration was interrupted, and it was made to re-dissolve. In addition, as a result of XRD analysis of the powder after drying the first centimeter, peaks at 2θ = 5.6°, 8.5°, 11.0°, 12.5°, 12.9°, 14.9°, 16.3°, and 19.1° were observed, and 3 centimeters This peak was not observed from the dried powder. From this, it became clear that the powder at the first centimeter contained crystals of a metastable form, and was pulverized as the phase transitioned gradually to a stable form.

When o-xylene was used as a good solvent in Reference Example 4-1 and methanol was used as a poor solvent in Reference Example 4-1, peaks at 2θ = 5.6°, 8.5°, 11.0°, 12.5°, 12.9°, 14.9°, 16.3°, and 19.1° is not observed and pulverization does not occur, so by using an aromatic hydrocarbon represented by o-xylene as a good solvent and an alcohol solvent represented by methanol as a poor solvent, particles having a large average particle diameter can be obtained. I think.

[Synthesis Example of Polymer]

<Reference Example 4-4>

Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (Compound 2) 26.63 parts by mass (0.042 mol), 10.78 parts by mass (0.075 mol) of CHDM, 33.58 parts by mass (0.230 mol) of ISB , DPC 56.33 parts by mass (0.263 mol) and calcium acetate monohydrate 5.36 x 10 ^-4 parts by mass (3.04 x 10 ^-6 mol) as a catalyst were put into a reaction vessel, and the heating bath temperature was 150 ° C. under a nitrogen atmosphere, The raw materials were dissolved (about 10 minutes) with stirring as needed. After dissolution, the temperature was raised to 220°C over 30 minutes as a step in the first stage of the reaction, and the reaction was performed at normal pressure for 60 minutes. Next, the pressure was reduced from the normal pressure to 13.3 kPa over 90 minutes, maintained at 13.3 kPa for 30 minutes, and the generated phenol was taken out of the reaction vessel.

Subsequently, as a step of the second stage of the reaction, the pressure was reduced to 0.10 kPa or less over 15 minutes while the temperature of the heating tank was raised to 240°C over 15 minutes, and the generated phenol was taken out of the reaction vessel. After reaching a predetermined torque, the reaction was terminated, and the produced polymer was extruded into water to obtain polyester carbonate pellets.

Table 7 shows measurement results such as refractive index anisotropy and retardation ratio (Re450/Re550) of the stretched film when the obtained resin composition is film-molded and stretched.

<Reference Example 4-5>

9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BHEPF) 62.40 parts by mass (0.142 mol), ISB 28.78 parts by mass (0.197 mol), DPC 73.40 parts by mass (0.343 mol), and As a catalyst, 7.28 x 10 ^-4 parts by mass (3.39 x 10 ^-6 mol) of magnesium acetate tetrahydrate was put into a reaction vessel, and the raw material was dissolved while stirring as needed at a heating bath temperature of 150° C. under a nitrogen atmosphere. (about 10 minutes). After dissolution, the temperature was raised to 220°C over 30 minutes as a step in the first stage of the reaction, and the reaction was performed at normal pressure for 60 minutes. Next, the pressure was reduced from the normal pressure to 13.3 kPa over 90 minutes, maintained at 13.3 kPa for 30 minutes, and the generated phenol was taken out of the reaction vessel.

Subsequently, as a step of the second stage of the reaction, the pressure was reduced to 0.10 kPa or less over 15 minutes while the temperature of the heating tank was raised to 240°C over 15 minutes, and the generated phenol was taken out of the reaction vessel. After reaching a predetermined torque, the reaction was terminated, and the produced polymer was extruded into water to obtain polycarbonate pellets.

Table 7 shows measurement results such as refractive index anisotropy and retardation ratio (Re450/Re550) of the stretched film when the obtained resin composition is film-molded and stretched.

From Table 7, when comparing the polyester carbonate using the compound 2 of Reference Example 4-4 and the polycarbonate using the BHEPF of Reference Example 4-5, the retardation ratio (Re450) /Re550) is equivalent, so it turns out that strong reverse wavelength dispersion is shown. Moreover, the photoelastic coefficient is also a value of half or less. From this, it can be said that the oligofluorenediester of this invention is a very excellent monomer.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention. This application is a Japanese patent application filed on February 27, 2014 (Japanese Patent Application No. 2014-037216), filed on March 19, 2014 (Japanese Patent Application No. 2014-056873), filed on April 4, 2014 It is based on the Japanese patent application of (Japanese Patent Application No. 2014-078068), and the Japanese patent application of an application on April 16, 2014 (Japanese Patent Application No. 2014-084649), the contents of which are incorporated herein by reference.

Claims (10)

As a polycondensation-based resin having a repeating structural unit containing an aromatic structure,
A resin characterized in that the content of the aromatic structure in the repeating structural unit satisfies the following formula (III), and the resin has a glass transition temperature of 110°C or higher and 160°C or lower.
5 ≤ A ≤ -22.5 × B + 34.8 (III)
provided that 0.75 ≤ B ≤ 0.93
A: Content of aromatic structure in the repeating structural unit constituting the resin [mass %]
B: Ratio (R450/R550) of the retardation (R450) at 450 nm and the retardation (R550) at 550 nm of the stretched film produced from the resin The method of claim 1,
Resin whose refractive index in sodium d line|wire (589 nm) is 1.49-1.56. The method of claim 1,
A resin having a storage modulus of 1 GPa or more and 2.7 GPa or less. The method of claim 1,
Resin whose melt viscosity in a measurement temperature of 240 degreeC and a shear rate of 91.2 sec ^-1 is 700 Pa.s or more and 5000 Pa.s or less. The method of claim 1,
The resin is at least one resin selected from the group consisting of polycarbonate, polyester, and polyester carbonate. The method of claim 1,
The resin in which the aromatic structure contained in the said repeating structural unit is fluorene only. The method of claim 1,
Resin containing the structural unit represented by following formula (3).

A transparent film containing the resin according to claim 1. A retardation film obtained by stretching the transparent film according to claim 8 in at least one direction. 10. The method of claim 9,
A retardation film consisting of a single layer and having a film thickness of 10 µm or more and 60 µm or less.

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