TWI673262B - Polycondensation resin and optical film formed from the resin - Google Patents

Abstract

An object of the present invention is to provide a resin that is well-balanced and excellent in various properties such as optical physical properties, heat resistance, mechanical physical properties, and thermal stability, and an optical film and a retardation film obtained by using the resin. The present invention relates to a resin characterized in that it is a polycondensation resin having a repeating structural unit including an aromatic structure, and the content of the aromatic structure in the repeating structural unit satisfies the following formula (I) and has a structure unit.

5 ≦ A ≦ -22.5 × B + 38.3 (I)

Among them, 0.75 ≦ B ≦ 0.93

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

B: The ratio (R450 / R550) of the retardation (R450) at 450nm to the retardation (R550) at 550nm of the stretched film made of resin

Description

Polycondensation resin and optical film made of the same

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

The present invention also relates to a novel tertiary diester, an oligomeric oligomeric diester composition containing the same, and a resin composition containing a polymer having a repeating unit derived from the novel trimeric diester, and a resin composition using the same. The obtained stretched film, circular polarizing plate, and image display device.

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

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

In recent years, demand for optical transparent resins used in optical systems such as optical lenses, optical films, and optical recording media has increased. Among them, thin flat panel displays (FPDs) typified by liquid crystal displays or organic EL displays have become popular. Various optical systems have been developed for the purpose of improving display quality such as improvement in contrast or coloration, widening of viewing angles, and prevention of external light reflection. Film and use it.

In organic EL displays, a quarter-wave plate is used to prevent reflection of external light. In order to suppress coloration and make pure black display possible, the retardation film used in a 1/4 wavelength plate requires a wide-band wavelength dispersion characteristic, that is, an ideal retardation characteristic can be obtained at each wavelength in the visible region. .

As the equivalent of the above-mentioned retardation film, for example, it is revealed that the following cases are about to be double-folded Two types of retardation films having different emission wavelength dispersions are laminated so that their respective late phase axes are orthogonal, thereby obtaining a wide-band retardation film (Patent Document 1). Also disclosed is a method of obtaining the above-mentioned wide-band retardation film by laminating the 1 / 2-wavelength plate and the 1 / 4-wavelength plate so that their respective late axes become a specific arrangement (Patent Document 2). Furthermore, a wide-band retardation film containing a cellulose acetate having a specific degree of acetylation (Patent Document 3) or a polycarbonate copolymer containing a bisphenol structure having a fluorene ring on a side chain is disclosed, and is shown. A retardation film having an inverse wavelength dispersion and a smaller retardation as the output wavelength becomes shorter (Patent Document 4).

In recent years, a variety of resins having a fluorene ring on the side chain have been reported, and materials that use optical characteristics or heat resistance derived from the fluorene ring have been proposed for use in optical applications (Patent Document 5).

Of these resins, relatively easy-to-obtain monomers are often used, namely 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene or 9,9-bis (4-hydroxy-3-methyl) Phenyl) fluorene (Patent Documents 6 and 7).

Furthermore, resins with novel structures have also been developed. Patent Document 8 discloses a diamine compound having a fluorene ring on a side chain, and further describes a stretched film of a polyimide resin using the same. Patent Document 9 discloses a polycarbonate resin used for a fluorene compound that does not contain an aromatic ring in the main chain. Patent Document 10 discloses a dihydroxy compound or diester compound having two fluorene rings in the same molecule, and further describes a stretched film of a polyester resin using the same.

Patent Documents 11 and 12 disclose a case where the content of a repeating unit having a fluorene ring in a polycarbonate resin is controlled to a specific range, whereby the stretched film including the polycarbonate resin exhibits a shorter wavelength and a phase. As the difference becomes smaller, the inverse wavelength dispersion property is excellent as a retardation film. The shorter the wavelength, the smaller the retardation, the so-called inverse wavelength dispersion retardation film can obtain the ideal retardation characteristics at each wavelength in the visible region. Useful for prevention or perspective correction.

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

It is known that a polyester using a difluorene compound having two fluorene rings has a relatively high glass transition temperature and negative birefringence, and therefore, it can be used for reflective polarizing plate applications (Patent Document 10). Furthermore, it is known to use two types of difluorene compounds having different functional groups at the ends as a resin raw material.

On the other hand, diamine compounds having only one reactive functional group at the terminal are known for the use of the protective group of the amine group synthesized by peptide solid phase (Patent Document 14, Non-Patent Document 1).

Patent Documents 11 and 12 disclose a case where the content of a repeating unit having a fluorene ring in a polycarbonate resin is controlled to a specific range, whereby the stretched film including the polycarbonate resin exhibits a shorter wavelength. The smaller the retardation becomes, the lower the wavelength dispersion is, so it has excellent performance as a retardation film. The shorter the wavelength, the smaller the retardation, the so-called inverse wavelength dispersion retardation film can obtain the ideal retardation characteristics at each wavelength in the visible region. As a circular polarizer, it reflects the outer light of the image display device. Useful for prevention or perspective correction.

As the dihydroxy compound having a fluorene ring on the side chain, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene or 9,9-bis ( 4-hydroxy-3-methylphenyl) fluorene.

On the other hand, it is known that although it is not used for inverse wavelength dispersion, when a specific diester compound is used as the raw material of polyester carbonate, from the viewpoint of light transmittance, the content of chlorine contained in the compound is set. It is equal to or less than a specific amount (Patent Document 15).

Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 5-27118

Patent Document 2: Japanese Patent Laid-Open No. 10-68816

Patent Document 3: Japanese Patent Laid-Open No. 2000-137116

Patent Document 4: Japanese Patent No. 3325560

Patent Document 5: Japanese Patent Laid-Open No. 10-101786

Patent Document 6: Japanese Patent No. 5119250

Patent Document 7: Japanese Patent No. 5204200

Patent Document 8: Japanese Patent Laid-Open No. 2008-112124

Patent Document 9: Japanese Patent Laid-Open No. 2008-222965

Patent Document 10: US Patent Application Publication No. 2012/0170118

Patent Document 11: International Publication No. 2006/041190

Patent Document 12: International Publication No. 2011/149073

Patent Document 13: US Patent No. 3324084

Patent Document 14: International Publication No. 1991/08190

Patent Document 15: Japanese Patent Laid-Open No. 2-20518

Non-patent literature

Non-Patent Document 1: Synthesis, 1992, 819.

The development of the FPD field has attracted much attention. For retardation films, it is required to further improve the optical characteristics, quality, reliability, etc., or to further thin the film. Furthermore, there are also requirements for reducing the cost of materials or improving productivity in each step such as film formation, stretching, and lamination. With this, retardation films are required to have various characteristics. For example, as a material for retardation films, the industry seeks to have various characteristics such as low photoelastic coefficient, high heat resistance, melt processability, and mechanical strength if it has the required wavelength dispersion, and its inherent birefringence is relatively low. Large, excellent in flexibility or elongation. A material with a higher molecular alignment can be obtained by extension.

However, regarding a method of laminating a retardation film like in Patent Document 1 or Patent Document 2, the polarizing plate becomes thick. In addition, there is a problem that the retardation films must be laminated so that the late phase becomes a specific arrangement, which results in deterioration in productivity or yield of the polarizing plate. The retardation film of Patent Document 3 or Patent Document 4 has inverse wavelength dispersion, and a film can obtain a wide-band retardation characteristic. However, the cellulose acetate of Patent Document 3 has insufficient heat resistance, and is caused by moisture absorption. The problem of image speckle caused by size change.

It is known that a retardation film containing a polycarbonate resin having a fluorene ring of Patent Documents 4, 6, and 7 is useful as a retardation film exhibiting reverse wavelength dispersion or a circular polarizer for preventing external light reflection of an image display device. . However, the inventors carried out research, and as a result, they learned the following: Regarding resins using 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, because the film is relatively brittle, a higher orientation is obtained. The degree of extension is difficult. Regarding resins using 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, although the extensibility is relatively excellent, the photoelastic coefficient is slightly higher, and it is reliable at high temperatures. Poor sex.

As a method for improving various characteristics, a method of changing a copolymerization component or adjusting a ratio may be considered. However, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene has very high heat resistance, and on the other hand, the resin is changed. The brittle nature makes it difficult to maintain moderate heat resistance while improving the flexibility of the resin. In addition, in the case of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, in order to exhibit the required reverse wavelength dispersion, it is necessary to contain about 50 to 70% by mass of these monomers. The body composition, and therefore the degree of freedom in the design of the copolymerized molecule is low, and it is difficult to take into account characteristics such as heat resistance or mechanical strength and optical characteristics.

In addition, a polycarbonate resin using a fluorene-containing diol described in Patent Document 9 is not sufficient in terms of properties such as reverse wavelength dispersion, photoelastic coefficient, and heat resistance. Regarding the polyester described in Patent Document 10, it is described that the negative refractive index anisotropy, that is, the refractive index in the extending direction is smaller than the refractive index in the extending orthogonal 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 the necessary condition. Further, there is no description of the wavelength dependency of the phase difference in Patent Document 10.

As described above, it is difficult for the conventional retardation film to obtain various properties such as inverse wavelength dispersion, optical characteristics, heat resistance, and mechanical strength with good balance. In order to improve the characteristics of the retardation film, a novel compound having an excellent balance of various characteristics is used as a raw material.

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

Moreover, it is known that the stretched film containing the polycarbonate resin which has a fluorene ring of patent document 11 or 12 is useful as a retardation film which shows a reverse wavelength dispersion property, or a circularly polarizing plate for preventing external light reflection of an image display device. However, the present inventors conducted research, and as a result, the resin using 9,9-bis (4-hydroxy-3-methylphenyl) fluorene in Patent Document 11 has high heat resistance, but it is necessary to show In contrast to the inverse wavelength dispersion, it is necessary to increase the ratio of the repeating unit having a fluorene ring, easily become a brittle film, and there are problems in terms of flexibility. On the other hand, although the resin using 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene in Patent Document 12 is excellent in flexibility, it is necessary to make it exhibit the required reverse wavelength dispersion property. The ratio of the repeating unit having a fluorene ring becomes high, and it is difficult to balance various physical properties such as heat resistance and optical physical properties. Therefore, in order to further improve various physical properties such as optical physical properties, heat resistance, and flexibility of the resin, a compound having excellent balance between various physical properties such as optical physical properties and mechanical strength is used as a raw material.

Patent Documents 13 and 10 disclose polyesters obtained using difluorene compounds, but their heat resistance is not satisfactory due to the difluorene structure. In addition, it cannot be used as a film in Patent Document 13 and its optical characteristics and the like are not known. In Patent Document 10, no research has been conducted as a retardation film, and the wavelength dependency of the phase difference is also unknown.

It is a second object of the present invention to provide a novel amidine compound which has sufficient heat resistance and uses a small amount of the amidine compound to produce a resin composition and perform film forming. It exhibits excellent optical characteristics, thereby improving the freedom of resin design. Furthermore, a resin composition obtained using a novel amidine compound is provided.

Further, as a method for imparting specific physical properties to a resin as described in Patent Document 10, a method of using two types of oligomeric fluorene compounds having different reactive functional groups at the terminals in combination can be cited. However, it is difficult to obtain an oligomeric fluorene compound. In order to produce a resin having desired physical properties, two kinds of oligomeric fluorene compounds must be synthesized as raw materials, which requires time and cost.

The present inventors conducted diligent research, and as a result, found that, as a method for imparting desired physical properties to a resin with high practicality, a method using an oligomeric fluorene compound having different reactive functional groups at both ends is useful. As a method for producing such an oligomeric fluorene compound, the following methods can be cited: first, an oligomeric fluorene compound having one reactive functional group is produced as a raw material, and then the oligomeric fluorene compound is introduced into a reaction different from the reactive functional group Sexual functional group.

As a method for producing an oligomeric fluorene compound having one reactive functional group, for example, a method described in Non-Patent Document 1 is known, but this method has the following problem: it is difficult to selectively obtain one reactive functional group Oligomeric fluorene compounds, it is difficult to efficiently produce oligomeric fluorene compounds having different reactive functional groups at both ends.

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

Furthermore, the present inventors have made intensive research on a resin composition for inverse wavelength dispersion, and as a result, they have found that by using a specific oligomeric fluorene diester compound as a raw material monomer, even if the content of the resin is low, The required optical characteristics are efficiently displayed, and the freedom of resin design can be improved.

In general, when manufacturing a resin composition, in order to set the polymerization rate or the physical properties of the obtained resin composition to a specific one, it is necessary to strictly control the amount ratio of the raw materials. Oligomeric diesterification The compound is usually a solid. In order to use the compound as a raw material for a resin composition and to control the amount thereof, it is preferable to use the oligomeric diester compound. The inventors conducted diligent research, and as a result, they found that the compound may be colored when subjected to a melting process according to the amount of metal contained in the compound, and it is difficult to use it as a monomer for a resin composition for optical applications.

On the other hand, there are various methods for producing a polyester carbonate resin using a diester compound. As a general method thereof, it is known that a glycol, a diaryl carbonate, and a diester are melted by a transesterification method. Melt polymerization method. This method has the following problems: In the case of using a diaryl carbonate and a dialkyl ester as a diester, the transesterification reaction and the polymerization rate of the polycarbonate differ greatly, so it is difficult for the dialkyl ester to exist. Since it is introduced into polyester carbonate resin, it is more preferable to use a diaryl ester as the diester. In addition, as a method for producing an oligomeric fluorene diaryl compound having an aryl group at both ends, a method of substituting an aryl group at both ends of the oligomeric fluorene diester compound can be cited, but it has been newly found that according to the oligomerization The amount of carboxylic acid contained in the perylene diester compound, the metal content in the obtained oligomeric perylene diaryl compound becomes high, and coloration occurs during the melting process.

Therefore, a fourth object of the present invention is to provide an oligomeric fluorene diester compound, which is suitable for use as a monomer of a resin composition for optical applications, and which can increase the freedom of resin design, and can suppress the The colorer will be produced during the melting process.

Furthermore, an object of the present invention is to provide an oligomeric fluorene diester compound which can be used as a raw material for producing an oligomeric fluorene diaryl ester compound capable of suppressing coloration.

The present inventors have made diligent research in view of the above-mentioned first objective, and as a result, have found that a resin exhibits excellent optical characteristics or mechanical physical properties, and the resin is characterized in that the content of the aromatic structure in the repeating structural unit constituting the resin is at a specific level Range, and exhibit the required wavelength dispersion to complete the present invention. That is, this invention has the following summary.

[1-1]

A resin characterized in that it is a polycondensation resin having a repeating structural unit including an aromatic structure, and the content of the aromatic structure in the repeating structural unit satisfies the following formula (I), At least one structural unit among the structural units represented by Formula (1) and Formula (2).

5 ≦ A ≦ -22.5 × B + 38.3 (I)

Among them, 0.75 ≦ B ≦ 0.93

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

B: The ratio (R450 / R550) of the retardation (R450) at 450nm to the retardation (R550) at 550nm of the stretched film made of resin

(In the formulae (1) and (2), 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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in R ⁴ to R ⁹ may be bonded to each other to form a ring).

[1-2]

A resin characterized in that it is a polycondensation resin having a repeating structural unit including an aromatic structure, and the content of the aromatic structure in the repeating structural unit satisfies the following formula (III), and the glass transition of the resin is The temperature is 110 ° C or higher and 160 ° C or lower.

5 ≦ A ≦ -22.5 × B + 34.8 (III)

Among them, 0.75 ≦ B ≦ 0.93

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

B: The ratio (R450 / R550) of the retardation (R450) at 450nm to the retardation (R550) at 550nm of the stretched film made of resin

[1-3]

The resin described in [1-1] or [1-2] has a refractive index in the sodium d-line (589 nm) of 1.49 to 1.56.

[1-4]

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

[1-5]

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

[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], which contains a structural unit represented by the following formula (3).

[1-9]

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

[1-10]

A retardation film is obtained by extending a transparent film as described in [1-9] in at least one direction.

[1-11]

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

The inventors of the present invention have conducted diligent research in view of the above-mentioned second object, and as a result, they have found that a specific trimer diester compound has sufficient heat resistance, and a resin composition is produced using a small amount of the trimer diester compound and a film is formed. The present invention achieves excellent optical characteristics from time to time.

That is, this invention has the following summary.

[2-1]

A trifluorene diester, which comprises three fluorene units a which may have a substituent, and The carbon atoms at position 9 of the fluorene unit a are directly bonded to each other, or are chain-bonded via an alkylene group which may have a substituent, an alkylene group which may have a substituent, or an alkylene group which may have a substituent. Knot.

[2-2]

The tertiary diester described in [2-1] is represented by the following general formula (1).

(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 alkylene group having 1 to 10 carbon atoms which can be substituted, an alkylene group having 4 to 10 carbon atoms which can be substituted, or an alkylene group having 6 to 10 carbon atoms which can be substituted base.

R ⁴ to R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in 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 tertiary diester described in [2-2], wherein R ¹⁰ in the general formula (1) is an aryl group having 4 to 10 carbon atoms which may be substituted.

[2-4]

An oligomeric fluorene diester composition, characterized in that the oligomeric fluorene diester composition comprises the tertiary diester described in any one of [2-1] to [2-3], and a difluorene diester; The diester contains two fluorene units b which may have a substituent, and the carbon atoms at the 9-position of the fluorene unit b are directly bonded to each other, or via an alkylene group which may have a substituent, an arylene group which may have a substituent, or The aralkyl group which may have a substituent is bonded in a chain.

[2-5]

The oligomeric fluorene diester composition according to [2-4], wherein the difluorene diester is represented by the following general formula (2).

(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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in 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 oligomeric fluorene diaryl ester composition according to [2-4] or [2-5], wherein the content ratio of the above-mentioned trifluorene diester to the total mass of the composition is 1% by mass or more.

[2-7]

A resin composition, characterized in that it is made of or contains a polymer having a divalent trifluorene as a repeating unit, and the divalent trifluorene includes three trifluorene units which may have a substituent. a, the carbon atoms at position 9 of the fluorene unit a are directly bonded to each other, or are chain-like via an alkylene group which may have a substituent, an alkylene group which may have a substituent, or an alkylene group which may have a substituent Ground bond.

[2-8]

The resin composition according to [2-7], in which the divalent tris (3) is represented by the following general formula (11).

(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 alkylene group having 1 to 10 carbon atoms which can be substituted, an alkylene group having 4 to 10 carbon atoms which can be substituted, or an alkylene group having 6 to 10 carbon atoms which can be substituted base.

R ⁴ to R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in R ⁴ to R ⁹ may be bonded to each other to form a ring).

[2-9]

The resin composition according to [2-7] or [2-8], which further has a bivalent difluorene as a repeating unit, and the divalent bifluorene includes two fluorene units b which may have a substituent. The carbon atoms at position 9 of the fluorene unit b are directly bonded to each other, or are chain-bonded via an alkylene group which may have a substituent, an alkylene group which may have a substituent, or an alkylene group which may have a substituent. .

[2-10]

The resin composition according to any one of [2-7] to [2-9], which has a phase difference (Re450) measured at a wavelength of 450nm and a phase difference (Re550) measured at a wavelength of 550nm The ratio satisfies the following formula (20).

Re450 / Re550 ≦ 1.0 (20)

[2-11]

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

[2-12]

An optical member, which is made of the resin composition according to any one of [2-7] to [2-10].

[2-13]

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

[2-14]

An extended film characterized by being obtained by extending the film according to [2-13] in at least one direction.

[2-15]

A 1 / 4λ plate, characterized in that it is made of an stretched film as described in [2-14].

[2-16]

A circular polarizing plate is characterized by having a 1 / 4λ plate as described in [2-15].

[2-17]

An image display device, comprising the circular polarizing plate as described in [2-16].

The inventors of the present invention have conducted diligent research in view of the above-mentioned third objective, and as a result, have found that the oligomeric fluorene compound having hydrogen at both ends thereof can be replaced with an olefin compound having a specific reactive functional group, thereby achieving high selectivity and high efficiency. To obtain the desired oligomeric fluorene compound, the oligomeric fluorene compound is suitable as a monomer or a monomer raw material of a resin composition for optical use, thereby completing the present invention.

That is, this invention has the following summary.

[3-1]

An oligomeric fluorene is characterized in that it includes carbon atoms at the 9-position of two or more fluorene units a which may have a substituent, via an alkylene group which may have a substituent, an arylene group which may have a substituent, Or an oligomeric fluorene structural unit (hereinafter, referred to as "oligomeric fluorene structural unit a") which may be chain-bonded by an aralkyl group having a substituent, and the oligomeric fluorene structural unit a The carbon atom at the 9th position of the fluorene unit a at either end has a reactive functional group represented by the following formula (A), and the carbon atom at the 9th position of the fluorene unit a at the other end has a hydrogen atom.

[Chemical 6]

(In the formula, R ^a to R ^c are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or 6 to 10 carbon atoms that can be substituted. The aralkyl group, X is an ester group, amidino group, a carboxyl group, a cyano group, or a nitro group. * Is a bond with the carbon atom at the 9-position of the a unit of a fluorene).

[3-2]

The oligomeric fluorene as described in [3-1] is represented by the following general formula (1).

(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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in 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 alkyl group having 1 to 10 carbon atoms which can be substituted, an aryl group having 4 to 10 carbon atoms which can be substituted or an aralkyl group having 6 to 10 carbon atoms which can be substituted .

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

n represents an integer value of 1 to 5).

[3-3]

An oligomeric fluorene is characterized in that it includes carbon atoms at the 9-position of two or more fluorene units a which may have a substituent, via an alkylene group which may have a substituent, an arylene group which may have a substituent, Or an oligomeric fluorene structural unit a which may be chain-bonded by an aralkyl group having a substituent, and the carbon at the 9th position of the fluorene unit a at any terminal in the oligomeric fluorene structural unit a The atom has a reactive functional group represented by the following formula (A), and the carbon atom at the 9-position of the fluorene unit a at the other end has a reactive functional group different from the reactive functional group.

(In the formula, R ^a to R ^c are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or 6 to 10 carbon atoms that can be substituted. The aralkyl group, X is an ester group, amidino group, a carboxyl group, a cyano group, or a nitro group. * Is a bond with the carbon atom at the 9-position of the fluorene unit).

[3-4]

The oligomeric fluorene as described in [3-3] is represented by the following general formula (2).

(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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in R ⁴ to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is a direct bond, an alkylene group having 1 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, or an alkylene group having 6 to 10 carbon atoms that can be substituted, Or selected from the group consisting of an alkylene group having 1 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, and an alkylene group having 6 to 10 carbon atoms that can be substituted Two or more radicals are a radical formed by bonding an oxygen atom, a sulfur atom that may be substituted, a nitrogen atom that may be substituted, or a carbonyl group.

R ^a to R ^c are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which can be substituted, an aryl group having 4 to 10 carbon atoms which can be substituted or an aralkyl group having 6 to 10 carbon atoms which can be substituted X is an ester group, amidino group, a carboxyl group, a cyano group, or a nitro group, and A is a hydroxyl group, an amine group, an ester group, a fluorenyl group, a carboxyl group, a cyano group, or a nitro group.

n represents an integer value of 1 to 5).

[3-5]

An oligomeric fluorene composition comprising the oligomeric fluorene (hereinafter referred to as "oligomeric fluorene A") as described in any one of [3-1] to [3-4], and having An oligomeric fluorene (hereinafter, referred to as "oligomeric fluorene B") having a chemical structure different from the oligomeric fluorene A, and the oligomeric fluorene B includes 9 positions of two or more fluorene units b which may have a substituent. Oligomeric fluorene structural units in which the carbon atoms are chain-bonded via an alkylene group which may have a substituent, an alkylene group which may have a substituent, or an alkylene group which may have a substituent (hereinafter, (Referred to as "oligomeric fluorene structure unit b"), the carbon atom at the 9-position of the fluorene unit b at both ends of the oligomeric fluorene structure unit b has The same reactive functional group represented by the following formula (B).

(In the formula, ^Rd to ^Rf are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or 6 to 10 carbon atoms that can be substituted For an aralkyl group, X ¹ is an ester group, amidino 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 composition characterized in that it is composed of the polymer of oligomeric fluorene as described in any one of [3-1] to [3-4] or the oligomeric fluorene of [3-5] Made of, or containing, polymers.

[3-7]

A film made of the resin composition as described in [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 stretch film according to [3-8].

[3-10]

A method for producing oligomeric fluorene, comprising reacting an oligomeric fluorene 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. Then, an oligomeric fluorene represented by the following formula (1) was obtained.

[Chemical 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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Amino groups of substituents, vinyl groups having 1 to 10 carbon atoms which may have substituents, ethynyl groups of carbon 1 to 10 which may have substituents, sulfur atoms having substituents, silicon atoms having substituents, halogen atoms, Nitro, or cyano. Among them, at least two adjacent groups in 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 alkyl group having 1 to 10 carbon atoms which can be substituted, an aryl group having 4 to 10 carbon atoms which can be substituted or an aralkyl group having 6 to 10 carbon atoms which can be substituted X is an ester group, amidino group, a carboxyl group, a cyano group, or a nitro group.

n represents an integer value of 1 to 5).

[3-11]

A method for producing an oligomeric fluorene, which comprises reacting the oligomeric fluorene represented by the above formula (1) obtained in the method [3-10] with an electrophilic compound to obtain the following formula (2) An oligomeric puppet.

[Chemical 12]

(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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in R ⁴ to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is a direct bond, an alkylene group having 1 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, or an alkylene group having 6 to 10 carbon atoms that can be substituted, Or selected from the group consisting of an alkylene group having 1 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, and an alkylene group having 6 to 10 carbon atoms that can be substituted Two or more radicals are formed by an oxygen atom, a sulfur atom that may be substituted, a nitrogen atom that may be substituted, or a carbonyl group. ^Ra to R ^c are each independently a hydrogen atom, and the number of carbons that may be substituted is 1 to An alkyl group of 10, an aryl group of 4 to 10 carbons which may be substituted or an arylalkyl group of 6 to 10 carbons which may be substituted, X is an ester group, amidino group, a carboxyl group, a cyano group, or a nitro group, A is a hydroxyl group, an amine group, an ester group, a sulfonylamino group, a carboxyl group, a cyano group, or a nitro group.

n represents an integer value of 1 to 5).

The present inventors have conducted diligent research in view of the above-mentioned fourth objective, and as a result, have found that the content ratio of the metal component contained in the oligomeric fluorene diester compound can be specifically adjusted. A certain range to improve the stability in the molten state and suppress coloration.

Further, it was found that by using an oligomeric fluorene diester compound having a carboxylic acid content ratio in a specific range as a raw material for producing an oligomeric fluorene diaryl ester compound capable of suppressing coloration, the obtained diaryl ester can be reduced. The content ratio of the metal component contained in the compound.

That is, this invention has the following summary.

[4-1]

An oligomeric fluorene diester, characterized in that it comprises two or more fluorene units which may have a substituent, and the carbon atoms at the 9-position of the fluorene unit are directly bonded to each other, or via an alkylene which may have a substituent. Group, an arylene group which may have a substituent, or an aralkyl group which may have a substituent are bonded in a chain, and the content ratio of the metal is 500 mass ppm or less.

[4-2]

The oligomeric fluorene diester as described in [4-1], wherein the metal is selected from the group consisting of long-period periodic table Group 1, Group 2, Group 12, Group 14, and transition metals At least 1 metal.

[4-3]

The oligomeric fluorene diester according to [4-1] or [4-2], which is represented by the following general formula (1).

(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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, a substituent shoulder A silicon atom, a halogen atom, a nitro group, or a cyano group. Among them, at least two adjacent groups in 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 oligomeric fluorene diester according to [4-3], wherein R ¹⁰ in the general formula (1) is an aryl group having 4 to 10 carbon atoms.

[4-5]

An oligomeric fluorene diester, which is characterized in that it includes two or more fluorene units which may have a substituent, and the carbon atoms at the 9-position of the fluorene unit are directly bonded to each other, or via an extension which may have a substituent. An alkyl group, an arylene group which may have a substituent, or an aralkyl group which may have a substituent are chain-bonded, and the content ratio of a carboxylic acid is 10 mass% or less.

[4-6]

The oligomeric fluorene diester according to [4-5], which is represented by the following general formula (1).

(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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in 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 oligomeric fluorene diaryl ester, characterized in that the oligomeric fluorene diester as described in [4-6] is used as a raw material, and the above-mentioned R ¹⁰ group is substituted with an aryl group to obtain a diaryl ester.

[4-8]

The manufacturing method of the resin composition characterized by using the oligomeric fluorene diester as described in any one of [4-1] to [4-6] as a raw material.

The resin of the present invention is excellent in balance among various characteristics such as optical characteristics, heat resistance, mechanical characteristics, and reliability. Therefore, the resin of the present invention can be preferably used for an optical film such as a retardation film.

In addition, the novel amidine compound of the present invention has sufficient heat resistance, and exhibits excellent optical characteristics when a resin composition is produced by using the amidine compound to form a film, thereby improving the freedom of resin design.

In addition, the oligomeric fluorene compound of the present invention selectively has a desired reactive function It can be preferably used as a monomer or a monomer raw material of a resin composition for optical applications.

In addition, the oligomeric fluorene diester compound of the present invention can be preferably used as a monomer or a monomer raw material of a resin composition for optical applications, and also improves the degree of freedom in resin design, thereby suppressing the generation of the resin composition during the melting process. Coloring.

FIG. 1 is a graph comparing the metal content in the oligomeric fluorene diesters of Examples 4-1 to 4-4 and Comparative Example 4-1 with the difference in absorbance before and after heating.

FIG. 2 is a graph showing particle size distributions of oligomeric fluorene diesters in Reference Examples 4-1 and 4-2.

Hereinafter, the embodiment of the present invention will be described in detail, but the description of the constituent elements described below is an example (representative example) of the embodiment of the present invention. The present invention is not limited to the following as long as it does not exceed the gist thereof. .

In addition, the so-called "repeating structural unit" in the present invention is a structural unit in which the same structure appears repeatedly in the resin, and the structural unit of the resin is constituted by respective connection. More specifically, if it is a polycarbonate resin, it is also called a repeating structural unit including a carbonyl group.

In addition, the "structural unit" refers to a partial structure constituting a resin and a specific partial structure included in a repeating structural unit. For example, it refers to the part of the structure held by the adjacent linking group in the resin, or the polymerizable reactive group existing at the terminal part of the polymer, and the part of the structure held between the linking group adjacent to the polymerizable reactive group. More specifically, for example, in the case of a polycarbonate resin, a partial structure sandwiched between adjacent carbonyl groups using a carbonyl group as a linking group is referred to as a structural unit.

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

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

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

"Invention 1"

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

The following general formulae (1) to (9) and (11) to (15) describe each structure in the present invention.

A first aspect of the present invention is a resin characterized in that it is a polycondensation resin having a repeating structural unit including an aromatic structure, and the content of the aromatic structure in the repeating structural unit satisfies the following formula (I ), The resin has at least one structural unit selected from the structural units represented by the following formula (1) and formula (2).

5 ≦ A ≦ -22.5 × B + 38.3 (I)

Among them, 0.75 ≦ B ≦ 0.93

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

B: The ratio (R450 / R550) of the retardation (R450) at 450nm to the retardation (R550) at 550nm of the stretched film made of resin

(In the formulae (1) and (2), R ¹ to R ³ are each independently a direct bond and 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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in R ⁴ to R ⁹ may be bonded to each other to form a ring).

A second aspect of the present invention is a resin characterized in that it is a polycondensation resin having a repeating structural unit including an aromatic structure, and the content of the aromatic structure in the repeating structural unit satisfies the following formula (III ), And the glass transition temperature of the resin is 120 ° C or higher and 160 ° C or lower.

5 ≦ A ≦ -22.5 × B + 34.8 (III)

Among them, 0.75 ≦ B ≦ 0.93

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

B: The ratio (R450 / R550) of the retardation (R450) at 450nm to the retardation (R550) at 550nm of the stretched film made of resin

<Resin of the present invention>

The resin of the present invention is a polycondensation resin. The so-called polycondensation resin refers to a resin obtained by polycondensation as defined in Glossary of basic terms in polymer science (IUPAC Recommendations 1996), and is a polymer chain that grows through a condensation reaction between molecules. Resin obtained by polymerization. The polycondensation resin of the present invention is preferably a resin having at least one bond selected from carbonate bonds and ester bonds, and more specifically, polycarbonate, polyester, and polyester carbonate Either resin. These resins include advantages such as excellent heat resistance, mechanical properties, and melt processability, and by copolymerizing a plurality of monomers, it is easy to control various physical properties such as optical properties, heat resistance, and mechanical properties to The required range.

If the resin of the present invention contains an aromatic structure, as the aromatic structure, An aromatic cyclic structure is assumed to include an arbitrary structure. More specific examples include benzene-like aromatic rings, non-benzene-like aromatic rings, and heteroaromatic rings. Among them, benzene-like aromatic rings or heteroaromatic rings are preferred. In the present invention, a method for calculating the content of the aromatic structure in the repeating structural unit constituting the resin will be described below with reference to specific examples.

[Calculated molecular weight of various aromatic structures]

The molecular weight of the aromatic structure in the present invention includes carbon atoms, hydrogen atoms, and heteroatoms in an aromatic cyclic structure. Carbon atoms or heteroatoms bonded to an aromatic cyclic structure are not included in the aromatic structure. In addition, when vinyl, ethynyl, carbonyl and the like are bonded to an aromatic cyclic structure, the conjugated system of the aromatic ring is extended to these functional groups, but the aromatic structure does not include a bond to Substituents for aromatic cyclic structures.

[Chemical 16]

[Chemical 17]

[Calculation example 1]

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]

When it is a copolymerized resin of repeating structural unit A and repeating structural unit B, and the molar ratio of repeating structural unit A and repeating structural unit B, that 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). It is more preferable to satisfy the following formula (II), and it is more preferable to satisfy the 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)

Among them, 0.75 ≦ B ≦ 0.93.

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

B: The ratio (R450 / R550) of the retardation (R450) at 450nm to the retardation (R550) at 550nm of the stretched film made of resin

In the case where the value of R450 / R550 of the above formula (I) is less than 1, the phase difference has inverse wavelength dispersion, and when used as a quarter-wave plate, a near-ideal value can be obtained in a wide range of wavelengths. Phase difference characteristics. As one of the methods of exhibiting the inverse wavelength dispersion property, there can be mentioned a method which makes the wavelength dispersion (wavelength dependence) of the refractive index larger than that of the main chain component of the polymer chain. The components are aligned in a direction perpendicular to the main chain. In general, the longer the aromatic conjugate system becomes, the larger the wavelength dispersion of the refractive index becomes. Therefore, it is preferable that the resin having an inverse wavelength dispersion property contains an aromatic structure. On the other hand, when the main chain component contains aromatics, the aromatic components on the main chain exhibit strong positive wavelength dispersion, and therefore, reverse wavelength dispersion is eliminated. In addition, when aromatic is contained in a large amount, the photoelastic coefficient or refractive index generally increases, and the optical properties are not good. The above formula (I) is intended to guide an aromatic structure with a higher expression efficiency of inverse wavelength dispersion, and suppress other aromatic components to the required minimum. By performing the above-mentioned molecular design, a resin having inverse wavelength dispersion and excellent balance of optical characteristics such as a photoelastic coefficient or alignment can be obtained. Specific and preferred molecular structures are described below.

The value of B (R450 / R550) is a value of wavelength dispersion measured in an evaluation using a stretched film obtained from an unstretched film made of a resin by a hot pressing method.

<Oligomerization unit>

The resin of the present invention preferably has one or more structural units selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). Hereinafter, this structural unit may be referred to as an oligomeric fluorene structural unit.

In the general formula (1) and the general formula (2), R ¹ to R ³ are each independently a direct bond and 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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano.

Among R ¹ and R ² , as the "alkylene group having 1 to 4 carbon atoms which may have a substituent", for example, the following alkylene groups can be used. Methylene, ethylene, n-propyl, n-butyl, etc. linear alkylene; methylmethylene, dimethylmethylene, ethylmethylene, propylmethylene, ( 1-methylethyl) methylene, 1-methylphenyl, 2-methylphenyl, 1-ethylphenyl, 2-ethylphenyl, 1-methylphenyl, 2 -Methylene, 1,1-dimethyl, ethyl, 2,2-dimethyl, and 3-methyl, and other alkylene groups having a side chain. Here, the positions of the side chains in R ¹ and R ² are represented by numbers assigned such that the carbon on the fluorene ring side becomes one position.

The choice of R ¹ and R ² has a particularly important effect on the appearance of the inverse wavelength dispersion. The above resin exhibits the strongest inverse wavelength dispersion property in a state where the fluorene ring is vertically aligned in the main chain direction (extending direction). In order to make the alignment state of the fluorene ring close to the above-mentioned state to exhibit strong inverse wavelength dispersion, it is preferable to use R ¹ and R ² having a carbon number of 2 to 3 on the main chain of the alkylene group. When the carbon number is 1, there may be a case where the inverse wavelength dispersion property does not appear unexpectedly. As the main reason, it can be considered that the orientation of the fluorene ring is fixed to a direction that is not perpendicular to the main chain direction due to the steric hindrance of a carbonate group or an ester group as a linking group of the oligomeric fluorene structural unit. On the other hand, when the number of carbons is too large, the fixation of the orientation of the fluorene ring may be weakened, and the reverse wavelength dispersion may be weakened. In addition, the heat resistance of the resin is also reduced.

As shown in the above general formula (1) and general formula (2), one end of R ¹ and R ² is an alkylene group bonded to a fluorene ring, and the other end is bonded to an oxygen atom or a carbonyl carbon contained in the linking group. Either. From the viewpoints of thermal stability, heat resistance, and inverse wavelength dispersion, the other end of the alkylene group is preferably bonded to a carbonyl carbon. As described below, as the monomer having an oligomeric fluorene structure, specifically, a structure of a diol or a diester (hereinafter, the diester is also one containing a dicarboxylic acid) can be considered, and the diester is preferably used for The raw materials are polymerized.

From the viewpoint of facilitating production, it is preferred that R ¹ and R ² use the same alkylene group.

In R ³ , as the "alkylene group having 1 to 4 carbon atoms which may have a substituent", for example, the following alkylene groups can be used. Straight-chain alkylenes such as ethylene, ethylene, n-propyl, n-butyl, etc .; methylmethylene, dimethylmethylene, ethylmethylene, propylmethylene, ( 1-methylethyl) methylene, 1-methylphenyl, 2-methylphenyl, 1-ethylphenyl, 2-ethylphenyl, 1-methylphenyl, 2 -Methylene, 1,1-dimethyl, ethyl, 2,2-dimethyl, and 3-methyl, and other alkylene groups having a side chain.

R ³ preferably has a carbon number of 1 to 2 on the main chain of the alkylene group, and particularly preferably has a carbon number of 1. In the case of using R ^{3 with} too many carbon atoms on the main chain, there is a possibility that the fixation of the ring is weak like R ¹ and R ² , resulting in a decrease in inverse wavelength dispersion and an increase in photoelasticity coefficient. , Reduction of heat resistance, etc. On the other hand, the one with a smaller number of carbons on the main chain has good optical properties or heat resistance. When the 9 positions of the two fluorene rings are connected by a direct bond, the thermal stability is deteriorated.

In R ¹ to R ³ , as the substituent which the alkylene group may have, the substituents exemplified below may be used, and substituents other than these may also be used. 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; Fluorenyl groups; fluorenyl groups such as acetamido, benzamidine and the like having a carbon number of 1 to 10; nitro; cyano; 1 to 3 hydrogen atoms may pass through the halogen atom, the alkoxy group, and the fluorenyl group 6-6 aryl groups such as substituted phenyl groups, substituted phenyl groups, naphthyl groups, and the like, such as the amidino group, the nitro group, and the cyano group.

The number of the above-mentioned substituents is not particularly limited, but is preferably 1-3. When there are two or more substituents, the kinds of the substituents may be the same or different. When there are too many substituents, there exists a possibility that reaction may be inhibited during a polymerization, or thermal decomposition may be performed. In addition, from the standpoint that it can be manufactured inexpensively industrially, R ¹ to R ^{3 are} preferably unsubstituted.

Among R ⁴ to R ⁹ , as the "alkyl group having 1 to 10 carbon atoms which may have a substituent", for example, the following alkyl groups can be used. Linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-decyl; isopropyl, 2-methylpropyl, 2,2-dimethyl Alkyl groups having side chains such as propyl and 2-ethylhexyl; cyclic alkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl.

The carbon number of the alkyl group is preferably 4 or less, and more preferably 2 or less. If it is within this range, the steric hindrance of the fluorene rings is difficult to occur, and the optical characteristics required from the fluorene rings tend to be obtained.

As the substituent which the above-mentioned alkyl group may have, the substituents exemplified below may be used, but other substituents may be used. 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; Fluorenyl groups; fluorenyl groups such as acetamido, benzamidine, and the like having a carbon number of 1 to 10; nitro; cyano; 6-6 aryl groups such as substituted phenyl groups, substituted phenyl groups, naphthyl groups, and the like, such as the amidino group, the nitro group, and the cyano group.

The number of the above-mentioned substituents is not particularly limited, but is preferably 1-3. When there are two or more substituents, the kinds of the substituents may be the same or different. When there are too many said substituents, there exists a possibility that reaction may be suppressed during a polymerization, or thermal decomposition may advance. In addition, from the viewpoint of industrially inexpensive production, it is preferable that R ⁴ to R ^{9 are} unsubstituted. Specific examples of the alkyl group include trifluoromethyl, benzyl, 4-methoxybenzyl, and methoxymethyl.

In R ⁴ to R ⁹ , as the "aryl group having 4 to 10 carbon atoms which may have a substituent", for example, the following aryl group may be used. Aryl groups such as phenyl, 1-naphthyl, and 2-naphthyl; heteroaryl groups such as 2-pyridyl, 2-thienyl, and 2-furyl.

The carbon number of the aryl group is preferably 8 or less, and more preferably 7 or less. If it is within this range, the steric hindrance of the fluorene rings is difficult to occur, and the optical characteristics required from the fluorene rings tend to be obtained.

In R ⁴ to R ⁹ , as the substituent that the aryl group may have, the substituents exemplified below may be used, and substituents other than these may also be used. Halogen atom selected from fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, isopropyl, etc .; carbon group having 1 to 10 carbon atoms such as methoxy and ethoxy Alkoxy; fluorenyl groups having 1 to 10 carbon atoms, such as ethenyl and benzamidine; fluorenyl groups having 1 to 10 carbon atoms, such as ethenylamino and benzamidine; nitro; cyano. The number of the above-mentioned substituents is not particularly limited, but is preferably 1-3. When there are two or more substituents, the kinds of the substituents may be the same or different. In addition, from the viewpoint of industrially inexpensive production, it is preferable that R ⁴ to R ^{9 are} unsubstituted.

Specific examples of the aryl group include 2-methylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 4-benzylphenyl, and 4-methoxybenzene. Methyl, 4-nitrophenyl, 4-cyanophenyl, 3-trifluoromethylphenyl, 3,4-dimethoxyphenyl, 3,4-methylenedioxyphenyl, 2 , 3,4,5,6-pentafluorophenyl, 4-methylfuryl and the like.

Among R ⁴ to R ⁹ , as the "fluorenyl group having 1 to 10 carbon atoms which may have a substituent", for example, the following fluorenyl groups may be used. Alimentary fluorenyl groups such as formamyl, acetamyl, propionyl, 2-methylpropanyl, 2,2-dimethylpropanyl, and 2-ethylhexyl; benzyl, 1 -Aromatic fluorenyl groups such as naphthylcarbonyl, 2-naphthylcarbonyl, and 2-furylcarbonyl.

The carbon number of the amidino group is preferably 4 or less, and more preferably 2 or less. If it is within this range, the steric hindrance of the fluorene rings is difficult to occur, and the optical characteristics required from the fluorene rings tend to be obtained.

As the substituent which the above-mentioned fluorenyl group may have, the substituents exemplified below may be used, but other substituents may be used. Selected from fluorine, chlorine, bromine and iodine Halogen atom of the child; Alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, isopropyl; Alkoxy group having 1 to 10 carbon atoms such as methoxy and ethoxy; Ethylamino, benzamidine Amine groups such as amine groups having 1 to 10 carbon atoms; nitro groups; cyano groups; 1 to 3 hydrogen atoms can pass through the above halogen atoms, alkoxy groups, acetamido groups, benzamidine groups, and other carbon numbers 1 to 10 6-10 carbon atoms, such as fluorenyl group, said fluorenylamino group, said nitro group, said cyano group, substituted phenyl group, naphthyl group, etc.

The number of the above-mentioned substituents is not particularly limited, but is preferably 1-3. When there are two or more substituents, the kinds of the substituents may be the same or different. In addition, from the viewpoint of industrially inexpensive production, it is preferable that R ⁴ to R ^{9 are} unsubstituted.

Specific examples of the above-mentioned fluorenyl group include chloroethenyl, trifluoroacetamyl, methoxyacetamyl, phenoxyacetamyl, 4-methoxybenzylamyl, and 4-nitro Benzamidine, 4-cyanobenzyl, 4-trifluoromethylbenzyl and the like.

Among R ⁴ to R ⁹ , as the "fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent", for example, the following fluorenyloxy group can be used. Aliphatic alkoxy groups such as formamyl, ethenyl, propionyl, butyl fluorenyl, propylene fluorenyl, methacryl fluorenyl; and aromatic fluorenyl oxy groups such as benzamyl.

The carbon number of the amidino group is preferably 4 or less, and more preferably 2 or less. If it is within this range, the steric hindrance of the fluorene rings is difficult to occur, and the optical characteristics required from the fluorene rings tend to be obtained.

As the substituent which the above-mentioned fluorenyloxy group may have, the substituents exemplified below may be used, but substituents other than these may also be used. Halogen atom selected from fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, isopropyl, etc .; carbon group having 1 to 10 carbon atoms such as methoxy and ethoxy Alkoxy; acetamido, benzamido, and other amines having 1 to 10 carbon atoms; nitro; 1 to 3 hydrogen atoms can pass through cyano; the above halogen atom, the above alkoxy, and acetamidine A fluorenyl group having 1 to 10 carbon atoms such as a phenyl group, a benzamidine group, an aryl group having 6 to 10 carbon atoms such as a substituted phenylamino group, the nitro group, and the cyano group, and a naphthyl group.

The number of the above-mentioned substituents is not particularly limited, but is preferably 1-3. When there are two or more substituents, the kinds of the substituents may be the same or different. In addition, from the viewpoint of industrially inexpensive production, it is preferable that R ⁴ to R ^{9 are} unsubstituted. Specific examples of the above-mentioned fluorenyl group include chloroethenyl, trifluoroacetamyl, methoxyacetamyl, phenoxyacetamyl, 4-methoxybenzylamyl, and 4-nitro Benzamidine, 4-cyanobenzyl, 4-trifluoromethylbenzyl and the like.

Among R ⁴ to R ⁹ , as the "alkoxy group or aryloxy group having 1 to 10 carbon atoms which may have a substituent", for example, the following alkoxy groups and aryloxy groups can be used. Alkoxy groups such as methoxy, ethoxy, isopropoxy, tertiary butoxy, and trifluoromethoxy; aryloxy groups such as phenoxy.

Among the alkoxy group and the aryloxy group, an alkoxy group is preferred, and the number of carbon atoms in the alkoxy group is preferably 4 or less, more preferably 2 or less. If it is within this range, the steric hindrance of the fluorene rings is difficult to occur, and the optical characteristics required from the fluorene rings tend to be obtained.

In R ⁴ to R ⁹ , as the specific structure of the “amino group which may have a substituent”, for example, the following amine groups may be used, but other amine groups may be used. Amino groups; N-methylamino, N, N-dimethylamino, N-ethylamino, N, N-diethylamino, N, N-methylethylamino, N- Aliphatic amine groups such as propylamino, N, N-dipropylamino, N-isopropylamino, N, N-diisopropylamino; N-phenylamino, N, N- Aromatic amino groups such as diphenylamino; fluorenylamino groups such as formamidine, acetamido, decylamino, benzamidine, and chloroacetamido; benzyloxycarbonylamino, third Alkoxycarbonylamino groups such as butoxycarbonylamino.

As the amine group, N, N-dimethylamino group, N-ethylamino group, or N which does not have a proton having a high acidity, has a small molecular weight, and has a tendency to increase the fluorene ratio is preferably used. N-diethylamino group, more preferably N, N-dimethylamino group.

In R ⁴ to R ⁹ , as the "vinyl or ethynyl group having 1 to 10 carbon atoms which may have a substituent", for example, the following vinyl groups and ethynyl groups may be used, but other vinyl groups may also be used. Wait. Vinyl, 2-methylvinyl, 2,2-dimethylvinyl, 2-phenylvinyl, 2-ethenylvinyl, ethynyl, methylethynyl, tert-butylethynyl, Phenylethynyl, ethenylethynyl, trimethylsilylethynyl.

The number of carbon atoms of the vinyl group and the ethynyl group is preferably 4 or less. If it is within this range, However, the steric hindrance of the fluorene rings is difficult to be generated, and the desired optical characteristics derived from the fluorene rings tend to be obtained. In addition, as the conjugation system of the cymbal ring becomes longer, it becomes easier to obtain stronger inverse wavelength dispersion.

In R ⁴ to R ⁹ , as the "sulfur atom having a substituent", for example, the following sulfur-containing groups can be used, but other sulfur-containing groups can also be used. Sulfo groups; alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl; arylsulfonyl such as phenylsulfonyl, p-tolylsulfonyl; Alkylsulfinyl sulfenyl groups such as methylsulfinyl sulfenyl, ethylsulfinyl sulfinyl, propylsulfinyl sulfinyl, isopropylsulfinyl sulfinyl; phenylsulfinyl sulfinyl, p-tolylsulfinyl sulfinyl Isoarylsulfinyl groups; alkylthio groups such as methylthio and ethylthio; arylthio groups such as phenylthio and p-tolylthio; alkoxy groups such as methoxysulfonyl and ethoxysulfonyl Sulfonyl; aryloxysulfonyl such as phenoxysulfonyl; aminesulfonyl; N-methylaminosulfonyl, N-ethylaminosulfonyl, N-third butyl Alkylsulfonyl groups such as aminosulfonyl, N, N-dimethylaminosulfonyl, N, N-diethylaminosulfonyl; N-phenylaminosulfonyl, N, Arylaminosulfonyl groups such as N-diphenylaminosulfonyl. Furthermore, the sulfo group may form a salt with lithium, sodium, potassium, magnesium, ammonium, and the like.

Among the above sulfur-containing groups, methylsulfinyl, ethylsulfinyl, or phenylsulfinyl, which does not have a high acidity proton and has a small molecular weight and can increase the ratio of amidine, is preferred. It is more preferable to use methylsulfinamilide.

Among the R ⁴ to R ⁹ , as the "silicon atom having a substituent", for example, the following silyl groups can be used. Trialkylsilyl groups such as trimethylsilyl group and triethylsilyl group; trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group. Among these, a trialkylsilyl group which can be stably handled is preferable.

In R ⁴ to R ⁹ , as the "halogen atom", a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be used. Among these, a fluorine atom, a chlorine atom, or a bromine atom, which is relatively easy to introduce and has a tendency to increase the reactivity at the 茀 -9 position due to its electron-withdrawing property, is more preferably a chlorine atom or a bromine atom.

In addition, two adjacent groups in 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 exemplified by the following [A] group.

[A]

As described above, by setting R ⁴ to R ⁹ as the specific atom or substituent as described above, there is less steric hindrance between the main chain and the fluorene ring, or between the fluorene ring and each other. Tendency of the required optical characteristics of the ring.

The fluorene ring contained in the oligomeric fluorene structure unit is 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 a halogen atom, a fluorenyl group, a nitro group, a cyano group, and Any of the groups consisting of a sulfo group, and R ⁵ to R ⁸ are any of the constitution of a hydrogen atom. In the case of the former constitution, a compound containing the above-mentioned oligomeric fluorene structural unit can be derived from industrially inexpensive fluorene. Moreover, in the case of having the latter constitution, the reactivity of the 茀 -position 9 is improved. Therefore, in the synthesis process of the compound containing the oligomeric fluorene structure unit, it is possible to adapt to various derivatization reactions. 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 any one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and a nitro group. In addition, R ⁵ to R ⁸ are each a structure of a hydrogen atom, and particularly preferably, R ⁴ to R ^{9 are} all a structure of a hydrogen atom. By adopting the above-mentioned configuration, the erbium ratio can be increased, and the steric hindrance of the erbium rings is difficult to occur, so that the optical characteristics required from the erbium rings can be obtained.

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

[B] group

[Chemical 22]

The oligomeric fluorene structural unit of the present invention and the structural unit derived from the commonly used 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (the following structural formula (9)) or derived from 9 The structural units of 9-bis (4-hydroxy-3-methylphenyl) fluorene (the following structural formula (10)) are compared and have the following characteristics.

‧ Aromatic components such as benzene rings that were previously introduced into the main chain of the polymer have not been introduced into the main chain of the polymer, so the photoelastic coefficient can be reduced.

‧The shorter the above-mentioned aromatic component introduced into the main chain is, the shorter the wavelength of positive light and the greater the birefringence is, the greater the positive wavelength dispersion. Therefore, the anti-wavelength dispersion of the ring from the side chain previously canceled out, so as the overall anti- Reduced wavelength dispersion. On the other hand, the aromatic component is not introduced into the main chain, whereby the inverse wavelength dispersion property can be more strongly exhibited.

‧ High heat resistance can be imparted by introducing two fluorene rings into one molecule.

‧ Since the main chain is composed of a soft alkylene chain, it can impart softness or melt processability to the resin.

The resin of the present invention contains a resin containing at least one of a carbonate bond and an ester bond and a oligomeric fluorene structural unit. Polycarbonates, polyesters, and polyester carbonates which are resins having the above-mentioned bonding group are excellent in heat resistance, mechanical properties, and melt processability. In addition, it has the advantages that by copolymerizing with other monomers, the above oligomeric fluorene structural unit can be relatively easily introduced into the resin, and the ratio of the oligomeric fluorene structural unit in the resin can be easily controlled as required range.

Examples of the method for introducing the oligomeric fluorene structural unit into the resin include a method of copolymerizing a diol or diester having the oligomeric fluorene structural unit and another diol or diester. Specifically, a polycarbonate can be obtained by polymerizing a combination of a diol and a carbonic acid diester represented by the following general formula (11). In addition, by polymerizing with a combination of a diol and a diester, a polyester can be obtained. In addition, polyester carbonate can be obtained by polymerizing a combination of a diol, a diester, and a carbonic acid diester.

[Chemical 24]

In the general formula (11), A ¹ and A ² are each 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. A ¹ and A ² may be the same or different. .

Examples of the monomer having the oligomeric fluorene structure unit include a specific diol represented by the following general formula (12) or a specific diester represented by the following general formula (13).

In the general formula (12) and the general formula (13), R ¹ to R ³ are each independently a direct bond and 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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano.

A ³ and A ⁴ are each a hydrogen atom or 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. A ³ and A ⁴ may be the same or different.

As said monomer which has the said divalent oligomeric fluorene structure unit, it is preferable to use the specific diester represented by the said General formula (13). The thermal stability of the specific diester is relatively better than the specific diol represented by the general formula (12), and the fluorene ring in the polymer is aligned in a better direction, which shows a stronger anti-wavelength dispersion property. tendency.

On the other hand, when a polycarbonate is compared with a polyester, a polycarbonate obtained by polymerization of a diol and a carbonic acid diester tends to have a good balance between heat resistance and mechanical properties. Therefore, the resin of the present invention is particularly preferably a polyester carbonate obtained by introducing the above-mentioned specific diester having an oligomeric fluorene structural unit into the structure of a polycarbonate.

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, it may be difficult to cause a polymerization reaction under the polymerization conditions of a polycarbonate generally used. . Therefore, A ³ and A ^{4 in} the general formula (13) are preferably aromatic hydrocarbon groups.

And when, also in the above general formula (11) represents the case where the carbonic acid diester to perform the polymerization reaction, when the general formula (11) of the A ^1, A A ^2, and the general formula (13) of ^3, All of A ⁴ have the same structure, and the components detached during the polymerization reaction are the same, so they can be easily recovered and reused. From the viewpoint of polymerization reactivity and usefulness in recycling, A ¹ to A ^{4 are} particularly preferably a phenyl group. When A ¹ to A ⁴ are phenyl, the component to be removed during the polymerization reaction is phenol.

In the resin of the present invention, in order to obtain the following positive refractive index anisotropy and sufficient inverse wavelength dispersion, it is necessary to adjust the ratio of the oligomeric fluorene structural unit in the resin to a specific range. Examples of the method for adjusting the ratio of the oligomeric fluorene structural unit in the resin include a method of copolymerizing a monomer having the oligomeric fluorene structural unit and other monomers, or a method having the oligomerization A method of blending a resin of a structural unit with another resin. In terms of accurately controlling the content of the oligomeric fluorene structure unit, and obtaining high transparency and uniformity of the entire surface of the film, it is preferable to make the monomer having the oligomeric fluorene structure unit as described above. Copolymerization with other monomers law.

The content of the oligomeric fluorene structure unit in the resin is preferably 1% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 35% by mass or less, and more preferably 15% by mass relative to the entire resin. Mass% or more and 32 mass% or less, particularly preferably 20 mass% or more and 30 mass% or less. When the content of the oligomeric fluorene structure unit is too much, there is a possibility that the photoelastic coefficient or reliability is deteriorated, or a high birefringence cannot be obtained by extension. In addition, since the ratio of the oligomeric fluorene structure unit to the resin becomes higher, the range of the molecular design becomes narrower, and it is difficult to improve when the modification of the resin is required. On the other hand, even if it is assumed that the required inverse wavelength dispersion property can be obtained due to a very small amount of oligomeric fluorene structural units, in this case, the optical characteristics are sensitively changed depending on the slight unevenness of the content of oligomeric fluorene. It is difficult to manufacture in such a manner that various characteristics are within a certain range.

The resin of the present invention is preferably obtained by copolymerizing a monomer having the oligomeric fluorene structure unit and other monomers. Examples of other monomers to be copolymerized include dihydroxy compounds and diester compounds.

From the viewpoints of optical characteristics, mechanical characteristics, and heat resistance, the resin of the present invention preferably contains a structural unit of the following general formula (3) as a copolymerization component.

Examples of the dihydroxy compound into which the structural unit represented by the general formula (3) can be introduced include isosorbide (ISB), isomannide, and isoiditol in a stereoisomeric relationship. These can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of acquisition and polymerization reactivity, it is most preferable to use ISB.

Regarding the structural unit represented by the general formula (3), it is preferable that 5 is contained in the resin. It is preferably at least 10% by mass and not more than 70% by mass, more preferably at least 10% by mass and not more than 65% by mass, and more preferably at least 20% by mass and not more than 60% by mass. When the content of the structural unit represented by the general formula (3) is too small, heat resistance may be insufficient. On the other hand, if the content of the structural unit represented by the general formula (3) is too large, the heat resistance becomes too high, and the mechanical properties or melt processability become poor. In addition, the structural unit represented by the general formula (3) is a structure having high hygroscopicity. Therefore, when the content is too large, the water absorption of the resin may increase, and there may be a fear of dimensional deformation in a high humidity environment.

In addition, the resin of the present invention may be combined with the structural unit of the general formula (3), or may include another structural unit without using the structure of the general formula (3). (Hereinafter, this structural unit may be referred to as "other structural unit.")

As the other structural unit described above, a structural unit represented by the following general formulae (4) to (8) which does not contain an aromatic component is particularly preferred.

In the general formula (4), R ^1-10 represents an alkylene group having 2 to 20 carbon atoms which may have a substituent.

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

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 which can introduce the structural unit of the said General formula (5), the following dihydroxy compound can be used, for example. 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, 2,2,4,4-tetramethyl-1,3-cyclobutane Diols such as diols and dihydric compounds of alicyclic hydrocarbons are exemplified.

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 which can introduce the structural unit of the said General formula (6), the following dihydroxy compound can be used, for example. 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 2,6-ten Hydronaphthalene dimethanol, 1,5-decahydronaphthalene dimethanol, 2,3-decahydronaphthalene dimethanol, 2,3-norhydronaphthalene Alkanedimethanol, 2,5-nor Dihydroxy compounds such as alkanedimethanol, 1,3-adamantanedimethanol, limonene, and the like, which are dihydroxy compounds derived from terpene compounds, are exemplified as the dihydroxy compounds of alicyclic hydrocarbon primary alcohols.

In the general formula (7), R ^1-13 represents an alkylene group having 2 to 10 carbon atoms which may have a substituent, and p is an integer of 1 to 40.

As the dihydroxy compound to which the structural unit of the general formula (7) can be introduced, for example, Use the following dihydroxy compounds. Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol and other oxyalkylene glycols.

In the general formula (8), R ^1-14 represents a group having an acetal ring having 2 to 20 carbon atoms which may have a substituent.

As the dihydroxy compound into which the structural unit of the general formula (8) can be introduced, for example, a spirodiol represented by the following structural formula (14) or two represented by the following structural formula (15) can be used. Alkanediols, etc.

In addition to the dihydroxy compounds described above, dihydroxy compounds containing an aromatic component as exemplified below may be used. 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethyl Phenyl) 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 Alkane, 2,2-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) -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 1,3-bis (4-hydroxyphenyl) pentane, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 1,3-bis (2- (4-hydroxybenzene ) -2-propyl) benzene, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) Samarium, 2,4'-dihydroxydiphenylsulfonium, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4-hydroxyphenyl) di Aromatic bisphenol compounds such as sulfides, 4,4'-dihydroxydiphenyl ether, 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-hydroxyethoxy) benzene, 4,4 ' -Bis (2-hydroxyethoxy) biphenyl, bis (4- (2-hydroxyethoxy) phenyl) fluorene, and other dihydroxy compounds having ether groups bonded to aromatic groups; 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4- Methyl-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-hydroxy Ethoxy) -3-third 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-tert-butyl-6-methylphenyl) fluorene, 9,9-bis (4- (3-hydroxy-2,2-dimethyl) Dihydroxy compounds having a fluorene ring such as propoxy) phenyl) fluorene.

Moreover, as a diester compound which can be used for copolymerization with the monomer which has the said oligomeric fluorene structure unit, the following dicarboxylic acid etc. can be used, for example. Terephthalic acid, phthalic acid, isophthalic acid, 4,4'-diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid Acids, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylphosphonium dicarboxylic acid, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid; 1,2-cyclic Alicyclic dicarboxylic acids such as hexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid; malonic acid, succinic acid, glutaric acid, Aliphatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. In addition, the dicarboxylic acid component may be a dicarboxylic acid itself as a raw material of the above-mentioned polyester carbonate, but depending on the manufacturing method, it may be a dicarboxylic acid ester such as a methyl ester body or a phenyl ester body, or a dicarboxylic acid halide such as a dicarboxylic acid halide. A carboxylic acid derivative is used as a raw material.

From the viewpoint of optical characteristics, it is preferable to use those that do not contain an aromatic component as the other structural units listed above. If the polymer's main chain contains aromatic components, the inverse wavelength dispersion of the fluorene ring can be offset as described above. Therefore, the content of the oligomeric fluorene structure unit must be increased, and the photoelasticity coefficient may be deteriorated. By using the other structural unit that does not contain an aromatic component, it is possible to prevent the aromatic component from being introduced into the main chain from the structural unit.

On the other hand, in order to ensure optical characteristics and to achieve a balance with heat resistance or mechanical characteristics, it may be effective to introduce an aromatic component into the main chain or side chain of the polymer. In this case, an aromatic component can be introduced into the polymer by, for example, the other structural unit containing the aromatic component.

From the viewpoint of achieving a balance of various characteristics, the structural unit containing an aromatic group in the resin (except for the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) The content of) is preferably 5% by mass or less.

As the monomer having the other structural units listed above, it is particularly preferable to use 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, spirodiol, 1,4-cyclohexanedicarboxylic acid (and Its derivative). The resin containing the structural unit derived from these monomers is excellent in balance of optical characteristics, heat resistance, mechanical characteristics, and the like.

In the case of the polyester carbonate which is particularly preferred in the present invention, the polymerization reactivity of the diester compound is relatively low. Therefore, from the viewpoint of improving the reaction efficiency, it is preferable not to use an oligomeric fluorene structural unit. Diester compounds other than diester compounds.

Dihydroxy compounds or diester compounds used to introduce other structural units may also be used alone or in combination of two or more depending on the required properties of the obtained resin. Others in resin The content of the structural unit is preferably 1% by mass or more and 60% by mass or less, further preferably 5% by mass or more and 55% by mass or less, and particularly preferably 10% by mass or more and 50% by mass or less. Other structural units are responsible for adjusting the heat resistance of the resin, or imparting flexibility or toughness. Therefore, if the content is too small, the mechanical properties or melt processability of the resin may be deteriorated. If the content is too large, the heat resistance or There is a concern that the optical characteristics may deteriorate.

<The manufacturing method of the resin of this invention>

Polycarbonates, polyesters, and polyester carbonates suitable for use as the resin of the present invention can be produced by a commonly used polymerization method. That is, the resin can be produced, for example, by a solution polymerization method or an interfacial polymerization method using carbochlorine or carboxylic acid halide, or a melt polymerization method in which a reaction is performed without using a solvent. Among these production methods, the production is preferably performed by a melt polymerization method that can reduce the environmental load by not using a solvent or a highly toxic compound and is also excellent in productivity.

When a solvent is used for polymerization, the glass transition temperature of the resin is lowered due to the plasticizing effect caused by the residual solvent in the resin. Therefore, it is difficult to control the molecular alignment to be fixed in the following extension step. When a halogen-based organic solvent such as dichloromethane remains in the resin, if a molded body using the resin is incorporated in an electronic device or the like, it may cause corrosion. Since the resin obtained by the melt polymerization method does not contain a solvent, it is also advantageous for the stability of the processing steps or product quality.

When the resin is produced by a melt polymerization method, a monomer having an oligomeric fluorene structural unit, a copolymerization monomer of another diol or diester, and a polymerization catalyst are mixed, and a transesterification reaction is performed under melting. The reaction rate is improved while removing the detached components to the outside. In the final stage of polymerization, the reaction is performed under high temperature and high vacuum conditions to the target molecular weight. After the reaction is completed, the resin in a molten state is extracted from the reactor to obtain a resin raw material that can be used for a molded product such as a retardation film.

In the present invention, a polycarbonate or a polyester carbonate may use a monomer containing at least an oligomeric fluorene structural unit, one or more dihydroxy compounds, and a carbonic acid diester as raw materials. Obtained by polycondensation.

Examples of the carbonic acid diester used in the polycondensation reaction include those represented by the general formula (11). These carbonic acid diesters may be used alone or in combination of two or more.

In the general formula (11), A ¹ and A ² are each 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. A ¹ and A ² may be the same or different. .

A ¹ and A ^{2 are} preferably a substituted or unsubstituted aromatic hydrocarbon group, and more preferably an unsubstituted aromatic hydrocarbon group. Examples of the substituent of the aliphatic hydrocarbon group include an ester group, an ether group, a carboxylic acid, an amino group, and a halogen atom. Examples of the substituent of the aromatic hydrocarbon group include an alkyl group such as a methyl group and an ethyl group.

Examples of the carbonic acid diester represented by the general formula (11) include substituted diphenyl carbonates such as diphenyl carbonate (DPC), xylyl carbonate, dimethyl carbonate, diethyl carbonate, and di-third carbonate. Butyl ester and the like are preferably diphenyl carbonate and substituted diphenyl carbonate, and particularly preferably diphenyl carbonate. In addition, the carbonic acid diester may contain impurities such as chloride ions, and may inhibit the polymerization reaction, or may deteriorate the hue of the obtained polycarbonate. Therefore, it is preferred to use carbon dioxide diester by distillation or the like as necessary. Refiner.

The polycondensation reaction can control the reaction speed or the molecular weight of the obtained resin by closely adjusting the molar ratio of all dihydroxy compounds and diester compounds used in the reaction. In the case of polycarbonate, the molar ratio of the carbonic acid diester to the total dihydroxy compound is preferably adjusted to 0.90 to 1.10, more preferably 0.96 to 1.05, and even more preferably 0.98 to 1.03. 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 even more preferably 0.85 to 1.00. In the case of polyester carbonate, Preferably, the molar ratio of the total amount of the carbonic acid diester and all diester compounds to all the dihydroxy compounds is adjusted to 0.90 to 1.10, more preferably 0.96 to 1.05, and even more preferably 0.98 to 1.03.

If the above-mentioned Mohr ratio greatly deviates from top to bottom, it becomes impossible to produce a resin having a desired molecular weight. In addition, if the above-mentioned molar ratio becomes too small, the hydroxyl end of the resin produced may increase, and the thermal stability of the resin may deteriorate. In addition, if the above-mentioned molar ratio becomes too large, there is a possibility that the rate of transesterification reaction decreases under the same conditions, or the residual amount of the carbonic acid diester or diester compound in the produced resin increases, and the residual The low-molecular component is volatile during film formation or stretching, which causes defects in the film.

The melt polymerization method is usually carried out in a plurality of steps of two or more stages. The polycondensation reaction can be carried out in two steps or more using one polymerization reactor in order to change the conditions, or it can be carried out in two or more steps by changing the respective conditions using two or more reactors. From the viewpoint of production efficiency, it is carried out by using two or more reactors, preferably three or more reactors. The polycondensation reaction may be any of a batch type, a continuous type, or a combination of a batch type and a continuous type. In terms of production efficiency and quality stability, the continuous type is preferred.

In the polycondensation reaction, it is important to properly control the temperature and pressure balance in the reaction system. If any one of temperature and pressure changes too quickly, unreacted monomer is distilled out of the reaction system. As a result, the molar ratio of the dihydroxy compound to the diester compound changed, and a resin having a desired molecular weight could not be obtained.

The polymerization rate of the polycondensation reaction is controlled by the balance between the hydroxyl terminal and the ester terminal or carbonate terminal. Therefore, especially in the case of continuous polymerization, if the balance of the terminal groups changes due to the distillation of unreacted monomers, it becomes difficult to control the polymerization rate to be fixed, and the molecular weight of the obtained resin There is a risk that the changes will become larger. The molecular weight of the resin is related to the melt viscosity. Therefore, when the obtained resin is melt-formed into a film, the melt viscosity changes, and it becomes difficult to maintain the quality of the film thickness, etc. Degradation of film quality or productivity.

Furthermore, if the unreacted monomer is distilled off, not only the balance of the terminal groups changes, but also the copolymerized composition of the resin may deviate from the desired composition, and the optical quality of the retardation film may also be affected. In the retardation film of the present invention, the wavelength dispersion of the following retardation is controlled by the ratio of the oligomeric fluorene and the copolymerized component in the resin. Therefore, if the ratio collapses during polymerization, the following risks may occur: It becomes impossible to obtain the optical characteristics such as design, or in the case of obtaining a long film, the optical characteristics change depending on the position of the film, and it becomes impossible to manufacture a fixed-quality polarizing plate.

Specifically, as the reaction conditions in the reaction in the first stage, the following conditions can be adopted. That is, the maximum 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, and more preferably 230 ° C. Set within the range below ℃. The pressure of the polymerization reactor is usually 70 kPa or less (hereinafter, the so-called pressure means absolute pressure), preferably 50 kPa or less, more preferably 30 kPa or less, and usually 1 kPa or more, preferably 3 kPa or more, and more preferably 5 kPa or more. Set within the range. The reaction time is set within a range of usually 0.1 hours or more, preferably 0.5 hours or more and usually 10 hours or less, preferably 5 hours or less, and more preferably 3 hours or less. The reaction in the first stage is carried out while distilling off the monohydroxy compound derived from the diester compound generated outside the reaction system. For example, when diphenyl carbonate is used as the carbonic acid diester, in the reaction in the first stage, the monohydroxy compound that is distilled out of the reaction system is phenol.

In the reaction in the first stage, the lower the reaction pressure, the more the polymerization reaction can be promoted, but on the other hand, the distillation of unreacted monomers increases. In order to balance the suppression of the distillation of unreacted monomers and the promotion of the reaction using reduced pressure, it is effective to use a reactor equipped with a reflux cooler. In particular, a reflux cooler can be used at the initial stage of the reaction with a large amount of unreacted monomers.

For the reactions after the second stage, the pressure of the reaction system is gradually reduced from the pressure of the first stage, and the monohydroxy compound generated next is removed outside the reaction system, and Finally, the pressure of the reaction system is set to 5 kPa or less, preferably 3 kPa or less, and more preferably 1 kPa or less. The maximum internal temperature is set within a range of usually 210 ° C or higher, preferably 220 ° C or higher and usually 270 ° C or lower, preferably 260 ° C or lower. The reaction time is set within a range of 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, and more preferably 3 hours or less. In order to suppress coloring or thermal degradation to obtain a resin with good hue or thermal stability, it is preferable that the maximum internal temperature in all reaction stages is 270 ° C or lower, preferably 260 ° C or lower, and more preferably 250 ° C or lower.

Transesterification reaction catalysts (hereinafter, referred to as catalysts and polymerization catalysts) that can be used at the time of polymerization can greatly affect the color tone or thermal stability of the resin obtained by polycondensation. The catalyst used is not particularly limited as long as it satisfies the transparency, hue, heat resistance, thermal stability, and mechanical strength of the manufactured resin. Examples include Group 1 in the long-period periodic table. Or basic compounds such as metal compounds of Group 2 (hereinafter, only "Group 1", "Group 2"), basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds. It is preferable to use at least one metal compound selected from the group consisting of metals and lithium of Group 2 of the long-period periodic table.

As the above-mentioned Group 1 metal compound, for example, the following compounds can be used, but other Group 1 metal compounds can also be used. Examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, and sodium acetate. , Potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, Sodium tetraphenylborate, potassium tetraphenylborate, lithium tetraphenylborate, cesium tetraphenylborate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid Dilithium hydrogen, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, dicesium phenyl phosphate, sodium, potassium, lithium, alcoholates, phenolates, and bisphenol A of cesium Disodium, dipotassium, dilithium, and dicesium salts Wait. Among these, a lithium compound is preferably used from the viewpoint of polymerization activity and hue of the obtained polycarbonate.

As the above-mentioned Group 2 metal compound, for example, the following compounds can be used, but Group 2 metal compounds other than these can also be used. Examples include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, and calcium acetate. , Barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc. Among these, a magnesium compound, a calcium compound, and a barium compound are preferably used. From the viewpoint of polymerization activity and the hue of the obtained polycarbonate, a magnesium compound and / or a calcium compound is more preferably used, particularly preferably Use calcium compounds.

In addition, basic compounds such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine-based compound may be used in combination with the above-mentioned Group 1 metal compound and / or Group 2 metal compound. Preferably, at least one kind of metal compound selected from the group consisting of metals and lithium of Group 2 of the long-period periodic table is used.

As the above-mentioned basic phosphorus compound, for example, the following compounds may be used, but other basic phosphorus compounds may also be used. Examples include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, or a quaternary phosphonium salt.

As the above-mentioned basic ammonium compound, for example, the following compounds can be used, but other basic ammonium compounds can also be used. Examples include: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, N, N, N-trimethylethanolamine (choline), trimethyl Ethyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide, trimethylphenyl ammonium hydroxide, triethylmethyl ammonium hydroxide, triethylbenzyl ammonium hydroxide, triethylphenyl ammonium hydroxide , Tributylbenzyl ammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylhydrogen Ammonium oxide, etc.

As the above-mentioned amine-based compound, for example, the following compounds can be used, but other amine-based compounds can also be used. Examples include: 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, and the like.

Regarding the amount of the above-mentioned polymerization catalyst, usually all the dihydroxy compounds used in the polymerization are 0.1 μmol to 300 μmol, preferably 0.5 μmol to 100 μmol. When using at least one metal compound selected from the group consisting of metals and lithium of Group 2 of the long-period periodic table as the above-mentioned polymerization catalyst, in particular, a magnesium compound and / or a living calcium compound are used as the above-mentioned polymerization. In the case of a catalyst, the above polymerization catalyst is generally used in an amount of 0.1 mol or more, preferably 0.3 mol or more, and more preferably 0.5 mol or more per 1 mol of all the dihydroxy compounds. In addition, the use amount of the polymerization catalyst may be 30 μmol or less, preferably 20 μmol or less, and particularly preferably 10 μmol or less.

When a polyester or a polyester carbonate is produced by using a diester compound as a monomer, a titanium compound, a tin compound, a germanium compound, an antimony compound, or a zirconium compound may be used in combination with the basic compound described above or in combination. Transesterification catalysts such as lead compounds, osmium compounds, zinc compounds, manganese compounds, etc. Regarding the amount of these transesterification catalysts, it is used in the range of usually 1 μmol to 1 mmol, and preferably in the range of 5 μmol to 800 μmol, based on the amount of metal, relative to 1 mol of all dihydroxy compounds used in the reaction. It is preferably 10 μmol to 500 μmol.

If the amount of the catalyst is too small, the polymerization rate will be slowed. Therefore, in order to obtain a resin having a desired molecular weight, the polymerization temperature has to be increased. Therefore, there is a high possibility that the hue of the obtained resin becomes worse, and there is a possibility that the molar ratio of the dihydroxy compound to the diester compound collapses due to the volatilization of unreacted raw materials during the polymerization, and the possibility of failing to reach the required molecular weight Sex. On the other hand, if the amount of the polymerization catalyst used is too large, side reactions that are not satisfactory may occur at the same time, which may cause deterioration of the hue of the obtained resin or the coloration of the resin during the molding process.

If a large amount of sodium, potassium, and cesium is contained in the resin in the Group 1 metal, there is a possibility that the hue may be adversely affected. In addition, these metals are mixed not only from the catalyst used, but also from the raw materials or reaction devices. Regardless of the origin of the total amount of the compounds of these metals in the resin, based on the amount of metal, each 1 mol of the above-mentioned dihydroxy compounds is preferably 2 μmol or less, further preferably 1 μmol or less, and more preferably 0.5 μmol. the following.

When a polyester carbonate is produced using a diester compound represented by the general formula (13) as a monomer having an oligomeric fluorene structure unit, it is preferable to use A ³ and A ⁴ as aromatic hydrocarbon groups. The diester compound is particularly preferably a diester compound in which A ³ and A ⁴ are phenyl groups. By using these diester compounds, the polymerization reactivity is good, the amount of catalyst used can be reduced, the hue or thermal stability of the obtained resin can be improved, and foreign matter in the resin can be reduced.

After the resin of the present invention is polymerized as described above, it is usually cooled and solidified, and granulated by a rotary cutter or the like. There is no limitation on the method of materializing the particles, and examples include: a method in which the resin is withdrawn from the polymerization reactor in the final stage in a molten state and cooled and solidified in the form of strands to form the particles; the resin is melted from the polymerization reactor in the final stage The state is supplied to a uniaxial or biaxial extruder, and the method of cooling and solidifying after melting and extrusion to pelletize the particles; or the resin is extracted from the polymerization reactor in the final stage in a molten state, and cooled and solidified in the form of a strand. After the particles are temporarily formed, the resin is supplied to a uniaxial or biaxial extruder again, and after the melt is extruded, it is cooled and solidified to form the particles.

The molecular weight of the resin obtained in the above manner can be expressed by the 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, the reducing viscosity is usually 0.20 dL / g or more, and preferably 0.30 dL / g or more. On the other hand, if the reducing viscosity of the resin is too large, the fluidity during molding tends to decrease, which tends to reduce productivity or moldability. Therefore, the reducing viscosity is usually 1.20dL / g or less, preferably 1.00dL / g Hereinafter, it is more preferably 0.80 dL / g or less. The reduction viscosity was measured using dichloromethane as a solvent, the polycarbonate concentration was accurately adjusted to 0.6 g / dL, and the temperature was 20.0 ° C. ± 0.1 ° C. using a black viscometer.

The above-mentioned reduction viscosity is related to the melt viscosity of the resin. Therefore, the stirring power of the polymerization reactor or the discharge pressure of a gear pump that transports the molten resin can be used as an indicator for operation management. That is, at the stage where the indicated value of the above-mentioned operating machine reaches the target value, the pressure of the reactor is returned to normal pressure, or the resin is withdrawn from the reactor, thereby stopping the polymerization reaction.

The melt viscosity of the resin of the present invention is preferably 700 Pa · s or more and 5000 Pa · s or less under the measurement conditions of a temperature of 240 ° C and a shear rate of 91.2 sec ^-1 . More preferably, it is 800 Pa · s or more and 4500 Pa · s or less, more preferably 900 Pa · s or more and 4000 Pa · s or less, and even more preferably 1000 Pa · s or more and 3500 Pa · s or less. The melt viscosity was measured using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.).

The glass transition temperature of the resin of the present invention is preferably from 110 ° C to 160 ° C, and more preferably from 120 ° C to 155 ° C. If the glass transition temperature is too low, there is a tendency that the heat resistance is deteriorated, and there is a possibility that a dimensional change is caused after the film is formed, or the reliability of the quality of the retardation film is deteriorated under the conditions of use. On the other hand, if the glass transition temperature is too high, unevenness in film thickness may occur during film formation, or the film may become brittle and the extensibility may deteriorate, and the transparency of the film may be impaired.

The storage elastic modulus of the above resin is 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 even more preferably 1.3 GPa or more and 2.2 GPa or less. . When the storage elastic modulus is in the above range, the film is excellent in operability or strength. The method for measuring the storage elastic modulus is described in the item of the examples.

In order to obtain a polycarbonate resin film with a specific range of storage elastic modulus as specified in the present invention, it can be achieved by adopting Polycarbonate resin with a fixed structure, and its melt viscosity will be adjusted appropriately; or its structural units will be appropriately selected; or the ratio of its structural units will be adjusted; or a plasticizer, etc. will be added to the polycarbonate resin for an appropriate combination, or an appropriate selection will be made. Film forming conditions or extension conditions.

When a diester compound is used in a polycondensation reaction, there is a possibility that a by-produced monohydroxy compound remains in the resin, volatilizes during film formation or stretching, becomes an odor, degrades the working environment, or pollutes The appearance of the film is impaired by conveying rollers and the like. Especially when using diphenyl carbonate (DPC), which is a useful carbonic acid diester, the by-product phenol has a relatively high boiling point, which is not sufficiently removed even by the reaction under reduced pressure, and is likely to remain in In resin.

Therefore, the monohydroxy compound derived from the carbonic acid diester contained in the resin of the present invention is preferably 1500 mass ppm or less. It is more preferably 1,000 mass ppm or less, and particularly preferably 700 mass ppm or less. Furthermore, in order to solve the above-mentioned problems, the smaller the content of the monohydroxy compound is, the better, but it is difficult to make the monohydroxy compound remaining in the polymer zero in the melt polymerization method, and excessive labor is required to remove the monohydroxy compound. Usually, the above-mentioned problem can be sufficiently suppressed by reducing the content of the monohydroxy compound to 1 mass ppm.

In order to reduce the low-molecular components, such as monohydroxy compounds derived from carbonate diesters, remaining in the resin of the present invention, it is effective to degas the resin using an extruder as described above, or to reduce the pressure in the final stage of polymerization It is set to 3 kPa or less, preferably 2 kPa or less, and further preferably 1 kPa or less.

When the pressure in the last stage of the polymerization is reduced, if the pressure of the reaction is excessively reduced, the molecular weight may increase sharply, and the control of the reaction may become difficult. Therefore, it is preferable to set the concentration of the terminal group of the resin to an excess of hydroxyl terminals Or, the excess of the terminal end of the ester group causes the terminal group to be unbalanced and manufactured. Among them, from the viewpoint of thermal stability, it is preferable that the amount of the hydroxyl terminal is 50 mol / ton or less, particularly 40 mol / ton or less. The amount of the hydroxyl terminal can be quantified by ¹ H-NMR or the like. The amount of the hydroxyl terminal can be adjusted by the molar ratio of the total amount of the dihydroxy compound and the total amount of the diester compound added.

In the resin of the present invention, if necessary, a heat stabilizer is blended in order to prevent a decrease in molecular weight or deterioration of hue during molding. Examples of the thermal stabilizer include a generally known hindered phenol-based thermal stabilizer and / or a phosphorus-based thermal stabilizer.

As the hindered phenol-based compound, for example, the following compounds can be used. Examples include: 2,6-di-third-butylphenol, 2,4-di-third-butylphenol, 2-third-butyl-4-methoxyphenol, 2-third-butyl-4, 6-dimethylphenol, 2,6-di-tertiary-butyl-4-methylphenol, 2,6-di-tertiary-butyl-4-ethylphenol, 2,5-di-tertiary-butyl Hydroquinone, n-octadecyl-3- (3 ', 5'-di-third-butyl-4'-hydroxyphenyl) propionate, 2-tert-butyl-6- (3 '-Third-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate, 2,2'-methylene-bis- (4-methyl-6- Tributylphenol), 2,2'-methylene-bis- (6-cyclohexyl-4-methylphenol), 2,2'-ethylene-bis- (2,4-bis-third Butylphenol), tetra- [methylene-3- (3 ', 5'-di-third-butyl-4'-hydroxyphenyl) propionate] -methane, 1,3,5-trimethyl -2,4,6-tri- (3,5-di-third-butyl-4-hydroxybenzyl) benzene and the like. Among these, tetra- [methylene-3- (3 ', 5'-di-third-butyl-4'-hydroxyphenyl) propionate] -methane, n-octadecyl-3- (3 ', 5'-di-third-butyl-4'-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tri- (3,5-di- Third butyl-4-hydroxybenzyl) benzene.

As the phosphorus-based compound, for example, phosphorous acid, phosphoric acid, phosphinic acid, phosphonic acid, and esters thereof described below can be used, but phosphorus-based compounds other than these compounds can also be used. Examples include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, and tris phosphite Octyl ester, tri-octadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, Monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-third-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-phosphite Methylene bis (4,6-di-third-butylphenyl) octyl ester, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-third-butylphenyl) pentaerythritol Diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, mono-o-biphenyl diphenyl phosphate, dibutyl phosphate , Dioctyl phosphate, Diisopropyl phosphate, 4,4'-biphenylene diphosphonate tetra (2,4-di-tert-butylphenyl), dimethyl phenylphosphonate, diethyl phenylphosphonate, phenylphosphonic acid Dipropyl ester and so on. These heat 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 during melt polymerization, or may be added to the resin using an extruder and kneaded. In the case of forming a film by a melt extrusion method, the film may be formed by adding the above-mentioned thermal stabilizer to the extruder, or by using the extruder in advance and adding the above-mentioned thermal stabilizer to the resin. Shaped into particles.

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

In the resin of the present invention, generally known antioxidants for the purpose of anti-oxidation can also be formulated as needed. As such an antioxidant, for example, compounds shown below may be used, but compounds other than these may be used. Examples include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and triethylene glycol-bis [3- (3-Third-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-third-butyl 4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tri (3,5-di-tert-butyl-4 -Hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-third-butyl-4-hydroxy-phenylpropanamine), 3,5-di-third-butyl-4 -Hydroxy-benzylphosphonate-diethyl ester, isocyanuric tris (3,5-di-third-butyl-4-hydroxybenzyl ester), 4,4'-biphenylphenylphosphonic acid tetra ( 2,4-di-third-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-third-butyl-4-hydroxy-5-methylbenzene Propyl) propanyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane and the like. These antioxidants may be used alone or in combination of two or more. Regarding the amount of these antioxidants, when the resin of the present invention is 100 parts by mass, it is preferably 0.0001 parts by mass or more, and more preferably 0.5 mass parts or more.

Furthermore, the resin of the present invention may contain an ultraviolet absorber, a mold release agent, an antistatic agent, a slip agent, a lubricant, a plasticizer, and a compatible agent, as long as the purpose of the present invention is not impaired. Agents, nucleating agents, flame retardants, inorganic fillers, impact modifiers, foaming agents, dyes and pigments.

In addition, the resin of the present invention can be modified with aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, and polystyrene for the purpose of improving the mechanical properties and solvent resistance of the resin. Polyolefin, acrylic, amorphous polyolefin, ABS, AS, polylactic acid, polybutylene succinate and other synthetic resins or rubber or one or more polymer alloys kneaded.

The above additives or modifiers can be mixed with the resin of the present invention by a mixer such as a roller, a V-shaped mixer, a Nautor mixer, a Banbury mixer, a kneading roller, an extruder, or It is manufactured by mixing in any order, and it is preferable to knead | mix by an extruder, especially a biaxial extruder from a viewpoint of improvement of a dispersibility.

The resin obtained in the above manner has small birefringence, excellent heat resistance and formability, and has less coloring, and has high transparency. Therefore, it can be used in optical films or optical discs, optical lenses, reading lenses, etc. In particular, it can be preferably used as a retardation film.

<Manufacturing method of unstretched film>

As a method for forming a non-stretched film using the resin of the present invention, a casting method in which the above-mentioned resin is dissolved in a solvent and the solvent is removed after casting, or the above-mentioned resin is melted without using a solvent to form a film Melt film forming method. Specific examples of the melt film-forming method include a melt extrusion method using a T-die, a calendering method, a hot-press method, a coextrusion method, a co-melt method, a multilayer extrusion, and an inflation molding method. The film-forming method of the unstretched film is not particularly limited, but the casting method may cause problems caused by residual solvents. Therefore, the melt-film-forming method is preferred. In other words, a melt extrusion method using a T-die is preferred.

When the unstretched film is formed by the melt film forming method, the forming temperature is preferably 270 ° C or lower, more preferably 265 ° C or lower, and even more preferably 260 ° C or lower. If the forming temperature is too high, there may be an increase in defects caused by the generation of foreign matter or bubbles in the obtained film, or the possibility of film coloring. Among them, if the molding temperature is too low, the melt viscosity of the resin may become too high, and the formation of the blank film may become difficult, making it difficult to manufacture an unstretched film with a uniform thickness. Therefore, the lower limit of the molding temperature is usually 200. ℃ or higher, preferably 210 ℃ or higher, and more preferably 220 ℃ or higher. Here, the molding temperature of the unstretched film refers to the temperature at the time of molding in the melt film-forming method, and is generally a value obtained by measuring the temperature at the exit of the die from which the molten resin is extruded.

In addition, if a foreign substance is present in the film, defects such as light leakage are found when the film is used as a polarizing plate. In order to remove foreign matters from the resin, the following method is preferred: a polymer filter is installed after the above extruder, the resin is filtered, and the film is extruded from a mold to form a film. In this case, the extruder, the polymer filter, and the mold must be connected by piping to convey the molten resin. However, in order to minimize thermal degradation in the piping, it is important to arrange the equipment so that the residence time is minimized. In addition, the steps of transporting or winding the extruded film are performed in a clean room, and it is required to take care to prevent foreign matter from adhering to the film as much as possible.

The thickness of the unstretched film is determined based on the design of the film thickness of the retardation film after stretching, or the stretching conditions such as the stretching ratio. However, if it is too thick, unevenness (unevenness) in thickness is likely to occur, and if it is too thin , There is a possibility of causing breakage during elongation. Therefore, it is usually 30 μm or more, preferably 40 μm or more, more preferably 50 μm or more, and usually 200 μm or less, preferably 160 μm or less, and further preferably 120 μm or less. In addition, if the thickness of the unstretched film is uneven (uneven), the phase difference of the retardation film is caused. Therefore, the thickness of the portion used as the retardation film is preferably set to a thickness of ± 3 μm or less, and more preferably The set thickness is ± 2 μm or less, and particularly preferably the set thickness is ± 1 μm or less.

The length of the unstretched film in the longitudinal direction is preferably 500 m or more, and more preferably 1000 m or more, particularly preferably 1500 m or more. From the viewpoint of productivity or quality, it is preferable to continuously stretch when manufacturing the retardation film of the present invention, but usually at the beginning of stretching, conditions must be adjusted in order to meet a specific retardation. Too short, the quantity of products that can be obtained after adjusting the conditions is reduced. Furthermore, in the present specification, the "long strip" means that the size in the length direction of the film is sufficiently larger than the size in the width direction of the film, and means that it can actually be rolled into a roll shape in the length direction. 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.

The internal haze of the unstretched film obtained in the above manner is preferably 3% or less, more preferably 2% or less, and even more preferably 1% or less. If the internal haze of the unstretched film is greater than the above-mentioned upper limit value, there is a case where light scattering is caused, for example, when laminated with a polarizing element, it may cause depolarized light. The lower limit of the internal haze is not particularly limited, but is usually 0.1% or more. In the measurement of internal haze, a transparent film with an adhesive having been previously measured for haze is attached to both sides of an unstretched film, and a sample in a state in which the influence of external haze is removed is used to measure from the above sample. The value obtained by subtracting the haze value of the transparent film with an adhesive is the value of the internal haze.

The b * value of the unstretched film is preferably 3 or less. If the b * value of the film is too large, problems such as coloration occur. The b * value is more preferably 2 or less, and even more 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 even more preferably 92% or more. If the transmittance is above the lower limit, a film with less coloration can be obtained. When bonded to a polarizing plate, it becomes a circular polarizing plate with a high degree of polarization or transmittance. When used in an image display device, it can show a high degree. The display taste. In addition, the upper limit of the total light transmittance of the film of the present invention is not particularly limited, and is usually 99% or less.

In addition to lowering the above-mentioned haze or b * value, the reflection of the film surface can be suppressed by reducing the refractive index of the resin, and the total light transmittance can be improved. In the case where the resin of the present invention is used for a circular polarizing plate for preventing external light reflection, improving the total light transmittance The reflectance of boundary light is reduced. The refractive index at the sodium d-line (589 nm) of the resin used in the present invention is preferably 1.49 to 1.56. The refractive index is more preferably 1.50 to 1.55, more preferably 1.51 to 1.54, and even more preferably 1.51 to 1.53. The resin used in the present invention contains an oligomeric fluorene structure unit, so the refractive index is higher than that of a full aliphatic polymer. However, since an aromatic compound is not used in the copolymerization component, the refractive index can be within the above range. .

The photoelastic coefficient of the resin of the present invention is preferably 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. If the photoelastic coefficient is too large, there may be a reduction in image quality such as a white and blurred image around the screen when the retardation film is bonded to the polarizing plate. This problem is particularly apparent when used in a large display device.

The unstretched film is preferably not brittlely broken in a bending test described below. If the film is brittlely broken, there is a concern that the film is likely to be broken during film formation or stretching, and the production yield is deteriorated. For making a film that is not brittle, it is important to design the molecular weight or melt viscosity and glass transition temperature of the resin used in the present invention to the above-mentioned preferred ranges. In addition, a method of adjusting the characteristics of the film by copolymerizing a component capable of imparting flexibility or blending it is also effective.

The saturated water absorption of the resin of the present invention is preferably greater than 1.0% by mass. When the saturated water absorption is greater than 1.0% by mass, the adhesiveness tends to be easily ensured when the film is bonded to another film or the like. For example, when bonding to a polarizing plate, the film is hydrophilic, so the contact angle of water is also low, and it is easy to design the adhesive freely, and a higher adhesive design can be performed. When the saturated water absorption is 1.0% by mass or less, it becomes hydrophobic and the contact angle of water is also high, so that the design of the adhesiveness becomes difficult. In addition, there is a tendency that the film becomes easily electrified and foreign matter is entrapped, and appearance defects are increased when the film is installed in a circularly polarizing plate or an image display device. On the other hand, when the saturated water absorption rate is greater than 3.0% by mass, the durability of the optical characteristics under a humidity environment tends to be deteriorated, which is not preferable. Resin of the present invention The saturated water absorption is preferably greater than 1.0% by mass, more preferably 1.1% by mass or more, still more preferably 3.0% by mass or less, and even more preferably 2.5% by mass or less. On the other hand, depending on the use conditions of the film or the image display device using the film, the saturated water absorption rate may be set to 1.0% by mass or less.

<Manufacturing method of retardation film>

A retardation film can be obtained by subjecting the unstretched film to stretch alignment. As the stretching method, a known method such as a longitudinal uniaxial stretching, a transverse uniaxial stretching using a tenter, or the like, a combination of simultaneous biaxial stretching, and a successive biaxial stretching can be used. The stretching may be performed in a batch manner, but in terms of productivity, the stretching is preferably performed continuously. Furthermore, compared with the batch type, a continuous stretcher can obtain a retardation film with less unevenness in the retardation within the film surface.

Regarding the elongation temperature, the glass transition temperature (Tg) of the resin used as a raw material is in a range of (Tg-20 ° C) to (Tg + 30 ° C), preferably (Tg-10 ° C) to (Tg + 20 ° C) ), More preferably in the range of (Tg-5 ° C) to (Tg + 15 ° C). The extension magnification is determined by the phase difference of the target. The vertical and horizontal ratios are 1.2 to 4 times, more preferably 1.5 to 3.5 times, and even more preferably 2 to 3 times. If the extension magnification is too small, the effective range of the required alignment degree and alignment angle can be narrowed. On the other hand, if the stretching ratio is too large, the stretched intermediate film may be broken or wrinkles may occur.

The elongation speed is also appropriately selected depending on the purpose, but the deformation speed meter expressed by the following formula can be usually 50% to 2000%, preferably 100% to 1500%, more preferably 200% to 1000%, and particularly preferably Choose from 250% ~ 500%. If the elongation speed is too large, there is a possibility of causing breakage during elongation or a change in optical characteristics caused by long-term use under high temperature conditions. In addition, if the elongation speed is too small, not only the productivity is reduced, but also the elongation ratio needs to be made too large in order to obtain the required phase difference.

Deformation speed (% / min) = (Extending speed (mm / min) / length of blank film (mm)) × 100

After the film is stretched, it can also be heat-fixed by a heating furnace if necessary. It can also control the width of the tenter, or adjust the peripheral speed of the roller to perform the relaxation step. The temperature of the heat-setting treatment is performed within a range of a glass transition temperature (Tg) of 60 ° C to (Tg), preferably 70 ° C to (Tg-5 ° C) with respect to a resin used for the unstretched film. If the heat treatment temperature is too high, there is a possibility that the alignment of the molecules obtained by extension is disordered, and the required phase difference is greatly reduced. In addition, in the case of providing a relaxation step, it can shrink by 95% to 100% with respect to the width of the film expanded by stretching, thereby eliminating the stress generated by the stretched film. At this time, the processing temperature applied to the film is the same as the heat-fixing processing temperature. By performing the heat-fixing treatment or the relaxation step as described above, it is possible to control changes in optical characteristics caused by long-term use under high temperature conditions.

The retardation film using the resin of the present invention can be produced by appropriately selecting and adjusting the processing conditions in the above-mentioned stretching steps.

The retardation film using the resin of the present invention preferably has an in-plane birefringence (Δn) at a wavelength of 550 nm of 0.002 or more, more preferably 0.0025 or more, and even more preferably 0.003 or more. The phase difference is proportional to the thickness (d) and birefringence (△ n) of the film. Therefore, by setting the birefringence to the above-mentioned specific range, a thin film can be easily displayed as a designed phase difference. To produce thin films suitable for thin machines. In order to show higher birefringence, it is necessary to lower the stretching temperature and increase the stretching ratio to improve the alignment of the polymer molecules. However, the film becomes easy to break under the above-mentioned stretching conditions. Therefore, the more excellent the toughness of the resin used, the better advantageous.

The thickness of the retardation film using the resin of the present invention also depends on the design value of the retardation, but the thickness is preferably 60 μm or less. The thickness of the retardation film is more preferably 50 μm or less, more preferably 45 μm or less, and even more preferably 40 μm or less. On the other hand, if the thickness is too thin, handling of the film becomes difficult, and wrinkles or cracks occur during manufacture. Therefore, the lower limit of the thickness of the retardation film of the present invention is preferably 10 μm or more, and more preferably 15 μm. the above.

Regarding the retardation film using the resin of the present invention, the ratio of the phase difference (R450) measured at a wavelength of 450nm to the phase difference (R550) measured at a wavelength of 550nm, that is, the wavelength color The value of dispersion (R450 / R550) is 0.75 or more and 0.93 or less. It is more preferably 0.78 or more and 0.91 or less, and particularly preferably 0.80 or more and 0.89 or less. If the value of the above-mentioned wavelength dispersion is in this range, an ideal phase difference characteristic in a wide wavelength range in the visible region can be obtained. For example, making a retardation film with the above-mentioned wavelength dependency as a quarter-wave plate, and bonding it to a polarizing plate, thereby making a circular polarizing plate, etc., and realizing a polarizing plate and display with less color-dependent wavelength dependence. Device. On the other hand, when the above ratio is outside the range, the wavelength dependence of the hue becomes large, the optical compensation disappears at all wavelengths in the visible region, and the coloration or contrast caused by light passing through the polarizing plate or display device Reduction and other issues.

<Application example of retardation film using resin of this invention>

The retardation film is laminated and bonded to a known polarizing film, and cut into a desired size to form a circular polarizing plate. Such a circular polarizing plate can be used, for example, for viewing angle compensation of various displays (liquid crystal display device, organic EL display device, plasma display device, FED field emission display device, SED surface electric field display device), prevention of external light reflection, color Compensation, conversion of linearly polarized light to circularly polarized light, etc. In particular, if it is used as a circular polarizing plate for preventing outer-boundary light reflection of an organic EL display, a clean black display becomes possible, and the reliability of quality is excellent. Furthermore, it has the performance that can cope with the thinning of future equipment.

As the above-mentioned polarizing film, a polarizing film having an absorption axis in either the width direction or the length direction can be used. Specific examples include adsorption of a dichroic substance such as iodine or a dichroic dye onto a polyvinyl alcohol-based film, a partially methylated polyvinyl alcohol-based film, an ethylene-vinyl acetate copolymer-based partially saponified film, and the like. A film of a hydrophilic polymer film that is uniaxially stretched, a polyene-based alignment film such as a dehydrated product of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride. Among these, a long polarizing film obtained by adsorbing a dichroic substance such as iodine on a polyvinyl alcohol-based film and uniaxially stretching it is particularly preferable because it has a higher polarization dichroism. The thickness of these long polarizing films is not particularly limited, and is usually about 1 to 80 μm.

A polarizing film obtained by adsorbing iodine on a polyvinyl alcohol-based film and uniaxially stretching it may be, for example, Dyeing is performed by immersing polyvinyl alcohol in an aqueous solution of iodine, and production is performed by extending to 3 to 7 times the original length. The above-mentioned aqueous solution may also contain boric acid, zinc sulfate, zinc chloride, etc., if necessary. Alternatively, polyvinyl alcohol may be immersed in an aqueous solution such as potassium iodide.

If necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. The polyvinyl alcohol-based film can be washed with water to clean the dirt or anti-blocking agent on the surface of the polyvinyl alcohol-based film. Furthermore, since the polyvinyl alcohol-based film swells, there is also an effect of preventing unevenness and unevenness in dyeing. The stretching may be performed after dyeing with iodine, or may be extended while dyeing, or may be dyed with iodine after stretching. It can also be extended in an aqueous solution such as boric acid or potassium iodide or in a water bath.

In the circular polarizing plate, the angle formed by the retardation 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 particularly preferably It is 42 ° or more and 48 ° or less. When it is out of the above range, there is a possibility that the outer boundary light reflectance increases or the reflected light is colored, so that the display quality of the image is lowered.

The retardation film and the polarizing film may be laminated via an adhesive. As the adhesive, a known adhesive can be used as long as the optical characteristics of the laminated film are not impaired.

The above-mentioned circularly polarizing plate has the following structure: it has sufficient optical characteristics as described above, and can be preferably used for a machine that requires precision, thinness, and homogeneity. Therefore, the above-mentioned circular polarizing plate can be preferably used, for example, in a liquid crystal panel used in a liquid crystal display or an organic EL panel used in an organic EL display. In particular, the organic EL panel is provided with a metal layer that can easily reflect external light, so it is easy to cause problems such as external light reflection or reflection of the background. In order to prevent such external light reflection and the like, it is effective to provide the circular polarizing plate on a light emitting surface.

"Invention 2"

Hereinafter, the tertiary diester of the present invention 2, an oligomeric oligomeric diester composition containing the same, and a resin composition containing a polymer having a repeating unit derived from the novel trimethyl diester, are used. The obtained extension film, circular polarizing plate, and image display device are used for detailed description.

The following general formulae (1), (1a) to (1e), (2) to (11), and (21) describe each structure in the present invention 2.

<1 trimer diester>

The trifluorene diester of the present invention includes three fluorene units a which may have a substituent.

The carbon atoms at the a position of the a unit of the arsine unit in the tri-fluorene diester are directly bonded to each other, or via an alkylene group which may have a substituent, an alkylene group which may have a substituent, or an alkylene group which may have a substituent Bonded in chains.

As described above, the tertiary diester of the present invention is considered to have a structure that is rigid due to the laminated structure of the fluorene ring, and thus has better heat resistance than the difluorene compound.

<1.1 alkylene, alkylene, alkylene>

In the tertiary diester of the present invention, the alkylene group bonded to the fluorene unit a is not particularly limited. From the viewpoint of increasing the ratio of fluorene described below, the number of carbon atoms is usually 1 or more, and usually 10 or less. It is preferably 5 or less, and more preferably 3 or less.

The specific structure of the above-mentioned alkylene group is enumerated below, and is not limited thereto, and examples thereof include straight chains such as methylene, ethylene, n-butylene, n-butylene, n-pentyl, and n-hexyl Shaped alkylene; methylmethylene, dimethylmethylene, ethylmethylene, propylmethylene, butylmethylene, (1-methylethyl) methylene, 1 -Methylethene, 2-Methylethene, 1-Ethylethene, 2-Ethylethene, 1-Methylethene, 2-Methylethene, 1,1-Dimethyl Methylethene, 2,2-dimethylpropane, 3-methylpropane, and other alkylene groups containing side chains (the value of the substitution position is set to the carbon attached to the ring side) ; As shown in the following [A] group, an alicyclic alkylene group having a straight or side chain alkylene bond at any two positions in the alicyclic structure [Chem. 34]

(The substitution positions of the two bonding bonds in each ring structure shown in the above [A] group are arbitrary, and the two bonding bonds can also be substituted on the same carbon); as shown in the following [B] group Heterocyclic alkylene having a linear or side chain alkylene bond in any 2 of the heterocyclic structure

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

Specific structure of the alicyclic structure shown in the above-mentioned [A] group, or the straight-chain or side-chain extended alkylene bond in the heterocyclic structure shown in the above-mentioned [B] group in any two places It is listed below and is not limited to these, and examples include linear methylene, ethylidene, n-propylidene, n-butylidene, n-pentylyl, and n-hexylyl linear alkylene; 1-formyl Ethylidene, 2-methylidene, 1-ethylidene, 2-ethylidene, 1-methylidene, 2-methylidene, 1,1-dimethyl Ethylene, 2,2-dimethylpropane, 3-methylpropane, and other alkylene groups containing side chains (here the value of the substitution position is set to the carbon bond self-bonded to the above ring structure The former). Examples of the substituent which the alkylene group may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); and an alkoxy group having 1 to 10 carbon atoms (for example, a methoxy group and an ethoxy group). Radicals, etc.); fluorenyl radicals having 1 to 10 carbon atoms (for example, ethenyl, benzamidine, etc.); fluorenyl radicals having 1 to 10 carbon atoms (for example, acetamidine, benzamidine, etc.) Nitrate Group; cyano group; may have a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.), Alkoxy groups (e.g., methoxy, ethoxy, etc.) having 1 to 10 carbon atoms, fluorenyl groups (e.g., ethenyl, benzamidine, etc.) having 1 to 10 carbon atoms, Arylamino (e.g., ethylamino, benzamidine, etc.), nitro, cyano, etc. 1 to 3 substituents, 6 to 10 carbon atoms (e.g., phenyl, naphthyl, etc.) )Wait. The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

Specific examples of the substituted alkylene include alkyl-substituted alkylene such as cyclobutylmethylene, cyclopentylmethylene, cyclohexylmethylene, and 1-cyclohexylpropyl; Phenylmethylene, 1-phenyleneethyl, 1-phenylenepropyl and other aryl substituted alkylenes; 1,1,2,2-tetrafluoroethylene, trichloromethylmethylene, triphenylene Halogen atoms such as fluoromethylmethylene are substituted for alkylene; alkoxy groups such as 2-methoxymethyl-2-methylpropylene are substituted for alkylene, etc. Carbon attachments).

In the tertiary diester of the present invention, the arylene group to which the fluorene unit a is bonded is not particularly limited. From the viewpoint of increasing the ratio of fluorene described below, the number of carbon atoms is usually 4 or more, and usually 10 or less, preferably 8 or less, and more preferably 6 or less.

The specific structure of the above-mentioned arylene group is listed below, and is not limited thereto. Examples include 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene. ; 1,5-naphthyl, 2,6-naphthyl and other arylenes; 2,5-pyridyl, 2,4-thienyl, 2,4-furanyl and other heteroarylenes.

Examples of the substituent which the arylene group may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); and an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, Isopropyl, etc.); alkoxy groups (e.g., methoxy, ethoxy, etc.) having 1 to 10 carbon atoms; fluorenyl groups (e.g., ethenyl, benzyl, etc.) having 1 to 10 carbon atoms; Amidino groups having 1 to 10 carbon atoms (for example, acetamido, benzamidine, etc.); nitro; cyano, and the like. Number of such substituents The amount is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

Specific examples of the arylene group which may be substituted include 2-methyl-1,4-phenylene, 3-methyl-1,4-phenylene, and 3,5-dimethyl-1 1,4-phenylene, 3-methoxy-1,4-phenylene, 3-trifluoromethyl-1,4-phenylene, 2,5-dimethoxy-1,4-phenylene Phenyl, 2,3,5,6-tetrafluoro-1,4-phenylene, 2,3,5,6-tetrachloro-1,4-phenylene, 3-nitro-1,4- Phenylene, 3-cyano-1,4-phenylene and the like.

Furthermore, in the tertiary diester of the present invention, the aralkyl group to which the fluorene unit a is bonded is not particularly limited. From the viewpoint of increasing the ratio of fluorene described below, its carbon number is usually 6 or more, and It is usually 10 or less, preferably 9 or less, and more preferably 8 or less.

The specific structure of the above-mentioned aralkyl group is exemplified below, and is not limited thereto. Examples include the aralkyl group shown in the following [C] group.

Examples of the substituent which the aralkyl group may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); and an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, Isopropyl, etc.); alkoxy groups (e.g., methoxy, ethoxy, etc.) having 1 to 10 carbon atoms; fluorenyl groups (e.g., ethenyl, benzyl, etc.) having 1 to 10 carbon atoms; Amidino groups having 1 to 10 carbon atoms (for example, acetamido, benzamidine, etc.); nitro; cyano; may have a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine) Atom), alkyl group with 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.), alkoxy group with 1 to 10 carbon atoms (for example, methoxy group, ethoxy group, etc.), carbon number 1 to 10 fluorenyl groups (for example, ethenyl benzamidine group, etc.), 1 to 10 carbon atoms of fluorenyl group (for example, acetamidine group, benzamidine group, etc.), nitro, cyano, etc. 1 to 3 An aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, etc.) as a substituent. The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

Specific examples of the substituted aralkyl group include 2-methyl-1,4-benzenedimethyl, 2,5-dimethyl-1,4-benzenedimethyl, 2-methyl Oxy-1,4-benzenedimethyl, 2,5-dimethoxy-1,4-benzenedimethyl, 2,3,5,6-tetrafluoro-1,4-benzenedimethyl, α, α-dimethyl-1,4-xylylene, α, α, α ', α'-tetramethyl-1,4-xylylene, etc.

Among these, from the viewpoint of increasing the ratio of fluorene and the rigidity of the structure, it is preferably an alkylene group, more preferably a methylene group, an ethylene group, a phenylene group, or a 1,4-benzenedimethyl group. Methylene is preferred. Especially in the case of a methylene group, it is particularly preferable because the synthesis of an oligomeric fluorene having one reactive functional group is easy.

<1.2 The substituent which the unit a may have>

In the trifluorene diester of the present invention, examples of the substituent that the fluorene unit a may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); an alkyl group having 1 to 10 carbon atoms (E.g., methyl, ethyl, isopropyl, etc.); alkoxy (e.g., methoxy, ethoxy, etc.) having 1 to 10 carbon atoms; fluorenyl (e.g., acetamidine) having 1 to 10 carbon atoms Group, benzamidine group, etc.); amidino group having 1 to 10 carbon atoms (for example, acetoamino group, benzamidine group, etc.); nitro group; cyano group; may have a halogen atom (for example, fluorine Atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.), alkoxy group having 1 to 10 carbon atoms (for example, methoxy group) , Ethoxy, etc.), fluorenyl groups having 1 to 10 carbons (for example, ethenyl, benzamidine, etc.), fluorenyl groups having 1 to 10 carbons (for example, acetamido, benzylamine) Aryl groups such as nitro, cyano and the like having 1 to 3 substituents and 6 to 10 carbon atoms (for example, phenyl, naphthyl, etc.). The number of such substituents is not particularly limited, but is preferably one to three. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

<1.3 ester group>

The trifluorene diester of the present invention can be set as follows: In the three fluorene units a, the substituents α ¹ and α ² are respectively bonded to the carbon atom at the 9-position of the fluorene unit a at the two ends, and The substituents α ¹ and α ^{2 are} bonded to an ester group. In this case, α ¹ and α ² may be the same or different. The substituents α ¹ and α ² may also include a direct bond, that is, an ester group is directly bonded to the carbon atom at the 9-position of the fluorene unit a.

The ester group of the tertiary diester of the present invention is not particularly limited. From the viewpoint of industrial availability, the ester group is preferably an ester having an organic substituent having 1 to 10 carbon atoms in the terminal group. base.

Specific examples of the organic substituent having 1 to 10 carbon atoms are listed below and are not limited thereto. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n- Linear alkyl groups such as decyl; isopropyl, 2-methylpropyl, 2,2-dimethylpropyl, 2-ethylhexyl and other alkyl groups containing side chains; cyclopropyl, cyclopentyl Cyclic alkyl groups such as alkyl, cyclohexyl, cyclooctyl; aryl groups such as phenyl, 1-naphthyl, 2-naphthyl; heteroaryl groups such as 2-pyridyl, 2-thienyl, 2-furyl; Aralkyl groups such as benzyl, 2-phenylethyl, and p-methoxybenzyl, and the like.

Among these, an alkyl group having 1 to 6 carbon atoms is preferable from the viewpoint that it is industrially available at low cost. In this case, the carbon number is preferably 2 or more from the viewpoint of easy hydrolysis and synthesis of a carboxylic acid in the synthesis, and by removing a low-boiling-point alcohol produced by transesterification with a dihydroxy compound From the viewpoint of efficiently synthesizing polyester and polyester carbonate, it is preferably 4 or less, and more preferably 2 or less. A particularly preferred substituent is ethyl.

On the other hand, in the case of an aryl group having 6 to 8 carbon atoms, the transesterification reaction easily proceeds. Therefore, the diester compound, dihydroxy compound, and carbonic acid diester of the present invention can be added to the reactor at one time. In the first stage, polyester carbonate, which is a better polymer, is synthesized, so it is better. In this case, the number of carbons is preferably 8 or less, more preferably 6 or less, from the viewpoint that the molecular weight is small and the distillation is easy to remove. Especially after the synthesis of polyester carbonate, phenyl which can be distilled off by phenol is particularly preferred. In the case of aryl, From the viewpoint of reactivity at the time of polymerization, it is preferable to use the following diaryl carbonates as the carbonic acid diester, and from the viewpoint of easily removing by-products, the aryl group in the ester group, Same as aryl group in diaryl carbonates.

<1.4 Substituents α ¹ and α ² >

The substituents α ¹ and α ^{2 are} not particularly limited, and examples thereof include a direct bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, an arylene group having 4 to 10 carbon atoms which may be substituted, or Substituted aralkyl groups having 6 to 10 carbons, or selected from substitutable carbon groups of 1 to 10 carbons, substitutable arylene groups of 4 to 10 carbons, and substitutable carbons Two or more groups in the group consisting of 6 to 10 aralkyl groups are groups formed by bonding oxygen atoms, sulfur atoms that may be substituted, nitrogen atoms that may be substituted, or carbonyl groups.

As the "alkylene group having 1 to 10 carbon atoms which may be substituted", examples exemplified as the alkylene group of the bonded fluorene unit a can be preferably used. In this case, it is preferable to use a carbon number of 2 or more from the viewpoint of exhibiting inverse wavelength dispersion. On the other hand, it is preferable to set the carbon number to 1 from the viewpoint of showing flat dispersibility. Furthermore, when the inverse wavelength dispersion property is exhibited, the number of carbons is preferably 5 or less from the viewpoint of efficiently obtaining the inverse wavelength dispersion characteristics with the orientation of the fluorene ring easily fixed to the main chain. 4 or less, more preferably 3 or less, and even more preferably 2 or less. On the other hand, from the viewpoint of imparting flexibility to the resin composition, the number of carbons is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.

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

"Selected from the group consisting of an alkylene group having 1 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, and an alkylene group having 6 to 10 carbon atoms that can be substituted The specific structure in which two or more groups are linked by an oxygen atom, a sulfur atom that may be substituted, a nitrogen atom that may be substituted, or a carbonyl group "is exemplified below, and is not limited to these. The divalent base is shown in the following [D] group.

Among these, it is preferred that two or more groups selected from the group consisting of an alkylene group, an arylene group, or an aralkylene group are bonded by an oxygen atom while maintaining transparency and stability of the resin composition and imparting flexibility. The formed group is more preferably a group formed by bonding an oxygen atom to an alkylene group shown in the following [E] group while imparting flexibility while increasing the glass transition temperature of the resin composition.

In addition, from the viewpoint of increasing the ratio of radon, in the case of using these connected bases, the number of carbons is preferably set to 2 or more, and further preferably set to 6 or less, more preferably Set it to 4 or less.

Among these, when at least one of the substituents α ¹ and α ² is a direct bond, or when the carbon number of at least one of the substituents α ¹ and α ² is 2 or more, the fluorene ring (茀 unit a ) Is aligned approximately perpendicularly to the main chain, and therefore tends to exhibit reverse wavelength dispersion even if the ratio of divalent triad in the resin composition is small. In the latter case, from the same viewpoint, it is preferable that both α ¹ and α ² have a carbon number of 2 or more. On the other hand, in a case where both of the substituents α ¹ and α ² are set to one carbon number (that is, a methylene group which may be substituted), the fluorene ring (fluorene unit) is not aligned substantially vertically to the main chain but Orientation is performed with a large inclination, so there is a tendency that even if the ratio of the divalent triad in the resin composition is changed in a wide range, it is easy to become a plane dispersion with a small difference in wide-band phase difference. Sex.

Among these, a direct bond, an alkylene group having 1 to 10 carbon atoms which can be substituted, an arylene group having 4 to 10 carbon atoms which can be substituted, or a group selected from the group consisting of 1 to 10 carbon atoms which can be substituted 2 or more of the group consisting of an alkylene group that can be substituted, an alkylene group that has 4 to 10 carbon atoms, and an alkylene group that can be substituted with 6 to 10 carbon atoms are composed of an oxygen atom, Substituted sulfur atom, a group which may be connected by a substituted nitrogen atom or a carbonyl group.

More preferred are a straight bond, a straight chain alkylene group, a side chain-containing alkylene group, and a linear or side chain-type alkylene group at any two positions of the alicyclic structure shown in the above [A] group. The alicyclic alkylene, phenylene, or bond selected from the group consisting of an alkylene having 1 to 10 carbon atoms that can be substituted, an alkylene having 4 to 10 carbon atoms that can be substituted, and a substituted one Two or more radicals in a group consisting of an aralkyl group having 6 to 10 carbon atoms are connected by oxygen atoms.

Further preferred are direct bonds, methylene, ethylidene, n-propylidene, n-butylidene, and methylmethylene, which have a tendency to achieve a lower photoelastic coefficient required for optical films because they do not have an aromatic ring. , 1-methylphenylethyl, 2-methylphenylethyl, 2,2-dimethylphenylpropyl, 2-methoxymethyl-2-methylphenylpropyl, or the following [F] group The alicyclic alkylene shown.

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

Furthermore, it is more preferably a direct bond, methylene, ethylidene, n-propylidene, n-butylidene, methylmethylene, 1-methylidene, 2-methylidene, or 2,2- Dimethylpropane. Especially preferred are methylene, ethyl, or n-propyl.

If the chain length is longer, the glass transition temperature tends to be lower. Therefore, a shorter chain-like base such as a base having 2 or less carbon atoms is preferred. Furthermore, since the molecular structure becomes smaller, the concentration of the fluorene ring (fluorene ratio) in the repeating unit tends to be high, so that the required optical physical properties can be developed efficiently. In addition, even if it is contained in an arbitrary mass with respect to the entire mass of the resin composition, there is a tendency that it can be a plane dispersion with a small phase dispersion and a small wavelength dispersion, and it also has the advantage that it can be introduced in a short stage and industrially inexpensively. Therefore, methylene is preferred.

On the other hand, in order to improve the mechanical strength or reliability at high temperature of the obtained film, it is preferred that the aryl group having a carbon number of 4 to 10 which can increase the glass transition temperature of the resin composition, or selected from the group consisting of An alkylene group having 1 to 10 carbon atoms and an arylene group having 4 to 10 carbon atoms that can be substituted. Two or more groups are connected by oxygen atoms, and more preferably 1,4- A phenylene group, a 1,5-naphthyl group, a 2,6-naphthyl group, or a divalent group represented by the following [D2] group.

When applying to a retardation film having inverse wavelength dispersion, it is important to appropriately select the substituents α ¹ and α ² . For example, a base of carbon number 1 represented by methylene has an unexpected tendency to have low inverse wavelength dispersion. Therefore, R ¹ and R ^{2 are} preferably a direct bond, or at least one of them is a base of carbon number 2 or more. .

More preferably, it is a direct bond, an alkylene group having 2 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, or an alkylene group having 1 to 10 carbon atoms that can be substituted. 2 or more of the group consisting of an arylene group having 4 to 10 carbon atoms that can be substituted and an aralkyl group having 6 to 10 carbon atoms that can be substituted are an oxygen atom, a sulfur atom that can be substituted 2. A group which can be linked by a substituted nitrogen atom or a carbonyl group.

Furthermore, it is preferably a direct bond, a linear alkylene, an alkylene containing a side chain, such as The alicyclic alkylene group having a linear or side chain alkylene bond at any two positions in the alicyclic structure shown in the above-mentioned [A] group, a phenylene group, or a group selected from the group consisting of Two or more of the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group having 4 to 10 carbon atoms that can be substituted and an alkylene group having 6 to 10 carbon atoms that can be substituted A radical formed by the bonding of oxygen atoms.

Furthermore, it is more preferable because it does not have an aromatic ring, and can achieve the lower photoelastic coefficient of the direct bond required by optical films. Ethyl, n-propyl, n-butyl, methylmethylene, 1-methyl ethylene Phenylene, 2-methylethenyl, 2,2-dimethylethenyl, 2-methoxymethyl-2-methylethenyl, or alicyclic type as shown in the above [F] group Alkyl, or 1,4-phenylene which can increase the glass transition temperature of the resin composition, selected from the group consisting of an alkylene group having 1 to 10 carbon atoms which can be substituted and an aromatic compound having 4 to 10 carbon atoms which can be substituted In the group consisting of two or more groups, two or more groups are connected by oxygen atoms.

Especially preferred are direct bond, ethyl, n-propyl, n-butyl, methylmethylene, 1-methylethyl, 2-methylethyl, or 2,2-dimethylene base.

Ethyl or propyl is preferred. If the chain length is longer, the glass transition temperature tends to be lower. Therefore, a shorter chain-like base such as a base having 3 or less carbon atoms is preferred. Furthermore, since the molecular structure becomes smaller, the concentration (fluorene ratio) of the fluorene ring in the repeating unit can be increased, and thus the required optical physical properties can be developed efficiently.

The same substituents α ¹ and α ² are preferred because they facilitate production.

<1.5 Specific Structure>

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

(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 alkylene group having 1 to 10 carbon atoms which can be substituted, an alkylene group having 4 to 10 carbon atoms which can be substituted, or an alkylene group having 6 to 10 carbon atoms which can be substituted base.

R ⁴ to R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbons which may have a substituent, an aryl group having 4 to 10 carbons which may have a substituent, and 1 to 10 carbon atoms which may have a substituent Group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have a substituent Amine group of the group, vinyl group having 1 to 10 carbons which may have a substituent, ethynyl group having 1 to 10 carbons which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom, Nitro, or cyano. Among them, at least two adjacent groups in 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 the general formula (1), R ^3a and R ^3b may be the same or different. In addition, each of R ⁴ to R ^{9 in the} general formula (1) may be the same or different. Similarly, two of R ¹⁰ in the general formula (1) may be the same or different.

In R ¹ and R ² of the above general formula (1), as "an alkylene group having 1 to 4 carbon atoms which may have a substituent", R ¹ and R ^{2 of the} above-mentioned "Invention 1" can be preferably used. Illustrated in the base.

Similarly, as R ^3a and R ^3b , those exemplified in <1.1 Alkenyl, Arylene, and Arylene> can be preferably used. In addition, in this specification, R ^3a and R ^{3b may} be described together with R ³ .

In addition, as R ¹⁰ , those exemplified as the organic substituent having 1 to 10 carbon atoms in <1.3 ester group> can be preferably used.

In R ⁴ to R ⁹ , the specific structure of the "alkyl group having 1 to 10 carbon atoms which may be substituted" is listed below, and is not limited thereto. Examples include methyl, ethyl, n-propyl, Linear alkyl groups such as n-butyl, n-pentyl, n-hexyl, n-decyl; isopropyl, 2-methylpropyl, 2,2-dimethylpropyl, 2-ethylhexyl, etc. Side chain alkyl groups; cyclic alkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl.

The number of carbon atoms in the alkyl group having 1 to 10 carbon atoms which may be substituted is preferably 4 or less, and more preferably 2 or less. If it is within this range, the steric hindrance of the fluorene rings is difficult to occur, and the optical characteristics required from the fluorene rings tend to be obtained.

Examples of the substituent that the alkyl group may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); and an alkoxy group (for example, a methoxy group, an ethoxy group) having 1 to 10 carbon atoms. Etc.); fluorenyl groups having 1 to 10 carbon atoms (for example, acetofluorenyl, benzamidine, etc.); fluorenyl groups having 1 to 10 carbon atoms (for example, acetamido, benzamidine, etc.); Nitro; cyano; may have a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.) , Alkoxy groups with 1 to 10 carbon atoms (for example, methoxy, ethoxy, etc.), fluorenyl groups with 1 to 10 carbon atoms (for example, ethyl fluorenyl, benzyl fluorenyl, etc.), carbon numbers 1 to 10 Sulfonylamino (for example, ethynylamine, benzamidine, etc.), nitro, cyano, etc. 1 to 3 substituents, 6-10 carbon atoms (for example, phenyl, naphthyl and many more. The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

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

The specific structure of the "aryl group having 4 to 10 carbon atoms which may be substituted" in R ⁴ to R ⁹ is listed below and is not limited thereto. Examples include: phenyl, 1-naphthyl, and 2-naphthalene Aryl groups such as alkyl; heteroaryl groups such as 2-pyridyl, 2-thienyl, and 2-furyl.

The number of carbon atoms in the aryl group having 4 to 10 carbon atoms that can be substituted is preferably 8 or less, and more preferably 7 or less. If it is within this range, it is difficult for steric rings to have steric hindrance to each other, and it is possible to obtain The desired optical characteristics of the ring.

Examples of the substituent which the aryl group may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); and an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, and isopropyl) Alkoxy groups (e.g., methoxy, ethoxy, etc.) having 1 to 10 carbon atoms; fluorenyl groups (e.g., ethenyl, benzyl, etc.) having 1 to 10 carbon atoms; carbon number 1 to 10 amido groups (for example, acetamido, benzamido, etc.); nitro; cyano and the like. The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

Specific examples of the aryl group which may be substituted include 2-methylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 4-benzylphenyl, 4-methyl Oxyphenyl, 4-nitrophenyl, 4-cyanophenyl, 3-trifluoromethylphenyl, 3,4-dimethoxyphenyl, 3,4-methylenedioxybenzene Group, 2,3,4,5,6-pentafluorophenyl, 4-methylfuryl and the like.

The specific structure of the "fluorenyl group having 1 to 10 carbon atoms which can be substituted" in R ⁴ to R ⁹ is enumerated below, and is not limited thereto. Examples include methylamyl, ethylamyl, and propylamyl , 2-methylpropanyl, 2,2-dimethylpropanyl, 2-ethylhexyl, and other aliphatic fluorenyl groups; benzylfluorenyl, 1-naphthylcarbonyl, 2-naphthylcarbonyl, Aromatic fluorenyl groups such as 2-furylcarbonyl.

The number of carbon atoms in the fluorenyl group having 1 to 10 carbon atoms that can be substituted is preferably 4 or less, and more preferably 2 or less. If it is within this range, the steric hindrance of the fluorene rings is difficult to occur, and the optical characteristics required from the fluorene rings tend to be obtained.

Examples of the substituent which the fluorenyl group may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); and an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, and isopropyl) Groups, etc.); alkoxy groups (e.g., methoxy, ethoxy, etc.) having 1 to 10 carbon atoms; fluorenyl groups (e.g., acetoamino, benzamidine, etc.) having 1 to 10 carbon atoms ; Nitro; cyano; may have a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc. ), Alkoxy with 1 to 10 carbons (For example, methoxy, ethoxy, etc.), fluorenyl groups having 1 to 10 carbon atoms (for example, ethenyl, benzamidine, etc.), and fluorenyl groups having 1 to 10 carbon atoms (for example, acetamido Phenyl group, benzamidine amino group, etc.), aryl groups having 1 to 3 substituents such as nitro and cyano groups, and aryl groups having 6 to 10 carbon atoms (for example, phenyl, naphthyl, etc.). The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

Specific examples of the fluorenyl group which may be substituted include chloroethylfluorenyl, trifluoroethylfluorenyl, methoxyethylfluorenyl, phenoxyethylfluorenyl, 4-methoxybenzomethylfluorenyl, 4 -Nitrobenzyl, 4-cyanobenzyl, 4-trifluoromethylbenzyl and the like.

The specific structure of the "alkoxy or aryloxy group having 1 to 10 carbon atoms which may be substituted" in R ⁴ to R ⁹ is listed below, and is not limited thereto. Examples include methoxy and ethoxy. Alkyl, isopropyloxy, tertiary butoxy, trifluoromethoxy, phenoxy and other alkoxy groups; aryloxy and other aryloxy groups.

Among the alkoxy or aryloxy groups having 1 to 10 carbon atoms that may be substituted, alkoxy groups are preferred, and the number of carbon atoms in the alkoxy group is preferably 4 or less, more preferably 2 or less. If it is within this range, the steric hindrance of the fluorene rings is difficult to occur, and the optical characteristics required from the fluorene rings tend to be obtained.

The specific structure of the "substitutable amine group" in R ⁴ to R ⁹ is listed below, and is not limited thereto. Examples include: amine group; N-methylamino group, N, N-dimethyl Amine, N-ethylamino, N, N-diethylamino, N, N-methylethylamino, N-propylamino, N, N-dipropylamino, N- Aliphatic amine groups such as isopropylamino group, N, N-diisopropylamino group; aromatic amine groups such as N-phenylamine group, N, N-diphenylamino group; formamidine group, ethyl group Fluorenylamino groups such as fluorenylaminodecanoylamino, benzamidineamino, chloroacetamidinyl; alkoxycarbonylamino groups such as benzyloxycarbonylamino, tertiary butoxycarbonylamino, and the like.

Among these, N, N-dimethylamino group and N-ethylamino group are preferred in terms of not having a proton having a relatively high acidity, having a small molecular weight, and a tendency to increase the ratio of pyrene. Or N, N-diethylamino, more preferably N, N-dimethylamino.

The specific structure of the "sulfur atom having a substituent" in R ⁴ to R ⁹ is listed below, and is not limited thereto. Examples include: sulfo, methanesulfonyl, ethylsulfonyl, and sulfonylsulfonyl , Alkylsulfonyl groups such as isopropylsulfonyl; arylsulfonyl groups such as phenylsulfonyl, p-tolylsulfonyl; methylsulfinyl, ethylsulfinyl, propylidene Alkyl sulfinyl sulfonyl groups such as sulfonyl, isopropylsulfinyl sulfinyl; arylsulfinyl phenyl sulfinyl, p-tolyl sulfinyl sulfinyl; methyl thio, ethyl thio Thio; arylthio, such as phenylthio, p-tolylthio; alkoxysulfonyl, such as methoxysulfonyl, ethoxysulfonyl; aryloxysulfonyl, such as phenoxysulfonyl ; Aminosulfonyl; N-methylaminosulfonyl, N-ethylaminosulfonyl, N-thirdbutylaminosulfonyl, N, N-dimethylaminosulfonyl Alkyl, sulfonyl groups such as N, N-diethylaminosulfonyl; arylaminosulfonyl groups such as N-phenylaminosulfonyl, N, N-diphenylaminosulfonyl Base etc. Furthermore, the sulfo group may form a salt with lithium, sodium, potassium, magnesium, ammonium, and the like.

Among these, in terms of not having a proton having a relatively high acidity, having a small molecular weight, and a tendency to increase the ratio of pyrene, methylsulfinyl sulfenyl, ethylsulfinyl sulfinyl, or benzene is preferred. The sulfinyl sulfenyl group is more preferably a methylsulfinyl sulfinyl group.

Examples of the "halogen atom" in 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 more preferable because it is relatively easy to introduce and tends to increase the reactivity at the 茀 -position due to an electron-withdrawing substituent. Atom or bromine atom.

As described above, by setting R ⁴ to R ⁹ as the specific atom or substituent as described above, there is a tendency that there is less steric hindrance between the main chain and the fluorene ring, or between the fluorene ring and each other. The required optical characteristics derived from the hafnium ring can be obtained.

Of these R ⁴ to R ⁹ , all of them are preferably hydrogen atoms, or R ⁴ and / or R ⁹ is any one selected from the group consisting of a halogen atom, a fluorenyl group, a nitro group, a cyano group, and a sulfo group. One of them, and R ⁵ to R ⁸ are hydrogen atoms. In the case where all of them are hydrogen atoms, they can be derived from industrially inexpensive osmium. When R ⁴ and / or R ⁹ is any one selected from the group consisting of a halogen atom, a fluorenyl group, a nitro group, a cyano group, and a sulfo group, and R ⁵ to R ⁸ are a hydrogen atom Since the reactivity of the 9th position is improved, there is a tendency to adapt to various derivative reactions. More preferably, all of them are a hydrogen atom, or R ⁴ and / or R ⁹ is any one 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 hydrogen atoms. Especially preferred is the case where all are hydrogen atoms. In addition, it is possible to increase the erbium ratio by setting to the above, and it is also difficult to generate steric hindrance between the erbium rings, so that it is possible to obtain required optical characteristics derived from the erbium rings.

<1.6 Specific Examples of Tris (III) Diester>

Specific examples of the tertiary diester of the present invention include a structure shown in the following [H] group.

[Chemical 43]

<1.7 Physical Properties of Tris (III) Diester>

The physical property value of the tertiary diester of the present invention is not particularly limited, and it is preferably one that satisfies the physical property values exemplified below.

Regarding the chlorine content in the tertiary diester of the present invention, it is preferably 100 mass ppm or less in terms of Cl conversion mass. It is more preferably 10 mass ppm or less. When the content of the chlorine component is large, the catalyst used in the polymerization reaction may be deactivated, the polymerization may not proceed to the required molecular weight, or the reaction may become unstable and the productivity may be deteriorated. In addition, the chlorine component may remain in the obtained polymer, which may reduce the thermal stability of the polymer.

It is preferable that the content ratio of the tertiary monoester in the tertiary diester of the present invention is 10% by mass or less based on the mass of all the tertiary compounds. It is more preferably 2% by mass or less. If the triammonium monoester is introduced into the polymer during the polymerization reaction, it will become a capping group. Therefore, if the triammonium monoester is increased, the polymerization will no longer proceed to the required molecular weight, or the polymer will be low. The residual amount of the low-molecular component such as a polymer may increase, so that the mechanical strength or heat resistance of the obtained polymer may decrease. In addition, it is considered that there is a possibility that the low-molecular component oozes out of the molded body and the like, thereby reducing the quality of the product. The term “monoester” means that any one of the terminal ester groups of the tertiary diester becomes a group other than the polymerization-reactive group.

In the tertiary diester of the present invention, there is a Group 1 metal such as sodium or potassium of the long-period periodic table containing a step derived from methylolation by the action of formaldehydes in the presence of a base, or Group 2 such as calcium. The possibility of metals is preferably 500 mass ppm or less, more preferably 200 mass ppm or less, still more preferably 50 mass ppm or less, and even more preferably 10 mass ppm or less. When there are many metal components, there exists a possibility that a polymer may become colored easily at the time of a polymerization reaction or processing a resin. In addition, there is a possibility that the metal component contained in the catalyst exhibits a catalyst effect or a catalyst deactivation effect, thereby causing polymerization to become unstable.

Among the tertiary diesters, especially tristearyl diaryl esters of the present invention, there are titanium, copper, iron, etc. which are derived from the step of transesterifying by the action of diaryl carbonates in the presence of a transesterification reaction catalyst. The possibility of transition metals, or Group 1 of the long-period periodic table such as sodium or potassium, or Group 2 metals such as magnesium and calcium, or Group 12 metals such as zinc or cadmium, or Group 14 metals such as tin, etc. The content ratio is preferably 500 mass ppm or less, more preferably 200 mass ppm or less, still more preferably 50 mass ppm or less, and even more preferably 10 mass ppm or less. When there are many metal components, there exists a possibility that a polymer may become colored easily at the time of a polymerization reaction or processing a resin. In addition, there is a possibility that the metal component contained in the catalyst exhibits a catalyst effect or a catalyst deactivation effect, thereby causing polymerization to become unstable.

In the trimethyl diester of the present invention, the color tone of the tetrahydrofuran solution of 10% by mass is preferably 50 or less. It is more preferably 10 or less. Trimethyl diester has the following properties: the absorption end is extended to be close to Areas that see light are easily colored when exposed to high temperatures due to polymerization or resin processing. In order to obtain a polymer with a good hue, it is preferred that the tri-methylene diester used in the polymerization reaction is colored as little as possible. Since the hue is proportional to the density, it can also be a value obtained by measuring at different concentrations and normalizing it to a concentration of 10% by mass. Here, the color tone (APHA value) of the tertiary diester can be prepared by diluting the chromaticity standard solution (1000 degrees) manufactured by Kishida Chemical Co., Ltd. with Sanshidi according to JIS-K0071-1 (1998). The ester was measured in a colorimetric tube with an inner diameter of 20 mm for comparison.

The 5% weight reduction temperature of the tertiary diester of the present invention under thermogravimetric measurement is preferably 230 ° C or more, and more preferably 250 ° C or more. The temperature is more preferably 270 ° C or higher. Samarium is a very electron-rich structure, and the reactivity of the substituents bonded to the samarium ring is improved, and it becomes easy to cause thermal decomposition. If a tertiary diester having a lower thermal decomposition temperature is used in the polymerization reaction, there is a possibility that thermal decomposition will be caused during the polymerization and the polymerization will no longer proceed to the desired molecular weight, or the obtained polymer will be colored.

In addition, the decomposition temperature of the tertiary diester of the present invention measured under a nitrogen environment is preferably 250 ° C or higher, more preferably 300 ° C or higher, even more preferably 330 ° C or higher, and usually 380 ° C or lower. Since the tertiary diester of the present invention has a rigid structure due to the laminated structure of the fluorene ring, the decomposition temperature tends to satisfy the above range. When the decomposition temperature satisfies the above range as described above, there is a tendency that the thermal stability of the polyester and polycarbonate obtained from the triglyceride can be improved. The decomposition temperature can be measured, for example, by TG-DTA (Thermo-Gravimetric-Differential Thermal Analysis).

Furthermore, the melting point (m.p.) of the tertiary diester of the present invention is preferably 120 ° C or higher, more preferably 130 ° C or higher, even more preferably 150 ° C or higher, and usually 200 ° C or lower. Since the tertiary diester of the present invention has a rigid structure due to the laminated structure of the fluorene ring, the melting point tends to satisfy the above range. When the melting point satisfies the above range as described above, there is a tendency that the glass transition temperature of the polyester and polycarbonate obtained from the triglyceride can be increased. The melting point can be measured by, for example, TG-DTA.

<1.8 Manufacturing Method of Tris (III) Diester>

There is no restriction on the production method of the tertiary diester used in the present invention, especially the tertiary diester represented by the general formula (1). For example, the production method A or the production method shown by the following formula can be used. B and other methods.

Furthermore, the difluorene diester can be produced under the same conditions as in the production method C after adjusting the amount of reagent corresponding to R ³ to obtain the difluorene diester according to the production method of the trifluorene compound (II).

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 alkylene group having 1 to 10 carbon atoms which can be substituted, an alkylene group having 4 to 10 carbon atoms which can be substituted, or an alkylene group having 6 to 10 carbon atoms which can be substituted R ⁴ to R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, and 醯 1 to 10 carbon atoms that can be substituted Group, alkoxy group having 1 to 10 carbon atoms which may be substituted, aryloxy group having 1 to 10 carbon atoms which may be substituted, amine group which may be substituted, sulfur atom having a substituent, halogen atom, nitro or Cyano. Among them, at least two adjacent groups in 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 Manufacturing Method A>

Production method A is a method in which fluorene (I) is converted into 9-hydroxymethyl fluorene (IV) as a raw material, and an olefin (V) synthesized by dehydration is reacted with a fluorenyl anion. Purification is performed from a mixture of oligomeric fluorenes by column purification or the like to produce a tertiary hydrazone compound (IIa) in which R ³ is a methylene group. Furthermore, unsubstituted 9-hydroxymethyl hydrazone can be purchased as a reagent. Here, it is also possible to prepare a tri-methylene diester (I) by introducing an ester group from the obtained tri-methylene compound (II) according to step (ii) of the manufacturing method C.

For example, a method is known in which 9-hydroxymethylfluorene is converted into dibenzofulvene and then a mixture of oligomeric fluorenes is synthesized by anionic polymerization (J. Am. Chem. Soc., 123, 2001, 9182-9183.). Using these as a reference, the trifluorene compound (II) can be produced by purification from the mixture.

<1.8.2 Manufacturing Method B>

Production method B is a method in which a cross-linking reaction of the amidine (I) of the raw material (step (i)) is performed to synthesize a triamidine compound (II), and then an ester group is introduced (step (ii)). This produces a tris (-) diester (1).

Wherein, R ¹ ~ R ¹⁰ the same line with the formula R (1) ¹ ~ R ¹⁰ in the meaning.

Hereinafter, the manufacturing method B is divided into the manufacturing method of the step (i) triamidine compound (II) and the manufacturing method of a step (ii) trimer diester (1).

<1.8.3 Step (i): Method for producing triamidine compound (II)>

In the formula, R ³ ~ R ⁹ based formula R (1) ~ ³ in the same meaning as R ^9.

Hereinafter, the production method of the stilbene compound (II) in step (i) will be described as a case where it is divided into R ³ .

<1.8.3.1 When R ³ is a direct bond: 9,9 ': 9', 9 "-Mitsumi's manufacturing method>

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

<1.8.3.2 Step (ia): Production method in a case where R ³ is methylene>

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

In the formula, R ⁴ ~ R ⁹ based same formula (1) in the meaning of R ⁴ ~ R ^9.

<1.8.3.2.1 Formaldehydes>

The so-called formaldehydes used in step (ia) are not particularly limited as long as they can supply formaldehyde to the reaction system. Examples include gaseous formaldehyde, aqueous formaldehyde solution, paraformaldehyde polymerized by formaldehyde, and Alkanes, etc. From the viewpoint that it is industrially inexpensive and easy to handle and can be accurately weighed due to the powder form, paraformaldehyde is more preferred. On the other hand, formaldehyde is more preferred from the viewpoint that it is industrially inexpensive and has less risk of exposure during addition due to liquid.

(Definition of theoretical quantity)

In the case of producing the target amidine compound (IIa), the theoretical amount (molar ratio) of formaldehydes relative to the amidine (I) of the raw material is represented by 2/3.

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

In the case where formaldehydes are used in an amount exceeding the theoretical amount with respect to the fluorene (I), there is a tendency that the ternary hydrazone compound (IIa) is more targeted than the fluorene crosslinked oligomeric fluorene compound. It can be seen that as the number of fluorene rings of an oligomeric fluorene compound increases, the solubility decreases. Therefore, when there are more than 4 fluorene ring-linked oligomeric fluorene compounds in the target, the purification load tends to increase. Therefore, in general, the amount of formaldehyde used is preferably less than 2/3 times the target theoretical amount.

(Why not better than the theoretical amount)

In addition, it can be seen that if the amount of formaldehydes used is significantly lower than 2/3 of the theoretical amount, there will be more than the target triamidine compound (IIa), and a diammonium compound with a smaller number of crosslinks of the amidine ring will become the main product, The amidine (I) of the raw materials remains unreacted, and therefore the yield tends to decrease significantly.

Therefore, the optimal amount of formaldehyde used is, in particular, 0.5 times mole or more, preferably 0.55 times mole or more, and more preferably 0.6 times mole relative to the raw material (I). Above the ear, it is usually 0.67 times mole or less, preferably 0.65 times mole or less, and still more preferably 0.63 times mole or less. As mentioned above, it can be seen that depending on the amount of formaldehyde used, the ratio of the structure of the main product to the product greatly changes. By using it under the condition that the amount of formaldehyde used is limited, the third target can be obtained in high yield. Tendency of the compound (IIa).

<1.8.3.2.2 Alkali>

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; sodium carbonate, and carbonic acid. Carbonates of alkali metals such as sodium hydrogen and potassium carbonate, carbonates of alkaline earth metals such as magnesium carbonate and calcium carbonate, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate and potassium phosphate, n-butyl lithium, third butyl lithium, etc. Organic lithium salts, sodium alkoxides of alkali metals such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide, alkali metal hydrides such as sodium hydride or potassium hydride, tertiary amines such as triethylamine and diazabicycloundecene , Tetramethylammonium hydroxide, Tetrabutylammonium hydroxide, etc. These may be used individually by 1 type, and may use 2 or more types together.

When the reaction is performed in a homogeneous system, among these, the alkali metal alkoxide having sufficient basicity in the reaction is preferred, and industrially inexpensive sodium methoxide or sodium ethoxide is more preferred. Here, the alkali metal alkoxide may be used in a powder form or in a liquid form such as an alcohol solution. It is also possible to prepare by reacting an alkali metal with an alcohol.

On the other hand, when the reaction is performed in a two-layer system, among these, an aqueous solution of an alkali metal hydroxide having sufficient basicity in the reaction is preferable, and industrially inexpensive sodium hydroxide, Or an aqueous solution of potassium hydroxide, and more preferably an aqueous solution of sodium hydroxide.

In addition, regarding the concentration of the aqueous solution, in the case of using an especially preferred sodium hydroxide aqueous solution, if the concentration is relatively thin, the reaction rate is significantly reduced. Therefore, it is generally used at 10 wt / wt% or more, preferably 25 wt / wt% or more, More preferably, it is an aqueous solution of 40 wt / wt% or more.

When the reaction is carried out in a homogeneous system, the upper limit of the amount of alkali used is not particularly limited with respect to the amidine (I) as a raw material, but if the amount is too large, the purification load after stirring or reaction becomes large Therefore, it is usually 10 times or less, preferably 5 times or less, and more preferably 1 time or less. On the other hand, if the amount of alkali used is too small, the reaction tends to slow down. Therefore, as the lower limit, it is usually 0.01 times the mole or more, and preferably 0.1 times the mole or more, relative to the raw material (I). , And more preferably 0.2 times mole or more.

On the other hand, in the case where the reaction is performed in a two-layer system, the upper limit of the amount of alkali used is not particularly limited with respect to the stilbene (I) as a raw material, but if the amount is too large, there may be stirring or reaction Since the refining load tends to increase, it is usually 10 times or less, preferably 5 times or less, and more preferably 2 times or less. On the other hand, if the amount of alkali used is too small, the reaction tends to slow down. Therefore, as the lower limit, it is usually 0.1 times or more, and preferably 0.3 times or more, relative to the type (I) of the material. , And more preferably 0.4 times mole or more.

<1.8.3.2.3 Solvents>

Step (ia) is preferably performed using a solvent. Specific examples of usable solvents include acetonitrile and propionitrile as the alkyl nitrile solvent, and diethyl ether, tetrahydrofuran, and 1,4-dicarbonate as the ether solvent. Alkane, methylcyclopentyl ether, third butyl methyl ether, and the like. Examples of the halogen-based solvent include 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane. Examples of the halogen-based aromatic hydrocarbon include chlorobenzene and 1,2-dichlorobenzene. Examples of the fluorene-based solvent include N, N-dimethylformamide and N, N, -dimethyl. Acetylamine, N-methylpyrrolidone and the like. Examples of the fluorene-based solvents include dimethyl fluorene and cyclobutane. Examples of the cyclic aliphatic hydrocarbon include cyclopentane and cyclohexane. , Monocyclic aliphatic hydrocarbons such as cycloheptane, cyclooctane; methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2- Dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, third butylcyclohexane , N-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; polycyclic forms such as decalin Aliphatic hydrocarbons; n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Examples of the acyclic aliphatic hydrocarbon include toluene, para-xylene, o-xylene, and meta-xylene. Examples of the alcohol-based solvent include methanol, ethanol, isopropanol, n-butanol, and Tributanol, hexanol, octanol, cyclohexanol, etc.

In the reaction of the homogeneous system, the anion generated from the amidine (I) has high solubility, and in terms of the tendency of the reaction to proceed well, a fluorene-based solvent or a subfluorinated solvent is preferred. Department of solvents. Among them, N, N-dimethylformamide is particularly preferred. The reason is that there is a tendency that the triamidine compound (IIa) has a low solubility in N, N-dimethylformamide, and the target substance precipitates rapidly after it is generated, and the progress of subsequent reactions is suppressed, and the target Material selectivity is improved.

In the two-layer reaction, two layers are formed with an alkaline aqueous solution. The anion generated from the amidine (I) has high solubility, and a polar solvent is preferred in terms of the tendency of the reaction to proceed well. An ether-based solvent or a halogen-based solvent. Among them, tetrahydrofuran is particularly preferred. its The reason is that there is a tendency that the triamidine compound (IIa) has a low solubility in tetrahydrofuran, and the target substance precipitates rapidly after it is generated, the subsequent reaction progress is suppressed, and the selectivity of the target substance increases.

These solvents may be used alone or in combination of two or more.

As the upper limit of the amount of the solvent used, an amount of 10 times the volume, preferably 7 times the volume, and more preferably 4 times the volume is used as the raw material (I). On the other hand, if the amount of the solvent used is too small, stirring tends to be difficult and the progress of the reaction tends to be slow. Therefore, as the lower limit, a volume of 1 times as much as the raw material (I) is preferably used, preferably 2 The volume-by-volume amount, and more preferably the volume-by-volume amount is 3 times.

<1.8.3.2.4 Reaction Form>

When performing step (ia), the reaction may take the form of a batch reaction, a flow-through reaction, or a combination of these, and the form is not particularly limited.

<1.8.3.2.5 Reaction conditions>

Regarding step (ia), in order to suppress the generation of the fluorene ring-crosslinked compound compared to the trifluorene compound (IIa), the reaction is preferably performed at a low temperature as much as possible. On the other hand, if the temperature is too low, a sufficient reaction rate may not be obtained.

Therefore, as a specific reaction temperature, the upper limit is usually 40 ° C, preferably 30 ° C, and more preferably 20 ° C. On the other hand, the lower limit is -50 ° C, preferably -20 ° C, and more preferably 0 ° C or higher.

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

<1.8.3.2.6 Separation and purification of target>

After completion of the reaction, the target compound (IIa) can be added to the reaction solution by adding the reaction solution to acidic water such as dilute hydrochloric acid, or by adding acidic water such as dilute hydrochloric acid to the reaction solution. IIa) Precipitation and single isolation.

After the reaction is completed, a solvent in which the target compound (IIa) is soluble and water may be added to the reaction solution to perform extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent. Among them, the solubility of the tertiary amidine compound (IIa) in a solvent at room temperature tends to be very low, and therefore, a method of precipitating it in contact with acidic water is generally preferred.

The obtained stilbene compound (IIa) can also be used directly as a raw material in step (ii), but it can also be used in step (ii) after purification. As the purification method, ordinary purification methods such as recrystallization, reprecipitation, extraction purification, and column chromatography can be used without limitation.

<1.8.3.3 Step (ib): Manufacturing method in a case where R ³ is other than a direct bond>

The tertiary amidine compound represented by the following general formula (IIb) is produced using the amidine group (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).

In the formula, R ³ , R ^3a , and R ^3b are an alkylene group having 1 to 10 carbon atoms that can be substituted, an arylene group having 4 to 10 carbon atoms that can be substituted, or 6 to 10 carbon atoms that can be substituted. the arylene group, the same as R ⁴ ~ R ⁹ based formula R (1) ⁴ ~ R ⁹ in the meaning. X represents a radical. Examples of the leaving group include a halogen atom (excluding fluorine, among others), a methanesulfonyl group, or a tosylsulfonyl group.

The trifluorene compound (IIb) can be coupled with an alkylating agent (VIIIa) by using n-butyllithium as a base to generate anions of the fluorene (I) (J. Am. Chem. Soc., 2007, 129, 8458.) for reference. However, in these methods using n-butyllithium, for industrial production, there is a tendency that it is very difficult both in terms of safety and cost.

Examples of the alkylating agent used in step (ib) include diiodomethane and 1,2-diiodo Ethane, 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, Dihalogenated linear alkyl groups such as 3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, and 1-bromo-3-chloropropane (Except fluorine atom), 2,2-dimethyl-1,3-dichloropropane and other alkyl dihalides containing side chains (except fluorine atom), 1,4-bis (bromomethyl) Aralkyl dihalides (excluding fluorine atoms) such as benzene, 1,3-bis (bromomethyl) benzene, ethylene glycol dimethyl sulfonate, ethylene glycol dimethyl sulfonate, propylene glycol dimethyl methanesulfonic acid Esters, diol disulfonates such as 1,4-butanediol dimethanesulfonate and the like.

<1.8.4 Manufacturing method of tris (3) diester (1)>

Hereinafter, the production method of the tertiary diester (1) in the step (ii) represented by the following formula is classified by the type of R ¹ and described.

Wherein, R ¹ ~ R ¹⁰ the same line with the formula R (1) ¹ ~ R ¹⁰ in the meaning. R _i , R _ii and R _iii each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or 6 to 10 carbon atoms that can be substituted Of aralkyl.

<1.8.4.1 Step (iia): Manufacturing Method by Using Michael Addition>

The tertiary diester represented by the following general formula (1a) is based on the reaction represented by the following step (iia) in the presence of a base, from the trifluoride compound (II) and the α, β-unsaturated ester (VI ) For manufacturing.

In the formula, ³ to the same meaning as R ¹⁰ R ¹⁰ R & lt lines ³ to the formula R (1) in the. R _i , R _ii and R _iii each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or 6 to 10 carbon atoms that can be substituted Of aralkyl.

<1.8.4.1.1 α, β-unsaturated ester>

The α, β-unsaturated ester system 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 each independently represent a hydrogen atom and a carbon number. An alkyl group of 1 to 10, an aryl group of 4 to 10 carbons that can be substituted, or an aralkyl group of 6 to 10 carbons that can be substituted. Specific examples include: methyl, ethyl, n-propyl, isopropyl, cyclohexyl, etc. (which may be straight or side chain) alkyl, phenyl, 1-naphthyl, 2-naphthyl , Aryl such as 2-thienyl, aralkyl such as benzyl, 2-phenylethyl, and p-methoxybenzyl.

Examples of the α, β-unsaturated ester (VI) include methyl acrylate, ethyl acrylate, phenyl acrylate, allyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. Acrylates such as 1,4-cyclohexanedimethanol monoacrylate, methyl methacrylate, ethyl methacrylate, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, Methacrylic esters such as 2-hydroxyethyl methacrylate, α-substituted unsaturated esters such as methyl 2-ethylacrylate and methyl 2-phenylacrylate, methyl cinnamate, ethyl cinnamate, butyl Β-substituted unsaturated esters such as methyl enoate and ethyl butenoate. Among these, an unsaturated carboxylic acid ester represented by the following general formula (VI-1) into which a polymerization-reactive group can be directly introduced is preferred.

[Chemical 51]

(In the formula, R ¹⁰ represents an organic substituent having 1 to 10 carbon atoms, and R _iii represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or Arylalkyl with 6 to 10 carbon atoms that can be substituted). The acrylates, methacrylates, or α-substituted unsaturated esters contained therein are more preferable, and from the viewpoint of reaction speed and reaction selectivity, it is more preferable that R _iii is a hydrogen atom or a methyl group. Acrylates or methacrylates. The smaller R ¹⁰ is industrially cheap and easy to be distilled and refined, and has high reactivity, so it is particularly preferably methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate, or Phenyl methacrylate.

On the other hand, the unsaturated carboxylic acid ester (VI-1) has a hydroxyalkyl group such as a 2-hydroxyethyl acrylate group, a 4-hydroxybutyl acrylate group, and a 1,4-cyclohexanedimethanol monoacrylate group. In the case of esters, polyester carbonate and polyester raw materials can be obtained in the first stage, which is particularly preferable.

It is also possible to use two or more different α, β-unsaturated esters (VI). In terms of simplicity of purification, it is preferable to use one type of α, β-unsaturated ester (VI).

The polymerization activity of α, β-unsaturated ester (VI) is relatively high. Therefore, if it is present at a high concentration, it tends to be easily polymerized due to external stimuli such as light, heat, acid, and alkali. At this time, there is a case where it becomes very dangerous due to a large heat release. Therefore, the use amount of the α, β-unsaturated ester (VI) is preferably not excessively used from the viewpoint of safety. It is usually 10 times or less, preferably 5 times or less, and more preferably 3 times or less, with respect to the tertiary amidine compound (II) as a raw material. The lower limit is 2 times the mole in terms of the theoretical amount of the raw material, and therefore is usually 2 times the mole or more. In order to speed up the reaction without leaving raw materials or intermediates, the amount of α, β-unsaturated ester (VI) used is 2.2 times more mols than that of the tris (3) compound (II) of the raw materials, which is more preferable. It is 2.5 times more than Mol.

<1.8.4.1.2 alkali>

As the base, 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 alkali metals such as sodium carbonate, sodium bicarbonate, and potassium carbonate can be used. Carbonate, magnesium carbonate, calcium carbonate and other alkaline earth metal carbonates, sodium phosphate, sodium hydrogen phosphate, potassium phosphate and other phosphoric acid alkali metal salts, organic lithium salts such as n-butyl lithium, third butyl lithium, sodium methoxide, Alkoxides of alkali metals such as sodium ethoxide, potassium tert-butoxide, etc., alkali metal hydrides such as sodium hydride or potassium hydride, tertiary amines such as triethylamine, diazabicycloundecene, and tetramethylammonium hydroxide , Tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and other tertiary ammonium hydroxide. 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 other cases, there is a tendency that the reactivity of the stilbene compound (II) is greatly different. Therefore, the case where R ³ is methylene is described separately from the case other than R ³ .

When R ³ is a methylene group, the trifluorene compound (II) is in a solvent, and a decomposition reaction is easily performed in the presence of a base. Therefore, when a reaction is performed in a two-layer system of an organic layer and an aqueous layer, a water-soluble inorganic base is preferably used in terms of suppressing side reactions such as decomposition reactions. Among these, in terms of cost and reactivity, an aqueous solution of an alkali metal hydroxide, particularly an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is more preferable, and an aqueous solution of sodium hydroxide is more preferable.

In addition, regarding the concentration of the aqueous solution, in the case of using an especially preferred sodium hydroxide aqueous solution, if the concentration is relatively thin, the reaction rate tends to be significantly reduced. Therefore, it is particularly preferred to use 10wt / wt% or more, preferably An aqueous solution of 30 wt / wt% or more, more preferably 40 wt / wt% or more.

When R ³ is other than methylene, the reaction is also performed in the two-layer system of the organic layer and the water layer. However, when the reaction is performed using an organic base dissolved in the organic layer, the reaction tends to proceed quickly. Therefore, it is preferable to use an organic base. Among these, an alkali metal alkoxide having sufficient basicity in this reaction is preferable, and industrially inexpensive sodium methoxide or sodium ethoxide is more preferable. Here, the alkali metal alkoxide may be used in a powder form or in a liquid form such as an alcohol solution. Alternatively, it may be prepared by reacting an alkali metal with an alcohol.

In the case where R ³ is methylene, the upper limit of the amount of alkali used is not particularly limited with respect to the compound (II) as a raw material. If the amount is too large, the purification load after stirring or reaction may change. In most cases, when an aqueous sodium hydroxide solution of 40 wt / wt% or more, which is a particularly preferred base, is used, it is usually 10 times or less the volume, and preferably 5 times or less the volume of the tris (II). It is more preferably 2 times the volume or less. If the amount of the base is too small, the reaction rate is significantly reduced. Therefore, the amount of the base is generally 0.1 times or more the volume of the stilbene compound (II) of the raw material. It is preferably at least 0.2 times the volume, more preferably at least 0.5 times the volume.

When R ³ is other than methylene, the upper limit of the amount of alkali used is not particularly limited relative to the compound (II) used as a raw material. If the amount is too large, there may be a purification load after stirring or reaction. When it becomes larger, when using sodium methoxide or sodium ethoxide as a particularly good base, it is usually 5 times or less, preferably 2 times or less, and more It is preferably less than 1 mole, particularly preferably less than 0.5 mole. If the amount of alkali is too small, the reaction rate tends to be significantly reduced. Therefore, the alkali is usually 0.005 times mole or more relative to the base (II) of the raw material. It is preferably at least 0.01 times the mole, more preferably at least 0.05 times the mole, and even more preferably at least 0.1 times the mole.

<1.8.4.1.3 Phase-to-phase transfer catalyst>

In the case where the reaction is performed in a two-layer system of an organic layer and an aqueous layer in step (iia), in order to increase the reaction speed, 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, Halides (except fluorine) of quaternary ammonium salts such as trioctylmethylammonium chloride, tetrabutylammonium iodide, acetamyltrimethylammonium bromide, benzyltriethylammonium chloride, etc. , N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl chloride- Halides (except fluorine) of quaternary pyrrolidinium salts such as N-methylpyrrolidinium, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholine bromide Halides (except fluorine) of quaternary morpholinium salts such as onium, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide (except fluorine), N chloride -Methyl-N-benzylpiperidinium, N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide, N-methyl-N-butylpiperium Halides (except fluorine) of quaternary piperidinium salts such as pyridinium acetate, N-methyl-N-ethylpiperidinium iodide, and crown ethers. A quaternary ammonium salt is preferable, and tetrabutylammonium bromide, benzyltrimethylammonium chloride, or benzyltriethylammonium chloride is more preferable.

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

Regarding the use amount of the phase transfer catalyst, if it is too much relative to the compound (II), which is a raw material, there is a tendency that side reactions such as hydrolysis of esters or successive Michael reactions tend to become obvious, and from the viewpoint of cost, In other words, it is usually 5 times or less, preferably 2 times or less, and even more preferably 1 time or less with respect to the trifluorene compound (II). If the amount of the interphase transfer catalyst used is too small, the reaction rate tends to be significantly reduced. Therefore, the amount of the interphase transfer catalyst used is usually 0.01 times the mole or more of the raw material of the stilbene compound (II). It is preferably at least 0.1 times mole, more preferably at least 0.5 times mole.

<1.8.4.1.4 Solvent>

Step (iia) is preferably performed using a solvent.

Specific solvents that can be used include acetonitrile and propionitrile as the alkyl nitrile solvent, and acetone, methyl ethyl ketone, and methyl isobutyl ketone as the ketone solvent. As the ester solvent, Examples include methyl acetate, ethyl acetate, propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, methyl 3-methoxypropionate, 3- Linear esters such as methyl methoxypropionate, methyl lactate, ethyl lactate; cyclic esters such as γ-butyrolactone, caprolactone; ethylene glycol monomethyl ether acetate, ethylene glycol Ether esters such as alcohol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol-1-monomethyl ether acetate, propylene glycol-1-monoethyl ether acetate, and the like, and examples thereof include ether solvents Diethyl ether, tetrahydrofuran, 1,4-bis Alkane, methylcyclopentyl ether, third butyl methyl ether, and the like. Examples of the halogen-based solvent include 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane. Examples of the halogen-based aromatic hydrocarbon include chlorobenzene and 1,2-dichlorobenzene. Examples of the fluorene-based solvent include N, N-dimethylformamide and N, N, -dimethyl. Acetylamine and the like include fluorene-based solvents such as dimethyl fluorene and cyclobutane, and examples of cyclic aliphatic hydrocarbons include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Monocyclic aliphatic hydrocarbons; methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1, 2 3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, third butylcyclohexane, n-butylcyclohexane, isopropyl Butylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; Polycyclic aliphatic hydrocarbons such as decalin; n-pentane, n-hexane Non-cyclic aliphatic hydrocarbons such as alkane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Examples of the aromatic hydrocarbon include toluene, para-xylene, o-xylene, and meta-xylene. Examples of the aromatic heterocyclic ring include pyridine. Examples of the alcohol-based solvent include methanol, ethanol, isopropyl alcohol, N-butanol, tertiary butanol, hexanol, octanol, cyclohexanol and the like.

When R ³ is a methylene group, it is known that by using a solvent separated from the aqueous phase, side reactions such as the decomposition reaction of the trifluorene compound (II) can be suppressed. Furthermore, in the case where a solvent that sufficiently dissolves the compound III of the raw material (II) is used, the reaction tends to proceed well. Therefore, it is preferable to use a solvent whose solubility of the compound III of the raw material (II) is 0.5% by mass or more. It is more preferable to use a solvent having a solubility of 1.0% by mass or more, and more preferably to use a solvent having a solubility of 1.5% by mass or more. Specifically, a halogen-based aliphatic hydrocarbon, a halogen-based aromatic hydrocarbon, an aromatic hydrocarbon, or an ether-based solvent is preferred, and dichloromethane, chlorobenzene, chloroform, 1,2-dichlorobenzene, tetrahydrofuran, 1,4-two Alkane, or methylcyclopentyl ether.

These solvents may be used alone or in combination of two or more.

With regard to the amount of solvent used, the upper limit is not particularly limited. If the production efficiency of the target substance in each reactor is considered, it is usually used as 20 times as much as the compound (II) of the raw material. The volume amount is preferably an amount of 15 times the volume amount, and more preferably an amount of 10 times the volume amount. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent becomes worse, the stirring becomes difficult, and the progress of the reaction tends to be slow. Therefore, as the lower limit, the compound (II), which is a raw material, is generally used. An amount of 1 volume, preferably an amount of 2 volume, and further preferably an amount of 4 volume.

When R ³ is other than methylene, it is known that the solubility of the organic base and the trifluorene compound (II) has a large influence on the reaction rate. In order to ensure the solubility, it is preferable to use Solvents with a dielectric constant above a certain value. As a solvent for sufficiently dissolving the organic base and the trifluorene compound (II), an aromatic heterocyclic ring, an alkylnitrile-based solvent, a fluorene-amine-based solvent, and a fluorene-based solvent are preferable, and pyridine, acetonitrile, N, N -Dimethylformamide, N, N-dimethylacetamide, dimethylmethane, cyclobutane. These solvents may be used alone or in combination of two or more.

Regarding the amount of solvent used, the upper limit is not particularly limited. If the production efficiency of the target of each reactor is taken into consideration, it is usually 20 times the volume, preferably 15 times the volume. And more preferably an amount of 10 times the volume. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent becomes worse, the stirring becomes difficult, and the progress of the reaction tends to be slow. Therefore, as the lower limit, it is usually used as the raw material of the third compound (II) 1 The volume-by-volume amount is preferably an amount of 2-volumes, and more preferably an amount of 4-volumes.

<1.8.4.1.5 Reaction Form>

When the step (iia) is performed, the form of the reaction may be a batch reaction, a flow-through reaction, or a combination of these, and the form is not particularly limited.

Regarding the method of feeding the reaction reagent into the reactor in the case of batch type, when α, β-unsaturated ester (VI) is added at one time at the start of the reaction, α, β-unsaturated ester (VI) is higher The concentration is present, so that the polymerization reaction of side reactions easily proceeds. Therefore, it is preferable to add the α, β-unsaturated ester (VI) one after another in small amounts and multiple times after adding the stilbene compound (II), the phase transfer catalyst, the solvent, and the base.

<1.8.4.1.6 Reaction conditions>

In the step (iia), if the temperature is too low, a sufficient reaction rate cannot be obtained. On the other hand, if the temperature is too high, the polymerization reaction of α, β-unsaturated ester (VI) tends to proceed easily. Therefore, temperature management is important. . Therefore, as the reaction temperature, the lower limit is usually 0 ° C, preferably 10 ° C, and more preferably 15 ° C. On the other hand, the upper limit is usually 40 ° C, preferably 30 ° C, and more preferably 20 ° C.

With regard to the usual reaction time in step (iia), the lower limit is usually 30 minutes, preferably 1 hour, and further preferably 2 hours, and the upper limit is not particularly limited, and is usually 20 hours, preferably 10 hours, and further It is preferably 5 hours.

<1.8.4.1.7 Separation and purification of target>

After the reaction, the tertiary diester (1a) as a target can be removed from the reaction solution by filtering by-produced metal halides and residual inorganic bases, and then concentrating the solvent or adding A method of a poor solvent for the target substance, etc., is to separate and separate the tri-methylene diester (1a) as the target substance.

In addition, after the reaction is completed, acid water and a solvent in which the trimer diester (1a) as a target substance is soluble may be added to the reaction solution to perform extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent.

The solvent that can be used during extraction is not particularly limited as long as it dissolves the target tertiary diester (1a), and aromatic hydrocarbon compounds such as toluene and xylene, and dichloromethane can be preferably used. Or one or more halogen-based solvents such as chloroform and chloroform.

The tertiary diester (1a) obtained here can be directly used as a precursor of polyester, polyester carbonate raw material monomer, or polycarbonate raw material monomer, but it can also be used after purification. As the purification method, ordinary purification methods such as recrystallization, reprecipitation, extraction purification, and column chromatography can be used without limitation. Moreover, you may dissolve a trimethyl diester (1a) in an appropriate solvent, and may process with activated carbon. The solvent that can be used at this time is the same as the solvent that can be used during extraction.

<1.8.4.2 Step (iib): Manufacturing method using alkylation>

The trimethyl diester (1b) can be produced by a method of an alkylation reaction of the trimethyl compound (II) with an alkylating agent (VIIIb) and (VIIIc).

Wherein, R ¹ ~ R ⁹ the same line with the formula R (1) ¹ ~ R ⁹ in the meaning. X represents a radical. Examples of the leaving group include a halogen atom (excluding fluorine), a methanesulfonyl group, or a tosylsulfonyl group.

The alkylation reaction of amidines is well known. For example, 9,9-bis (bromohexyl) fluorene or 9,9-bis (iodohexyl) fluorene and other 9,9-bis (haloalkyl) fluorene (J. Org. Chem., 2010, 75, 2714.). Based on these findings, it is possible to synthesize a triester diester (1b) by using the killer compound (II) as a raw material.

Examples of the alkylating agent used in step (iib) include methyl chloroacetate, methyl bromoacetate, methyl iodoacetate, ethyl chloroacetate, ethyl bromoacetate, ethyl iodoacetate, and propyl chloroacetate. , N-butyl chloroacetate, third butyl chloroacetate, third butyl bromoacetate, third butyl iodoacetate, methyl 2-chloropropionate, methyl 2-bromopropionate, methyl 2-iodopropionate Esters, ethyl 2-chloropropionate, tertiary butyl 2-chloropropionate, tertiary butyl 2-bromopropionate, ethyl 2-bromopropionate, ethyl 2-iodopropionate, 3-chlorobutane Methyl ester, methyl 3-bromobutyrate, methyl 3-iodobutyrate, ethyl 3-chlorobutyrate, ethyl 3-chlorobutyrate, ethyl 3-iodobutyrate, 2-iodopropionate Alkyl alkanoates such as tributyl ester, aryl chloroacetates, phenyl bromoacetate, phenyl iodoacetate, 4-chloromethylbenzoate, 4-bromomethylbenzoate Esters, alkyl 4-halomethylbenzoates, ethyl 4-chloromethylbenzoate, ethyl 4-bromomethylbenzoate, methyl 3-chloromethylbenzoate, methyl 3-bromomethylbenzoate, etc. Wait.

<1.8.4.3 Production method of triamyl diaryl ester of general formula (1c) (production method of trimamyl diaryl ester compound (1c) after esterification reaction of triammonium diester compound (1))>

The tris-diaryl ester compound (1c) can be prepared through the step of synthesizing the tris-diester compound (1) (step (iia) or step (iib), and the subsequent ester with the diaryl carbonate (11a) It is produced by a method of an exchange reaction (step (iic)).

Wherein, R ¹ ~ R ¹⁰ the same line with the formula R (1) ¹ ~ R ¹⁰ in the meaning. Ar ¹ represents an aryl group having 4 to 10 carbon atoms which may be substituted.

<1.8.4.3.1 Method for producing trisaryldiaryl ester of general formula (1c) (manufacturing method of trisaryldiaryl ester compound (1c) using transesterification reaction)>

Ar ¹ is a triaryl diaryl ester compound (1c) which can be substituted with an aryl group having 4 to 10 carbon atoms. In the presence of a transesterification catalyst, according to the reaction shown in step (iic), (1) and diaryl carbonates (11a).

<1.8.4.3.1.1 Diaryl carbonates>

Examples of the diaryl carbonates used as a reaction reagent include diphenyl carbonate, xylyl carbonate, bis (chlorophenyl) carbonate, m-tolyl carbonate, dinaphthyl carbonate, and bis (biphenyl) carbonate. Wait. Among them, diphenyl carbonate, which is inexpensive and commercially available, is preferred. These diaryl carbonates may be used singly or in combination of two or more kinds.

Regarding the amount of diaryl carbonate used, the upper limit is not particularly limited with respect to the trimer diester (1) as a raw material. If the amount used is too large, the refining load after the reaction tends to increase, so it is usually three. The perylene diester is 20 times or less, preferably 10 times or less, and more preferably 5 times or less.

On the other hand, if the amount of the base used is too small, the following may be used as the tertiary diester (1) or intermediates of the raw material, as shown below. Therefore, as the lower limit, it is usually relative to the raw material. The tertiary diester (1) is 1 times mole or more, preferably 1.5 times mole or more, and further preferably 2 times mole or more.

Wherein, R ¹ ~ R ¹⁰ the same line with the formula R (1) ¹ ~ R ¹⁰ in the meaning. Ar ¹ represents an aryl group having 4 to 10 carbon atoms which may be substituted.

<1.8.4.3.1.2 Transesterification reaction catalyst>

Examples of the transesterification catalyst include tetrabutoxytitanium, tetraisobutoxytitanium, tetramethoxytitanium, tetraisopropoxytitanium, tetraethoxytitanium, and tetrakis (2-ethylhexyloxy). Titanium compounds such as titanium, tetrakis (octadecyloxy), titanium tetraphenoxy, titanium (IV) acetoacetone, titanium (IV) bis (ethylacetone) isopropoxy titanium; lithium carbonate, lithium Alkali metal compounds such as lithium butylamino, lithium acetoacetone, sodium phenoxide, potassium phenol; cadmium compounds such as cadmium acetoacetone, cadmium carbonate; zirconium compounds such as zirconium acetoacetone, zirconocene, etc. Lead compounds such as lead, lead, lead, carbonate, lead acetate, tetrabutyl lead, tetraphenyl lead, triphenyl lead, dimethoxy lead, diphenoxy lead, etc. Copper compounds such as copper acetone acetone, copper oleate, butyl copper, dimethoxy copper, and copper chloride; iron hydroxide, iron carbonate, triethoxy iron, trimethoxy iron, and triphenoxy iron Other iron compounds; zinc compounds such as zinc diacetamate acetone, zinc diethoxylate, dimethoxyzinc, diethoxyzinc, and diphenoxyzinc; di-n-butyltin oxide, diphenyltin oxide , Di-n-octyltin oxide, di-n-butyltin methoxide, di-n-butyltin diacrylate, di-n-butyltin dimethacrylate, di-n-butyltin dilaurate, tetramethoxytin, tetraphenoxytin, Butyl-1,3-diethoxylated stannoxanes, etc. Organic tin compounds; aluminum compounds such as aluminum acetate, aluminum methoxide, aluminum ethoxide, and aluminum phenoxide; vanadium compounds such as vanadium dichloride, vanadium trichloride, vanadium tetrachloride, and vanadium sulfate; phosphonium salts such as tetraphenylphenol rhenium, and the like. These may be used individually by 1 type, and may use 2 or more types together.

Among these, it is preferable to use a sulfonium salt, a lithium compound, a zirconium compound, an organic tin compound, or a titanium compound in terms of being industrially inexpensive and having an advantage in reaction operation. Among these, an organic tin compound or Titanium compounds.

Regarding the amount of the transesterification catalyst used, the upper limit is not particularly limited relative to the trimer diester (1) as a raw material. If the amount used is too large, the refining load after the reaction tends to increase, so it is usually 通常20 mol% or less, preferably 10 mol% or less, and further preferably 5 mol% or less.

On the other hand, if the amount of the transesterification reaction catalyst is too small, the reaction time may become too long. Therefore, as the lower limit, it is usually 0.1 mol% or more relative to the trimer diester of the raw material, preferably 0.5. Molar% or more, and more preferably 1 Molar% or more.

<1.8.4.3.1.3 Solvent>

In step (iic), a reaction solvent may also be used, but it is preferred that the reaction is performed without using the reaction solvent and using only the tertiary diester (1), the diaryl carbonate, and the transesterification reaction catalyst. However, the reaction solvent may be used in the case where the tertiary diester (1) and the diaryl carbonate of the raw material are solid at normal temperature and it is difficult to stir. In the case of using a reaction solvent, any kind can be used as long as it is a solvent which can dissolve and / or disperse the tertiary diesters (1), diaryl carbonates, and transesterification reaction catalysts of the above materials appropriately.

Specific solvents that can be used include acetonitrile and propionitrile as the alkyl nitrile solvent, and acetone, methyl ethyl ketone, and methyl isobutyl ketone as the ketone solvent, and ether solvents as the ketone solvent. , Including diethyl ether, tetrahydrofuran, 1,4-di Alkane, methylcyclopentyl ether, third butyl methyl ether, and the like. Examples of the halogen-based solvent include 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane. Examples of the halogen-based aromatic hydrocarbon include chlorobenzene and 1,2-dichlorobenzene. Examples of the fluorene-based solvent include N, N-dimethylformamide and N, N, -dimethyl. Acetylamine and the like include fluorene-based solvents such as dimethyl fluorene and cyclobutane. Examples of the cyclic aliphatic hydrocarbon include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. And other monocyclic aliphatic hydrocarbons; its derivatives are methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1 , 3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, third butylcyclohexane, n-butylcyclohexane, Isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; polycyclic aliphatic hydrocarbons such as decahydronaphthalene; n-pentane, Non-cyclic aliphatics such as n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Hydrocarbons, examples of aromatic hydrocarbons include toluene, para-xylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3 , 4-tetrahydronaphthalene, etc. Examples of the aromatic heterocyclic ring include pyridine.

This reaction is preferably carried out at a high temperature of generally 100 ° C or higher. Therefore, among the above solvents, solvents having a boiling point of 100 ° C or higher, that is, chlorobenzene, 1,2-dichlorobenzene, trichlorobenzene, toluene, p- Xylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, tetralin, decalin, N , N-dimethylformamide, N, N-dimethylacetamide, dimethylmethylene, or cyclobutane, the trimethyl diester (1) of the raw material can be better dissolved, and From the viewpoint that the boiling point is 130 ° C or higher and the reaction can be performed at a higher temperature, 1,2-dichlorobenzene, xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene are particularly preferred. Methylbenzene, or tetralin, decalin.

These solvents may be used alone or in combination of two or more.

With regard to the amount of solvent used, the upper limit is not particularly limited. If the production efficiency of the target substance in each reactor is considered, 15 times the volume, preferably 10 times, of the tri-methylene diester (1), which is the raw material, is usually used. A volume amount, more preferably an amount of 5 times the volume amount. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent becomes worse, the stirring becomes difficult, and the progress of the reaction tends to be slow. Therefore, as the lower limit, a trimer diester (1), which is a raw material, is usually used. The amount is 1 times the volume, preferably 2 times the volume, and more preferably 4 times the volume.

<1.8.4.3.1.4 Reaction Form>

When the step (iic) is performed, the form of the reaction may be a batch reaction, a flow-through reaction, or a combination of these, and the form is not particularly limited.

<1.8.4.3.1.5 Reaction conditions>

In the step (iic), if the temperature is too low, a sufficient reaction rate may not be obtained. Therefore, the lower limit is usually 50 ° C, preferably 70 ° C, and more preferably 100 ° C. On the other hand, the upper limit is implemented at usually 250 ° C, preferably 200 ° C, and more preferably 180 ° C.

Regarding the usual reaction time in step (iic), the lower limit is usually 1 hour, preferably 2 hours, and further preferably 3 hours, and the upper limit is not particularly limited, but is usually 30 hours, preferably 20 hours, and further It is preferably 10 hours.

In step (iic), in order to shift the equilibrium to the product side, the reaction may be performed while distilling off by-products under reduced pressure. The pressure in the case of reduced 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 degree of reduced pressure is too high, even diaryl carbonates used as reagents may also sublime. Therefore, it is usually performed at 0.1 kPa or more, preferably 0.5 kPa or more, and more preferably 1.0 kPa or more.

<1.8.4.3.1.6 Separation and purification of target>

After the completion of the reaction, the tris (diaryl) ester (1c) as the target can be isolated by adding a poor solvent to the reaction solution to precipitate the tris (tri) diaryl (1c) as the target.

In addition, after the reaction is completed, a trisaryldiaryl ester (1c), which is a target substance, may be added to the reaction solution for extraction with a soluble solvent and water. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent.

The obtained stilbene diaryl ester (1c) can also be directly used for polymerization as a polycarbonate raw material containing polyester carbonate or a polyester raw material. As the purification method, ordinary purification methods such as recrystallization, reprecipitation, extraction purification, and column chromatography can be used without limitation.

<2 oligomeric fluorene diester composition>

The oligomeric fluorene diester composition of the present invention comprises the above-mentioned trifluorene diester, and a difluorene diester. By including not only the tri-fluorene diester but also the di-fluorene diester, there is a tendency that the heat resistance or optical characteristics can be easily adjusted to a desired one.

<2.1 Dimethyldiester>

The difluorene diester contained in the oligomeric fluorene diester composition of the present invention includes two fluorene units b which may have a substituent, and the carbon atoms at the 9-position of the fluorene unit b are directly bonded to each other or may have a substituent The alkylene group, the alkylene group which may have a substituent, or the alkylene group which may have a substituent are chain-bonded.

As the fluorene unit b, those exemplified as the fluorene unit a can be preferably used. The fluorene unit b in the difluorene diester contained in the oligomeric fluorene diester composition may be the same as or different from the fluorene unit a in the trifluorene diester included.

As the alkylene group of the bonded fluorene unit b, those exemplified as the alkylene group of the bonded fluorene unit a can be preferably used. The alkylene group of the bond unit b in the diester of the oligomeric diester composition may be the same as or different from the alkylene group of the bond unit a of the tertiary diester.

Similarly, as the arylene group of the bonded fluorene unit b, the exemplified as the arylene group of the bonded fluorene unit a can be preferably used. The arylene group of the bonded fluorene unit b in the dimer diester contained in the oligomeric fluorene diester composition may be the same as or different from the arylene group of the bonded fluorene unit a in the trimer diester included.

Furthermore, as the aralkyl group of the bonded fluorene unit b, the exemplified as the aralkyl group of the bonded fluorene unit a can be preferably used. The aralkyl group of the bonded fluorene unit b in the difluorene diester contained in the oligomeric fluorene diester composition may be the same as the aralkyl group of the bonded fluorene unit a in the trimethyl diester included different.

The difluorene diester contained in the oligomeric fluorene diester composition of the present invention can be set as follows: the substituents α ³ and α ⁴ are respectively bonded to the carbon atom at the 9th position of the fluorene unit b at the two ends, An ester group is bonded to the substituents α ³ and α ⁴ . In this case, α ³ and α ⁴ may be the same or different. In addition, the substituents α ³ and α ⁴ may include a direct bond, that is, an ester group is directly bonded to the carbon atom at the 9-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 the ester group, those exemplified as the ester group in the trimethyl diester can be preferably used.

<2.2 Specific Structure of Dimethyldiester>

As the difluorene diester contained in the oligomeric fluorene diester composition of the present invention, specifically, those represented by the following general formula (2) can be preferably used.

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} independently an alkylene group having 1 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, or an alkylene group having 6 to 10 carbon atoms that can be substituted, R ⁴ to R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, a fluorenyl group having 1 to 10 carbon atoms that can be substituted, and Substituted fluorenyloxy group having 1 to 10 carbon atoms, alkoxyl group having 1 to 10 carbon atoms that can be substituted, aryloxy group having 1 to 10 carbon atoms that can be substituted, amine group that can be substituted, substituted A sulfur atom, a halogen atom, a nitro group, or a cyano group. Among them, at least two adjacent groups in 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, R ⁴ to R ⁹ each having two in formula (2) may be the same or different. Similarly, two R ¹⁰ in formula (2) may be the same or different.

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

<2.3 Specific examples of difluorene diesters>

Specific examples of the difluorene diester contained in the oligomeric fluorene diester composition of the present invention include a structure shown in the following [I] group.

[Chemical 57]

<2.4 Physical properties of dioxin diester>

The physical property value of the difluorene diester contained in the oligomeric fluorene diester composition of the present invention is not particularly limited, but it is preferably one that satisfies the physical property values exemplified below.

The decomposition temperature of the diester of the present invention measured under a nitrogen environment is preferably 250 ° C or higher, more preferably 270 ° C or higher, even more preferably 290 ° C or higher, and usually 300 ° C or lower. The difluorene diester of the present invention has a rigid structure due to the laminated structure of the fluorene ring, and therefore has decomposition. The temperature tends to satisfy the above range. When the decomposition temperature satisfies the above range as described above, the thermal stability of polyesters and polycarbonates obtained from diesters tends to be improved. The decomposition temperature can be measured by, for example, TG-DTA.

Furthermore, the melting point (m.p.) of the diester of the present invention is preferably 100 ° C or higher, more preferably 120 ° C or higher, even more preferably 140 ° C or higher, and usually 150 ° C or lower. The difluorene diester of the present invention has a rigid structure due to the laminated structure of the fluorene ring, and therefore the melting point tends to satisfy the above range. When the melting point satisfies the above range as described above, the thermal stability of polyesters and polycarbonates obtained from diesters tends to be improved. The melting point can be measured by, for example, TG-DTA.

<2.5 Composition of oligomeric fluorene diester composition>

Regarding the content ratio of the tertiary diester contained in the oligomeric fluorene diester composition of the present invention, there is no particular limitation. From the viewpoint of improving heat resistance and obtaining the required optical characteristics in a smaller amount, With respect to the total mass of the composition, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 3% by mass or more, and even more preferably 5% by mass or more. It is usually 30% by mass or less.

On the other hand, there is no particular limitation on the content ratio of the dimer diester contained in the oligomeric dimer diester composition. From the viewpoint of adjusting the flexibility and optical characteristics, it is more than the total mass of the composition. It is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 1% by mass or more, still more preferably 3% by mass or more, even more preferably 5% by mass or more, and from the viewpoint of improving heat resistance. In other words, it is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

The content ratios of the di- and di-diesters contained in the oligomeric fluorene diester composition are not particularly limited. From the viewpoint of adjusting the flexibility and optical characteristics, the content contained in the composition is not limited. The molar ratio of the diesters to diesters (the die number of diesters / the die number of diesters) is preferably 0.001 or more, more preferably 0.003 or more, and still more preferably 0.01 or more , And more preferably 0.03 or more, particularly preferably 0.05 or more, and it also improves heat resistance From the standpoint of sex, it is preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.3 or less.

The molar number of the di- or di-tri-ester contained in the oligomeric di-diester composition is, for example, an area% that can be analyzed by HPLC (high performance liquid chromatography), and a calibration curve is used. And make estimates.

<3 resin composition>

The resin composition of the present invention is a polymer containing a trivalent difluoride as a repeating unit.

As described above, the resin composition of the present invention may contain, in addition to a polymer having divalent trifluorene as a repeating unit, other polymers described below, and may also contain additives. In addition, the resin composition of the present invention may be made of a polymer having divalent trifluorene as a repeating unit.

<3.1 Three Price of Two Price>

The polymer contained in the resin composition of the present invention has divalent trifluorene as a repeating unit. As described above, by having a trivalent trifluorene as a repeating unit, there is a tendency that a small amount of the trifluorene can be used to obtain the required optical characteristics, and good heat resistance can be developed.

The polymer contained in the resin composition of the present invention may further have a divalent difluorene as a repeating unit as described below. There are cases in which both tritium and dipyridine are collectively referred to as oligomeric tritium.

The divalent trifluorene is a product of 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 carbon atoms at the 9th position of the fluorene unit a pass through each other The alkylene group which may have a substituent, the alkylene group which may have a substituent, or the alkylene group which may have a substituent are chain-bonded.

As the fluorene unit a, those exemplified as the fluorene unit a as a trifluorene diester can be preferably used.

Similarly, as the alkylene group of the bonded fluorene unit a, it can be preferably used as The ester bond is exemplified by the alkylene group of the fluorene unit a. In addition, as the arylene group of the bonded fluorene unit a, the exemplified as the arylene group of the bonded fluorene unit a of the trifluorene diester can be preferably used. Furthermore, as the aralkyl group of the bonded fluorene unit a, the aralkyl group exemplified as the bonded fluorene unit a of the trifluorene diester can be preferably used.

Regarding the above-mentioned divalent trisene, the substituents α ¹ and α ^{2 may be} respectively bonded to the carbon atoms at the 9th position of the tertiary unit a in the three tertiary units a, and the substituent α ¹ And α ^{2 is} a divalent basis. In this case, α ¹ and α ² may be the same or different. The substituents α ¹ and α ² may include a direct bond, that is, a carbon atom at the 9-position of the fluorene unit a may be a divalent group. As the substituents α ¹ and α ² , those exemplified as the substituents α ¹ and α ² in the trimethyl diester can be preferably used.

Especially when the carbon atom at the 9th position of the fluorene unit a at both ends is a divalent radical, or when the carbon atom at the 9th position of the fluorene unit a at both ends is substituted, respectively When the radicals α ¹ and α ^{2 are} bivalent radicals, and when the number of carbons of at least one of α ¹ and α ² is 2 or more, the fluorene ring (fluorene unit a) is aligned substantially perpendicular to the main chain. Therefore, even if the ratio of the divalent oligomeric fluorene in the resin composition is small, it tends to exhibit reverse wavelength dispersion. In the latter case, from the same viewpoint, it is preferable that both α ¹ and α ² have a carbon number of 2 or more. On the other hand, when α ¹ and α ² of the carbon atoms at the 9-position of the fluorene unit a, which are respectively bonded to both ends, are set to a divalent base, and both α ¹ and α ² are set to a carbon number of 1 (I.e., a methylene group that may be substituted), the fluorene ring (fluorene unit a) is not aligned substantially vertically to the main chain but is aligned with a large inclination. Therefore, even if the The ratio of the divalent oligomeric fluorene changes over a wide range, and it is easy to become a plane dispersion with a small difference in wideband phase difference.

As described above, the resin composition of the present invention contains a polymer having a repeating unit in which a carbon atom at the 9-position of three fluorene units a is connected to each other by a specific carbon-carbon bond, whereby the source can be obtained more efficiently. Optical characteristics of self-loop.

As the trivalent divalent compound, specifically, the following general formula (11) can be preferably used: Presenter.

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, and R ^3a and R ^3b are each independently an alkylene group having 1 to 10 carbon atoms which may be substituted. R ⁴ to R ⁹ are each independently a hydrogen atom, and a substituted carbon number 1 is a aryl group having ⁴ to 10 carbon atoms which may be substituted, or an aralkyl group having 6 to 10 carbon atoms which may be substituted. ~ 10 alkyl groups, aryl groups with 4 to 10 carbon atoms that can be substituted, fluorenyl groups with 1 to 10 carbon atoms that can be substituted, fluorenyloxy groups with 1 to 10 carbon atoms that can be substituted, and An alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 1 to 10 carbon atoms that can be substituted, an amine group that can be substituted, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. Among them, at least two adjacent groups in 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 the same or different. In addition, each of R ⁴ to R ⁹ in Formula (11) may be the same or different.

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

<3.2 2nd Price 2nd 茀>

The polymer in the resin composition of the present invention may further have divalent difluorene as a repeating unit. Since the divalent trifluoride is contained in addition to the divalent trifluoride, there is a tendency that the heat resistance or optical characteristics can be easily adjusted to a desired one.

The bivalent difluorene system includes two fluorene units b which may have a substituent, and the fluorene unit b-9 The carbon atoms at the y position are directly bonded to each other, or the carbon atoms at the 9 position of the fluorene unit b are mutually via an alkylene group which may have a substituent, an alkylene group which may have a substituent, or an alkylene group which may have a substituent An aralkyl group is bonded in a chain.

As the fluorene unit b, those exemplified as the fluorene unit b as a difluorene diester can be preferably used.

Similarly, as the alkylene group of the bonded fluorene unit b, those exemplified as the alkylene group of the bonded fluorene unit b of a difluorene diester can be preferably used. In addition, as the arylene group of the bonded fluorene unit b, the exemplified as the aryl group of the bonded fluorene unit b of a difluorene diester can be preferably used. Further, as the aralkyl group of the bonded fluorene unit b, an aralkyl group exemplified as the bonded fluorene unit b of a difluorene diester can be preferably used.

Regarding the above-mentioned divalent difluorene, the substituents α ³ and α ^{4 may be} respectively bonded to the carbon atom at the 9th position of the fluorene unit b at both ends of the position, and the substituents α ³ and α ^{4 may} be made divalent. The base. In this case, α ³ and α ⁴ may be the same or different. In addition, the substituents α ³ and α ⁴ may include a direct bond, that is, a carbon atom at the 9-position of the fluorene unit b may be a divalent group. As the substituents α ³ and α ⁴ , those exemplified as the substituents α ³ and α ⁴ in the diester diester can be preferably used.

Especially when the carbon atom at the 9th position of the fluorene unit b at both ends is a divalent base, or when the carbon atom at the 9th position of the fluorene unit b at both ends is substituted When the bases α ³ and α ^{4 are} bivalent bases, and the carbon number of at least one of α ³ and α ⁴ is 2 or more, the fluorene ring (fluorene unit b) is aligned substantially vertically to the main chain. Therefore, even if the ratio of the divalent oligomeric fluorene in the resin composition is small, it tends to easily exhibit reverse wavelength dispersion. In the latter case, from the same viewpoint, it is preferable to set both α ³ and α ⁴ to a carbon number of 2 or more. On the other hand, when α ³ and α ⁴ of the carbon atoms at the 9th position of the fluorene unit b bonded to the both ends are respectively set to a divalent base, and both α ³ and α ⁴ are set to a carbon number of 1 (I.e., a methylene group that may be substituted), the fluorene ring (fluorene unit b) is not aligned substantially vertically to the main chain but is aligned with a large inclination. Therefore, even if the The ratio of the divalent oligomeric fluorene changes over a wide range, and it is easy to become a plane dispersion with a small difference in wideband phase difference.

As the above-mentioned divalent difluorene, specifically, those represented by the following general formula (21) can be preferably used.

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, and R ^{3 is} independently an alkylene group having 1 to 10 carbon atoms which may be substituted. Substituted arylene groups with 4 to 10 carbon atoms, or substituted aralkyl groups with 6 to 10 carbon atoms, R ⁴ to R ⁹ are each independently a hydrogen atom, and 1 to 10 carbon atoms can be substituted. Alkyl, aryl with 4 to 10 carbons that can be substituted, fluorenyl with 1 to 10 carbons that can be substituted, fluorenyl with 1 to 10 carbons that can be substituted, 1 with carbons that can be substituted An alkoxy group of ~ 10, an aryloxy group having 1 to 10 carbon atoms that may be substituted, an amine group that may be substituted, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. Among them, at least two adjacent groups in R ⁴ to R ⁹ may be bonded to each other to form a ring.

As R ¹ to R ⁹ in the above formula (21), those exemplified as R ¹ to R ⁹ in the above formula (2) can be preferably used.

Furthermore, R ⁴ to R ⁹ each having two in formula (21) may be the same or different.

<3.3 polymer>

The polymer contained in the resin composition of the present invention has a trivalent difluoride as a repeating unit. For example, a polymer in which trivalent trivalent divalents are connected to each other by an arbitrary linking group can be mentioned. The polymer may be a copolymer having divalent difluorene or any repeating unit other than these.

<3.4 link base>

The specific structure of the linking group that can be used in the above polymer is listed below, and is not limited thereto. Examples include the linking groups shown in the following [J] group.

(In each linking group shown in the above-mentioned [J] group, Z represents a portion connected by a repeating unit, and Y represents a linking portion with another linking group, or a portion connected by any structural unit that links the linking groups to each other) It is also possible to use a plurality of these linking bases in combination. When the linking group is asymmetric, the linking group may be linked to the repeating unit in any orientation. Among these, preferred are the linking groups represented by the following [K] group of polyesters, polycarbonates, and polyester carbonates that have excellent balance between heat resistance and melt processability or mechanical strength.

In each linking group shown in the above-mentioned [K] group, Z represents a portion to which a repeating unit is linked.

The linking group may be used singly or in combination.

As a polymer in which repeating units are connected by a linking group, specifically, Examples: Polyolefins, polyesters, polycarbonates, polyamides, polyimides, polyurethanes, epoxy resins, polyacrylates, polymethacrylates, or polymers containing polyfluorene and The polymer used in combination is preferably a polymer containing polyolefin, polyester, polycarbonate, epoxy resin, or polyacrylate, which is generally highly transparent, and particularly preferably containing heat resistance and melt processability, or A polymer of polyester or polycarbonate having excellent balance of mechanical strength is particularly preferably a polymer containing polycarbonate which is generally excellent in heat resistance or chemical resistance.

When a polymer using a plurality of linking groups is produced, the combination of the linking groups is not particularly limited, and examples thereof include a polymer using a carbonate structure and an ester structure as a linking group, and a carbonate structure and an amine in combination. Polymers having a urethane structure as a linking group and polymers using an ester structure and amidine as a linking group are preferably exemplified by polymers in which a carbonate structure and an ester structure are used as a linking group. Here, as specific examples of a polymer in which a plurality of types of linking groups are used in combination, polyester carbonate, polyurethane having a carbonate bond, polyester amidamine, polyester amine, etc. Among them, polyester carbonates having excellent balance between heat resistance and melt processability or mechanical strength are preferred. In this specification, a polymer having a carbonate bond is referred to as a polycarbonate. In addition to a polymer having only a carbonate bond as a linking group, a polyester carbonate (a polymer having an ester bond and a carbonate bond) is also included. ), A polyurethane having a carbonate bond, and the like. Here, the ratio of the carbonate bond in the polymer containing polycarbonate may be an arbitrary value. In order to impart the resin composition with excellent properties such as heat resistance and chemical resistance, the carbonate bond is provided. The ratio of the bonds is preferably a certain ratio or more. The mole fraction of the carbonate bonds in all the linking groups is preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, and even more preferably 70%. Above, and usually below 100%.

<3.5 copolymer>

The polymer having divalent trifluorene as a repeating unit may be a copolymer further containing an arbitrary divalent trivalent organic group (except for the trivalent difluoride and the divalent difluorene) as the repeating unit. In this case, it is preferable that the repeating units are connected to each other by the above-mentioned linking group. By.

Among the copolymers, as an arbitrary divalent organic group that can be used in combination with the trivalent trivalent, from the viewpoint of controlling the range of optical properties and physical properties necessary for the resin composition, the following can be preferably used: A divalent organic group represented by the general formula (3). In this case, a divalent organic group other than the divalent organic group represented by the general formula (3) may be used in combination as an arbitrary divalent organic group.

In the formula, R ²⁰ represents an alkylene group having 2 to 20 carbon atoms that can be substituted, an alkylene group having 4 to 20 carbon atoms that can be substituted, an alkylene ether group having 2 to 100 carbon atoms that can be substituted, An organic group having an alicyclic structure having 4 to 20 carbon atoms that can be substituted or an organic group having a heterocyclic structure with 4 to 20 carbon atoms that can be substituted.

When the polymer contains a divalent organic group represented by the general formula (3), in addition to exerting a function of imparting positive refractive index anisotropy to the resin composition, there is also a tendency that the phase difference can be reduced. Optical properties such as wavelength dispersion and photoelasticity, or various resin properties such as mechanical strength, heat resistance, and melt processability are controlled to a preferable range, and the properties of the resin composition can be arbitrarily controlled.

Furthermore, it is known that a resin composition which does not have an aromatic ring vertically aligned with the main chain, or has the above-mentioned aromatic ring, and whose proportion is small in the whole, generally exhibits positive refractive index anisotropy. Because it is a repeating unit of a divalent organic group represented by the general formula (3) above, except that the side chain has an aromatic ring, all of them exhibit a structure with positive refractive index anisotropy. The divalent organic group resin composition represented by the general formula (3) exhibits positive refractive index anisotropy.

<3.6 Specific Examples of Organic Groups>

As described above, R ²⁰ in the general formula (3) represents an alkylene group having 2 to 20 carbon atoms that can be substituted, an alkylene group having 4 to 20 carbon atoms that can be substituted, and 2 to 20 carbon atoms that can be substituted. An alkylene ether group of 100, an organic group having an alicyclic structure with 4 to 20 carbon atoms that can be substituted or an organic group having a heterocyclic structure with 4 to 20 carbon atoms that can be substituted.

The specific structure of the "alkylene group having 2 to 20 carbon atoms which can be substituted" is listed below, and is not limited to these. Examples include: ethylene, n-propyl, n-butyl, n-pentyl, Straight-chain alkylene groups such as n-hexyl; 1-methyl-ethyl, 2-methyl-ethyl, 1-ethyl-ethyl, 2-ethyl-ethyl, 1-methyl-propyl, 2-Methenyl, 2,2-Dimethylbutanyl, 3-Methylbutanyl and the like include an alkylene group having a side chain. The carbon number is preferably 2 or more and 12 or less, and more preferably 6 or less. Among these, a linear alkylene group represented by the following general formula (5), which has appropriate hydrophobicity and flexibility and tends to impart a low photoelastic coefficient, is preferred.

(In the formula, R ^2-11 represents a linear alkylene group having 0 to 18 carbon atoms which may be substituted.)

The specific structure of the "linear alkylene group having 0 to 18 carbon atoms which can be substituted" is listed below, and is not limited to these. Examples include: ethylene, n-propyl, n-butyl, and n-butyl Pentyl, hexyl, etc. The carbon number is preferably 2 or more, more preferably 10 or less, and even more preferably 4 or less.

The specific structure of the "arylene having 4 to 20 carbon atoms which can be substituted" is listed below, and is not limited to these. Examples include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, etc. phenylene; 1,5-alkylene, 2,6-naphthyl, etc .; 2-phenylene, 2,4-phenylene Heteroaryl groups such as thienyl and 2,4-furanyl. The carbon number is preferably 4 or more and 8 or less, and more preferably 6 or less. Among these, 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene is preferable from a viewpoint that it can be obtained industrially inexpensively.

As "substitutable alkylene group with 2 to 20 carbon atoms", "substitutable linear alkylene group with 0 to 18 carbon atoms" and "substitutable alkylene group with 4 to 20 carbon atoms that can be substituted" "The substituents which may be included are: halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom); alkyl groups having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.) ; Alkoxy groups with 1 to 10 carbons (for example, methoxy, ethoxy, etc.); Alkyl groups with 1 to 10 carbons (for example, ethyl fluorenyl, benzyl, etc.); 1 to 10 carbons Hydrazone (for example, acetamido, benzamido, etc.); nitro; cyano; may have a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), carbon number Alkyl groups of 1 to 10 (e.g. methylethyl, isopropyl, etc.), alkoxy groups of 1 to 10 carbons (e.g., methoxy, ethoxy, etc.), and fluorenyl groups of 1 to 10 carbons (E.g., ethylamido, benzamidine, etc.), 1 to 10 carbon atoms (for example, ethylamido, benzamidine, etc.), 1 to 3 of nitro, cyano, etc. An aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, etc.) as a substituent. The number of these substituents is not particularly limited, but is preferably 1-3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

Specific examples of the alkylene group having a substituent include phenylethynyl, 1-phenylethynyl, 1-cyclohexylethynyl, 1,1,2,2-tetrafluoroethynyl and the like.

Specific examples of the arylene group having a substituent include 2-methyl-1,4-phenylene, 5-methyl-1,3-phenylene, and 2,5-dimethyl-1 1,4-phenylene, 2-methoxy-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2,5-dimethoxy-1,4-phenylene Phenyl, 2,3,5,6-tetrafluoro-1,4-phenylene, etc. are substituted for arylene.

The specific structure of the "arylene group having 6 to 20 carbon atoms which can be substituted" is listed below, and is not limited to these. Examples include the alkylene group shown in the following [L] group.

The carbon number is preferably 6 or more, 10 or less, and more preferably 8 or less. Among these, from the viewpoint of industrially available inexpensiveness, it is preferably o-xylylene, m-xylylene, or p-xylylene.

Examples of the substituent which the "arylene group having 6 to 20 carbon atoms which may be substituted" may have: a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); a carbon atom having 1 to 10 carbon atoms; Alkyl (for example, methyl, ethyl, isopropyl, etc.); alkoxy (for example, methoxy, ethoxy, etc.) having 1 to 10 carbons; fluorenyl (for example, Ethanoyl, benzamidine, etc.); amidino groups having 1 to 10 carbon atoms (for example, acetoamino, benzamidine, etc.); nitro; cyano; may have a halogen atom selected (for example , Fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.), and alkoxy group having 1 to 10 carbon atoms (for example, methyl (Oxy, ethoxy, etc.), fluorenyl groups having 1 to 10 carbon atoms (for example, ethenyl, benzamidine, etc.), fluorenyl groups having 1 to 10 carbon atoms (for example, acetamido, benzyl) Sulfonylamino groups, etc.), aryl groups having 1 to 3 substituents such as nitro and cyano groups, and aryl groups having 6 to 10 carbon atoms (for example, phenyl, naphthyl, etc.). The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

The so-called "substitutable alkylene ether group having 2 to 100 carbon atoms" is a divalent group having one or more alkylene groups and etheric oxygen atoms. Its carbon number is preferably 4 or more, more preferably 6 or more, still more preferably 60 or less, more preferably 50 or less, even more preferably 40 or less, and even more preferably 30 or less. More specifically, the following formula (7):

( ^Wherein R ^2-13 represents an alkylene group having 2 to 10 carbon atoms which can be substituted, and p is an integer of 1 to 40), or the following general formula (8)

( ^Wherein R ^2-14 represents an alkylene group having 2 to 10 carbon atoms which can be substituted, and R ^2-15 represents an alkylene group having 12 to 30 carbon atoms which can be substituted).

In the general formula (7) and the general formula (8), R ^2-13 and R ^2-14 represent an alkylene group having 2 to 10 carbon atoms which may be substituted. Its specific structure is enumerated below, and is not limited to these. Examples include straight-chain alkylene groups such as ethylene, n-propyl, n-butyl, n-pentyl, and n-hexyl; 1-form Ethylidene, 2-methylidene, 1-ethylidene, 2-ethylidene, 1-methylidene, 2-methylidene, 2,2-dimethyl An alkylene group including a side chain (here, the numerical value of the substitution position is set to be attached from a carbon on the terminal side) and the like, such as propylene and 3-methyl propyl.

The number of carbon atoms is preferably 2 or more, 8 or less, and more preferably 4 or less.

Examples of the substituent which the "alkylene group having 2 to 100 carbon atoms which can be substituted" and the alkylene group having 2 to 10 carbon atoms which can be substituted include a halogen atom (for example, a fluorine atom). , Chlorine atom, bromine atom, iodine atom); alkyl groups having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.); alkoxy groups having 1 to 10 carbon atoms (for example, methoxy, Ethoxy, etc.); fluorenyl groups having 1 to 10 carbon atoms (for example, acetamyl, benzamidine, etc.); fluorenyl groups having 1 to 10 carbon atoms (for example, acetamidine, benzamidine) Etc.); nitro, cyano; may have a halogen selected from (For example, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.), alkoxy group having 1 to 10 carbon atoms ( For example, methoxy, ethoxy, etc.), fluorenyl groups having 1 to 10 carbons (for example, ethenyl, benzamidine, etc.), fluorenyl groups having 1 to 10 carbons (for example, acetamido) , Benzamidine amino group, etc.), aryl groups having 6 to 10 carbon atoms (for example, phenyl, naphthyl, etc.) having 1 to 3 substituents such as nitro and cyano. The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

Specific examples of the alkylene group having a substituent include phenylethynyl, 1-phenylethynyl, 1-cyclohexylethynyl, 1,1,2,2-tetrafluoroethynyl and the like.

Among these R ^2-13 and R ^2-14 , straight chain alkylene is preferred because it does not have an asymmetry point and the quality control of the monomer is easy. It is more preferably industrially inexpensive and can be introduced. Ethylene which imparts softness and water absorption.

In the general formula (7), p is an integer of 1 to 40, preferably 1 or more, more preferably 2 or more, still more preferably 30 or less, and even more preferably 20 or less.

In the general formula (8), R ^2-15 represents an arylene group having 12 to 30 carbon atoms which may be substituted. The specific structure is listed below, and is not limited to these. From the viewpoint of improving the glass transition temperature of the resin composition, it is preferable to mention Nobuyoshi as shown in the following [M] group. base.

Examples of the substituent which the "arylene group having 12 to 30 carbon atoms which may be substituted" may have: a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); an alkane having 1 to 10 carbon atoms (For example, methyl, ethyl, isopropyl, etc.); alkoxy (for example, methoxy, ethoxy, etc.) having 1 to 10 carbons; fluorenyl (for example, ethyl, 1 to 10) Fluorenyl group, benzamidine group, etc.); fluorenylamino group having 1 to 10 carbon atoms (for example, acetamidine group, benzamidine group, etc.); nitro group; cyano group; may have a halogen atom (for example, Fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.), alkoxy group having 1 to 10 carbon atoms (for example, methoxy Group, ethoxy group, etc.), fluorenyl group having 1 to 10 carbon atoms (for example, ethenyl benzamidine group, etc.), fluorenyl group having 1 to 10 carbon atoms (for example, acetamidine group, benzamidine group) Aryl groups such as nitro, cyano and the like having 1 to 3 substituents and 6 to 10 carbon atoms (for example, phenyl, naphthyl, etc.). The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

The specific structure of the formula (7) is listed below, and is not limited thereto, and examples thereof include an alkylene ether group represented by the following [N] group

(In the above [N] group, the diastereomeric structure may be any diastereomer or a mixture of diastereomers).

The specific structure of the formula (8) is listed below, and is not limited to these. Examples include alkylene ether groups represented by the following [O] group.

(In the above [O] group, regarding the structure which can be a diastereomer, it can be any diastereomer or a mixture of diastereomers).

The specific structure of the "organic group having an alicyclic structure with 4 to 20 carbon atoms that can be substituted or the heterocyclic structure with 4 to 20 carbon atoms that can be substituted" is listed below and is not limited to Among these, in terms of the tendency to increase the glass transition temperature and reduce the photoelastic coefficient, a preferable example is that the alicyclic structure or the heterocyclic structure at any two places as shown in the following [P] group has An organic group that is a linear or side chain alkylene bond.

(The substitution positions of the two bonding bonds in each ring structure shown in the above-mentioned [P] group are arbitrary, and the two bonding bonds may be substituted on the same carbon). Here, the so-called bonding bond is a direct bond, or a linear or side chain-shaped alkylene having 1 to 5 carbon atoms, and the lengths of the two bonding bonds may be different. The preferred bond is a direct bond, or a methylene group, with a lower reduction in glass transition temperature.

Examples of the substituent which the "organic group having an alicyclic structure having 4 to 20 carbon atoms that can be substituted or an organic group having a heterocyclic structure having 4 to 20 carbon atoms that can be substituted" may include: a halogen atom ( For example, fluorine atom, chlorine atom, bromine atom, iodine atom); alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.); alkoxy group having 1 to 10 carbon atoms (for example, Methoxy, ethoxy, etc.); fluorenyl groups having 1 to 10 carbons (for example, ethenyl, benzamidine, etc.); fluorenyl groups having 1 to 10 carbons (for example, acetamido, benzene) Methylamino, amino, etc.); nitro; cyano; may have a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (for example, methyl , Ethyl, isopropyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, etc.) having 1 to 10 carbon atoms, and fluorenyl groups (e.g., ethenyl, benzamidine, etc.) having 1 to 10 carbon atoms Groups), fluorenylamino groups with 1 to 10 carbon atoms (e.g., acetamidoamine, benzamidine amino groups, etc.), aryl groups with 1 to 3 carbon atoms such as nitro and cyano groups, and aromatic groups with 6 to 10 carbon atoms (E.g., phenyl, naphthyl, etc.). The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

Preferred specific structures of the "organic group having an alicyclic structure with 4 to 20 carbon atoms that can be substituted or the heterocyclic structure with 4 to 20 carbon atoms that can be substituted" are enumerated below, and Without being limited to these, the following general formula (4) which tends to give higher transparency and glass transition temperature, water absorption, birefringence, and lower photoelasticity coefficient can be listed.

The base represented by the following general formula (6) [Chem. 72]

( ^Wherein R ^2-12 represents a cycloalkylene group having 4 to 20 carbon atoms which may be substituted), or the following general formula (9)

(In the formula, R ^2-16 represents a group having an acetal ring having 2 to 20 carbon atoms which may be substituted.)

In the general formula (6), R ^2-12 represents a cycloalkylene group having 4 to 20 carbon atoms which may be substituted. The specific structure is listed below, and it is not limited to these. In terms of the tendency to increase the glass transition temperature and reduce the photoelastic coefficient, it can be preferably listed as follows: [Q] Cycloalkylene

(In the above [Q] group, the diastereomeric structure may be any diastereomer or a mixture of diastereomers).

Examples of the substituent which the "cycloalkylene group having 4 to 20 carbon atoms which may be substituted" may have: a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); a carbon atom having 1 to 10 carbon atoms; Alkyl (e.g. methyl, ethyl, isopropyl, etc.); alkoxy with 1 to 10 carbons (eg (E.g., methoxy, ethoxy, etc.); fluorenyl groups having 1 to 10 carbon atoms (for example, ethenyl, benzamidine, etc.); fluorenyl groups having 1 to 10 carbon atoms (for example, acetamido) , Benzamidine, amidino, etc.); nitro; cyano; may have a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (for example, Methyl, ethyl, isopropyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, etc.) having 1 to 10 carbon atoms, and fluorenyl groups (e.g., ethenyl, benzene, etc.) having 1 to 10 carbon atoms Formamidine groups, etc.), Amido groups having 1 to 10 carbon atoms (for example, acetoamino, benzamidine, etc.), 1 to 3 substituents such as nitro, cyano, etc., having 6 carbon atoms ~ 10 aryl groups (for example, phenyl, naphthyl, etc.) and the like. The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

Specific structures of the general formula (6) are listed below, and are not limited thereto. Examples thereof include organic groups having an alicyclic structure represented by the following [R] group.

(In the above-mentioned [R] group, regarding the structure which may be a diastereomer, it may be any diastereomer or a mixture of diastereomers). Among these, an organic group having an alicyclic structure represented by the following [R-2] group is preferable from the viewpoint that it can be obtained industrially and inexpensively.

In the general formula (9), R ^2-16 represents a group having an acetal ring having 2 to 20 carbon atoms which may be substituted. The specific structure is listed below, and is not limited to these. In terms of the tendency to increase the glass transition temperature and birefringence, and to reduce the photoelastic coefficient, it can be preferably listed as follows: S] Group of the acetal ring.

(In the above-mentioned [S] group, the structure which may be a diastereomer may also be an arbitrary diastereomer).

Examples of the substituent which the "acetal ring having 2 to 20 carbon atoms which may be substituted" may have: a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); an alkane having 1 to 10 carbon atoms (For example, methyl, ethyl, isopropyl, etc.); alkoxy (for example, methoxy, ethoxy, etc.) having 1 to 10 carbons; fluorenyl (for example, ethyl, 1 to 10) Fluorenyl group, benzamidine group, etc.); fluorenylamino group having 1 to 10 carbon atoms (for example, acetamidine group, benzamidine group, etc.); nitro group; cyano group; may have a halogen atom (for example, Fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.), alkoxy group having 1 to 10 carbon atoms (for example, methoxy Group, ethoxy group, etc.), amidino group having 1 to 10 carbon atoms (for example, ethanoyl group, benzamidine group, etc.), amidino group having 1 to 10 carbon atoms (eg, acetamido group, benzamidine group, etc.) Sulfonylamino groups, etc.), aryl groups having 1 to 3 substituents such as nitro and cyano groups, and aryl groups having 6 to 10 carbon atoms (for example, phenyl, naphthyl, etc.). The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

Among the divalent organic groups represented by the general formula (3), the preferred ones are those in which the main chain does not have an aromatic ring, or the main chain contains a portion of structures other than aromatic rings, so that the comparison required for an optical film can be achieved. The tendency of a low photoelasticity coefficient is a substituted alkylene group, a substituted alkylene ether group, an organic group having a substituted alicyclic structure, or an organic group having a substituted heterocyclic structure. More preferably, it is selected from the following general formula (4) which tends to impart higher transparency and glass transition temperature, water absorption, birefringence, and lower photoelastic coefficient.

The following general formula (5), which has appropriate hydrophobicity and softness, and has a tendency to impart a low photoelastic coefficient

( ^Wherein R ^2-11 represents a linear alkylene group having 0 to 18 carbon atoms which can be substituted) or the following general formulas which tend to impart higher transparency, glass transition temperature, and appropriate flexibility Equation (6)

( ^Wherein R ^2-12 represents a cycloalkylene group having 4 to 20 carbon atoms which may be substituted) or the following general formula (7) which tends to impart softness and water absorption and a low photoelastic coefficient [Chemical 81]

(In the formula, R ^2-13 represents an alkylene group having 2 to 10 carbon atoms which can be substituted, and p is an integer of 1 to 40), or the following general formula which tends to give higher transparency and glass transition temperature Equation (8)

(In the formula, R ^2-14 represents an alkylene group having 2 to 10 carbon atoms that can be substituted, and R ^2-15 represents an alkylene group having 12 to 30 carbon atoms that can be substituted), or has a higher transparency Properties and the tendency of glass transition temperature and birefringence, the following general formula (9)

(In the formula, R ^2-16 represents a group having an acetal ring having 2 to 20 carbon atoms which may be substituted.) Furthermore, it is preferred that the above-mentioned general formula (4) has a tendency to impart higher physical properties as a retardation film by providing higher transparency and glass transition temperature, water absorption, and lower photoelastic coefficient. base.

The divalent organic group represented by the general formula (3) may be used singly or in combination of two or more kinds. From the viewpoint of reducing uneven quality control for each batch of optical or mechanical properties, it is preferable to use one type alone. On the other hand, from the viewpoint of taking both optical characteristics and mechanical properties into consideration, it is preferable to use two or more types together, and it is usually four or less types, and more preferably Use 3 or less.

When two or more types of divalent organic groups represented by the general formula (3) are used in combination, the combination thereof is not particularly limited. For example, in order to impart 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. The organic group represented by the general formula (5) or the organic group represented by the general formula (7) is preferable. On the other hand, in order to impart high transparency, glass transition temperature, and appropriate flexibility, it is preferable. It is an organic group represented by the above-mentioned general formula (6), and among these, a combination of the organic groups corresponding to the desired purpose may be selected. Specifically, the repeating unit derived from ISB (isosorbide) belonging to the organic group represented by the general formula (4) and the CHDM (1) derived from the organic group represented by the general formula (6) are preferable. , 4-cyclohexanedimethanol), or a combination of SPG (spirodiol) -derived repeating units belonging to the organic group represented by the general formula (9) and the general formula (6) The organic group is a combination of repeating units derived from CHDM.

<3.7 copolymerization composition>

As described above, when a copolymer containing at least a divalent trifluorene, a divalent difluorene, and a divalent organic group represented by the general formula (3) as a repeating unit is used, the following expressions are required: Within the range of optical physical properties, the above copolymer may contain a divalent trifluorene, a divalent difluorene, and a divalent organic group represented by the general formula (3) in any mass.

Regarding the sum of the content ratios of the trivalent trivalent and bivalent trivalent, in order to exhibit inverse wavelength dispersion and maintain melt processability or mechanical strength, it is preferable that the mass of the copolymer is 5% by mass or more. , More preferably 10% by mass or more, further preferably 12% by mass or more, particularly preferably 15% by mass or more, still more preferably 90% by mass or less, even more preferably 80% by mass or less, and still more preferably 70% by mass Hereinafter, it is particularly preferably 60% by mass or less.

In addition, from the viewpoint of obtaining the required optical characteristics with a smaller amount of use, the content ratio of the trivalent difluoride to the mass of the entire copolymer is preferably 1% by mass or more, and more preferably 3% by mass. Above, further preferably at least 5 mass%, particularly preferably at least 10 mass% The above is more preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

From the viewpoint of imparting anisotropy to a positive refractive index, the preferable content ratio of the divalent organic group represented by the general formula (3) is preferably 10% by mass relative to the mass of the entire copolymer. Above, more preferably 20% by mass or more, further preferably 30% by mass or more, particularly preferably 40% by mass or more, still more preferably 95% by mass or less, even more preferably 90% by mass or less, and still more preferably 88% by mass % Or less, particularly preferably 85% by mass or less, and most preferably 80% by mass or less.

<3.8 polymer blend>

The resin composition of the present invention is a polymer containing a trivalent difluoride as a repeating unit. The resin composition of the present invention may contain other components in addition to the polymer.

Regarding the resin composition of the present invention, it is expected that the other effects of the blend are exhibited, and any polymer may be contained as other components. That is, in addition to a polymer having a trivalent trivalent divalent group as a repeating unit, any polymer may be present together.

Here, the term “coexistence” means that two or more kinds of polymers are present in the resin composition, and the method is not particularly limited. Examples thereof include mixing two or more kinds of polymers in a solution state or a molten state. A method, a method of polymerizing in a solution or a melt containing one or more polymers, and the like.

For example, a polymer having a divalent organic group represented by the general formula (3) as a repeating unit may be blended, and a polymer having an arbitrary repeating unit may be blended. The polymer having a divalent organic group represented by the general formula (3) as a repeating unit may be a polymer having a divalent organic group other than the general formula (3) as a repeating unit, or may have two types. The divalent organic group represented by the above general formula (3) is a repeating unit. Here, as the divalent organic group represented by the general formula (3), those exemplified in the copolymer can be preferably used.

Especially from the viewpoint that it can be preferably used as a retardation film, Blends of polymers or oligomers with positive refractive index anisotropy or co-existence of copolymers have a good optical performance and are more likely to be melt-formed or solution-casted. Coexist a thermoplastic resin. Specific examples of the coexistent polymers 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. Among them, polyester or polycarbonate is preferred.

More specifically, olefin-based polymers such as polyethylene and polypropylene; bisphenol A or bisphenol Z, polycarbonate having a structural unit derived from isosorbide, and the like; polyethylene terephthalate , Polyesters such as polybutylene terephthalate, polynaphthalate, polycyclohexane dimethylene dicarboxylate, polycyclohexane dimethylene terephthalate, etc., can also be used in combination Two or more of these polymers.

When the resin composition of the present invention is formed into a film, the film is preferably optically transparent. Therefore, the polymer to be blended is preferably a polymer having a refractive index and a trivalent divalent trivalent polymer as a repeating unit. Closer, or a combination with compatibility.

<3.9 Composition of Resin Composition>

From the viewpoint of showing inverse wavelength dispersion and maintaining melt processability or mechanical strength, the sum of the content ratios of the trivalent divalent and divalent bivalent in the resin composition is relative to the entire resin composition. The mass 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 more preferably 90 mass. % Or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, even more preferably 60% by mass or less. From the same viewpoint, the preferred content ratio of the divalent organic group represented by the general formula (3) is preferably 10% by mass or more, more preferably 20% with respect to the mass of the entire resin composition. More than mass%, more preferably 30 mass% or more, particularly preferably 40 mass% or more, still more preferably 95 mass% or less, more preferably 90 mass% or less, still more preferably 88 mass% or less, particularly preferably 85 mass% or less, and most preferably 80 mass% or less.

In addition, the resin composition of the present invention may contain two or more kinds of divalent organic groups represented by the above-mentioned general formula (3). For example, a repeating unit derived from ISB (isosorbide) and a source derived from CHDM ( In the case of a repeating unit of 1,4-cyclohexanedimethanol, the content ratio is not particularly limited. From the viewpoint of higher glass transition temperature, birefringence, and water absorption, the repeating unit derived from ISB Relative to the molar fraction of the resin composition, it is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably 95% by mass or less, and even more preferably 90% by mass. Mass% or less, and more preferably 80 mass% or less.

When the repeating unit derived from ISB and the repeating unit derived from CHDM are used in combination, the content ratio is not particularly limited. From the viewpoint of flexibility, the repeating unit derived from CHDM is combined with the resin. Molar fraction of the material is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 15 mass% or more, still more preferably 60 mass% or less, and even more preferably 50 mass% or less. It is more preferably 40% by mass or less.

When a repeating unit derived from SPG (spirodiol) and a repeating unit derived from CHDM are used in combination, these content ratios are not particularly limited. From the viewpoint of higher glass transition temperature, birefringence, and water absorption In other words, based on the molar fraction of the repeating unit derived from SPG relative to the resin composition, it is preferably 30 mol% or more, more preferably 40 mol% or more, and further preferably 50 mol% or more. It is preferably 95 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less.

When the repeating unit derived from SPG and the repeating unit derived from CHDM are used in combination, the content ratio is not particularly limited. From the viewpoint of flexibility, the repeating unit derived from CHDM is combined with the resin. Molar fraction of the material is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 15 mass% or more, still more preferably 60 mass% or less, and even more preferably 50 mass% or less. It is more preferably 40% by mass or less.

<3.10 Physical property value>

The physical property value of the resin composition of the present invention is not particularly limited, and it is preferable to satisfy the physical property values exemplified below.

<3.20 Abbe number>

The resin composition of the present invention preferably has an Abbe number of 35 or less in the case of a wide-band zero birefringence material such as an imaging optical lens. The imaging optical lens is designed by using the resin composition of the present invention, and the one with a lower Abbe number is preferred. Therefore, the Abbe number is more preferably 30 or less, particularly preferably 25 or less, and usually 15 or more.

<3.21 Orientation of the Ring>

Regarding the resin composition of the present invention, the strength of the stretching direction of absorption of 740 cm ^-1 derived from the alignment of the cymbal ring and the vertical direction is preferably 1.2 or more, more preferably 1.3 or more, further preferably 1.4 or more, and usually Below 2.0. When the resin composition of the present invention is used as an inverse-wavelength dispersion film, the strength of the stretching direction of the absorption of 740 cm ^-1 derived from the orientation of the ring is higher than that of the vertical direction, and the tendency is as follows: The proportion of the repeating unit with a fluorene ring contained in the substance is small, and the inverse wavelength dispersion is also exhibited. The intensity ratio can be measured by the following method.

First, an stretched film was prepared from the resin composition of the present invention and subjected to polarized ATR analysis. In the analysis results, the intensity ratio of the extension direction of the absorption of 1245 cm ^-1 derived from the orientation of the carbonyl group to the vertical direction (2 color ratio: the strength of the extension direction / the strength of the vertical direction) is 1.2 or more, and the main chain direction is confirmed Extension direction alignment. Then, the intensity ratio of the extension direction of absorption of 740 cm ^-1 originating from the orientation of the cymbal ring to the vertical direction was calculated.

<3.22 Angle formed by the main chain and 茀>

Regarding the resin composition of the present invention, it is expected that when the specific configuration (conformation) of the divalent triad is not in a torsional configuration as a stable configuration, the main chain and transcyclic configuration of the trans configuration When the angle is 50 ° or more, preferably 60 ° or more, and more preferably 70 ° or more, the inverse wavelength dispersion property is exhibited.

The calculation of the energy of a specific configuration (conformation) of the divalent triad and the calculation of the angle formed by the tritium ring and the main chain in the configuration can be calculated in the following manner.

The software system uses a PC manufactured by the US Wave function company in accordance with the AM1 law Spartan Pro 1.0.5 (Windows (registered trademark) 32bit version). In addition, all input values related to the calculation accuracy, such as the focus judgment value, use the software default values.

Here, in the case of a polycarbonate resin composition, the trivalent divalent trivalent is calculated based on a structure obtained by methylating both ends of a repeating unit, and is combined with a polyester or a polyester carbonate resin. In the case of a substance, the calculation is performed on a structure obtained by methylating both ends of the repeating unit.

The AM1 method was used to calculate the energy difference between the two side chains present in each monomer in a trans configuration and a configuration with two intertwisted configurations. In addition, for the trans configuration and the intertwisted configuration (the stable of the two intertwisted configurations), the angle formed by the main chain and the loop is calculated.

The angle formed by the main chain and the cymbal ring is determined in the following manner. First, the straight line connecting the carbon atoms of the methyl groups at the two ends is set to the main chain direction, and the plane passing through the carbon atoms at the 3rd, 6th, and 9th positions of 茀 is the 茀 plane. At this time, the straight line on the 茀 -plane crossing the direction of the main chain exists infinitely, but the straight line on the 茀 -plane where the angle with the direction of the main chain becomes the smallest. Let this angle be the angle formed by the main chain and the loop.

<3.23 Introduction method of organic group>

As a method for introducing the divalent organic group represented by the above-mentioned general formula (3) as a repeating unit into the resin composition of the present invention, from the viewpoint of transparency or uniformity of the obtained resin composition, it is preferably : 1. A method of copolymerizing a dihydroxy compound having a trifluorene and a dihydroxy compound represented by the following formula (21) having an organic group represented by the general formula (3); 2. Using a compound having the general formula The organic group represented by the formula (3) is a dihydroxy compound represented by the following formula (21), after transesterification of the trimethyl diester compound, and the following formula having the organic group represented by the general formula (3) (21) A method for introducing a dihydroxy compound represented by (2) into a two-stage copolymerization method; (3) placing a tris (a) diaryl ester compound under an organic group having the general formula (3) A method for copolymerizing a dihydroxy compound represented by the formula (21); 4. a dihydroxy compound having a trifluorene and an organic group represented by the general formula (3) and represented by the following general formula (28) A method for copolymerizing a dicarboxylic acid compound and a dihydroxy compound represented by the following general formula (21) having an organic group represented by the general formula (3).

HO-R ²⁰ -OH (21)

HOCOR ²⁰ -OOOH (28)

In formulae (21) and (28), R ²⁰ is the same as R ^{20 in} the general formula (3).

Here, as the divalent organic group represented by the general formula (3), a single type may be used, or different types of organic groups may be used in combination. The use of a combination of different plural organic groups is achieved by using different plural kinds of dihydroxy compounds represented by the general formula (21) and / or dicarboxylic acids represented by the general formula (28). Compound.

<3.24 phase difference ratio>

When the resin composition of the present invention is intended to be used for a retardation film, the ratio of the phase difference (Re450) measured at a wavelength of 450nm to the phase difference (Re550) measured at a wavelength of 550nm, that is, the phase difference is better. To satisfy the following formula (20).

Re450 / Re550 ≦ 1.0 (20)

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

The phase difference ratio is measured by the following method. The resin composition was pressed with a hot press to produce a film. This film was cut into a specific size, and the free end was uniaxially stretched to produce a stretched film. The phase difference (Re450) at a wavelength of 450 nm and the phase difference (Re550) at a wavelength of 550 nm of this stretched film were measured using a phase difference measuring device (KOBRA-WPR manufactured by Oji Measurement Co., Ltd.). When the phase difference ratio (Re450 / Re550) with respect to the extension direction satisfies the above formula (20), the resin composition appears as a phase Differential films have useful wavelength dispersion.

When the use of the inverse wavelength dispersion film in the retardation film of the resin composition of the present invention is assumed, the upper limit of the retardation ratio (Re450 / Re550) is preferably 1.0 or less, more preferably less than 1.0, and still more preferably 0.95 or less. It is more preferably 0.93 or less, and even more 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 0.50 or more, still more preferably 0.70 or more, particularly preferably 0.75 or more, and most preferably 0.80 or more.

If the value of the phase difference ratio (Re450 / Re550) is within the above range, the longer the wavelength, the more the phase difference will appear, and the ideal phase difference characteristic 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 property as a 1 / 4λ plate that changes the phase of polarized light that vibrates in directions perpendicular to each other by a 1/4 wavelength (90 °), By attaching it to a polarizing plate, a circular polarizing plate and the like can be produced, and a circular polarizing plate and an image display device having excellent blackness with the function of preventing external light reflection at all wavelengths can be realized. On the other hand, when the value of the phase difference ratio (Re450 / Re550) is out of the above range, there is a tendency that the discoloration caused by the wavelength becomes large, and the circular polarizing plate or the image display device has a coloring problem.

"Invention 3"

Hereinafter, the oligomeric fluorene of this invention 3, the oligomeric fluorene composition containing the same, and the resin composition obtained using this oligomeric fluorene are described in detail.

In addition, the following general formulae (1) to (5), (4-1), (2a), (2b), (2c-1), (2c-2), (2d), ( 7) to (9), (11), (A), (A-1), and (B) are explanations of each structure in the present invention 3.

<1 Oligomeric amidine compound A1 having one reactive functional group>

The oligomeric fluorene having one reactive functional group in the present invention (hereinafter referred to as "oligomeric fluorene A1") includes an oligomeric fluorene structural unit a, which is a fluorene unit having two or more substituents. The carbon atoms at position 9 of a each have an alkyl group which may have a substituent, A carbon atom at position 9 of the fluorene unit a at any terminal of the oligomeric fluorene structural unit a It has a reactive functional group represented by the following formula (A), and the carbon atom at the 9-position of the fluorene unit a at the other end has a hydrogen atom.

In formula (A), R ^a to R ^c are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or 6 carbon atoms that can be substituted Aralkyl of ~ 10, X is ester, amido, carboxy, cyano, or nitro. * Is a bond to a carbon atom at position 9 of the a unit of fluorene.

As described above, it can be obtained industrially by setting the reactive functional group to a specific structure, and it can be preferably used as a raw material for a monomer of a resin composition for optical applications.

<1.1 alkylene, alkylene, alkylene>

It is the same as that described in the item "1.1 Alkenyl, Aryl, and Arylalkyl" in "Invention 2" above.

<1.2 The substituent which the unit a may have>

It is the same as that described in the item "Substituents which the 1.2" unit a may have in the "Invention 2" above.

<1.3 reactive functional group>

The oligomeric fluorene A1 of the present invention has a carbon atom at the 9-position of the fluorene unit a at either end having a reactive functional group represented by the following formula (A). The so-called reactive functional group is not only a group that can be used directly in a polymerization reaction, but also a group that can be used in a polymerization reaction after a conversion reaction.

[Chemical 85]

In formula (A), R ^a to R ^c are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or 6 carbon atoms that can be substituted Aralkyl of ~ 10, X is ester, amido, carboxy, cyano, or nitro. * Is a bond to a carbon atom at position 9 of the a unit of fluorene.

R ^a ~ R ^c above, the specific structure "may be substituted with the alkyl group having 1 to 10 carbon atoms The" within the system listed below is not limited to these, include: methyl, ethyl, n-propyl Straight-chain alkyl groups such as n-butyl, n-pentyl, n-hexyl, n-decyl; isopropyl, 2-methylpropyl, 2,2-dimethylpropyl, 2-ethylhexyl, etc. Including side chain alkyl groups; cyclic alkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl and the like.

The number of carbon atoms in the alkyl group having 1 to 10 carbon atoms which may be substituted is preferably 4 or less, and more preferably 2 or more. If it is in this range, introduction of a reactive functional group tends to be easy.

Examples of the substituent that the alkyl group may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); and an alkoxy group (for example, a methoxy group, an ethoxy group) having 1 to 10 carbon atoms. Etc.); fluorenyl groups having 1 to 10 carbon atoms (for example, acetofluorenyl, benzamidine, etc.); fluorenyl groups having 1 to 10 carbon atoms (for example, acetamido, benzamidine, etc.); Nitro; cyano; may have a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, etc.) , Alkoxy groups with 1 to 10 carbon atoms (for example, methoxy, ethoxy, etc.), fluorenyl groups with 1 to 10 carbon atoms (for example, ethyl fluorenyl, benzyl fluorenyl, etc.), carbon numbers 1 to 10 Sulfonylamino (for example, ethynylamine, benzamidine, fluorenylamino, etc.), nitro, cyano, etc. 1 to 3 substituents and 6 to 10 carbon atoms (for example, phenyl, Naphthyl, etc.). The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

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

R ^a ~ R ^c above, the "aryl group may be substituted with the carbon atoms of 4 to 10" in the system configuration will be specifically enumerated below, not limited to these, include: phenyl, 1-naphthyl, 2 -Aryl groups such as naphthyl; heteroaryl groups such as 2-pyridyl, 2-thienyl, 2-furyl.

The number of carbon atoms in the aryl group having 4 to 10 carbon atoms that can be substituted is preferably 8 or less, more preferably 7 or less, still more preferably 4 or more, and even more preferably 5 or more. If it exists in this range, introduction of a reactive functional group will become easy.

Examples of the substituent which the aryl group may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); and an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, and isopropyl) Alkoxy groups (e.g., methoxy, ethoxy, etc.) having 1 to 10 carbon atoms; fluorenyl groups (e.g., ethenyl, benzyl, etc.) having 1 to 10 carbon atoms; carbon number 1 to 10 amido groups (for example, acetamido, benzamido, etc.); nitro; cyano and the like. The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

Specific examples of the substituted aryl group include 2-methylphenyl, 4-methylphenyl, 4-chlorophenyl, 3,5-dimethylphenyl, and 4-benzylphenylbenzene. Methyl, 4-methoxyphenyl, 4-nitrophenyl, 4-cyanophenyl, 3-trifluoromethylphenyl, 3,4-dimethoxyphenyl, 3,4-methylene Dioxyphenyl, 2,3,4,5,6-pentafluorophenyl, 4-methylfuryl and the like.

The specific structure of the "aralkyl group having 6 to 10 carbon atoms which may be substituted" in the above R ^a to R ^c is listed below and is not limited thereto. Examples include: benzyl, 2-phenylethyl , P-methoxybenzyl and the like.

The number of carbon atoms in the aralkyl group having 6 to 10 carbon atoms that can be substituted is preferably 9 or less, more preferably 8 or less, still more preferably 6 or more, and even more preferably 7 or more. If it exists in this range, introduction of a reactive functional group will become easy.

Examples of the substituent that the aralkyl group may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); and an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, iso Propyl, etc.); alkoxy groups (e.g., methoxy, ethoxy, etc.) having 1 to 10 carbon atoms; fluorenyl groups (e.g., ethenyl, benzamidine, etc.) having 1 to 10 carbon atoms; carbon 1 to 10 fluorenylamino groups (for example, acetamido, benzamidine, etc.); nitro; cyano and the like. The number of these substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the kinds of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted in view of the fact that it can be manufactured inexpensively industrially.

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

Among these, from the viewpoint that the introduction of a reactive functional group tends to be facilitated, the following general formula (A-1) in which R ^a and R ^b are hydrogen atoms is preferred. Furthermore, from a viewpoint that a raw material can be obtained cheaply industrially, R ^{c is} preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

The specific structure of the "ester group" in X is not particularly limited, and examples thereof include ester groups in which the terminal group is an organic substituent having 1 to 10 carbon atoms.

Specific examples of the organic substituent having 1 to 10 carbon atoms are listed below and are not limited thereto. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n- Linear alkyl groups such as decyl; isopropyl, 2-methylpropyl, 2,2-dimethylpropyl, 2-ethylhexyl and other alkyl groups containing side chains; cyclopropyl, cyclopentyl Cyclic alkyl groups such as alkyl, cyclohexyl, cyclooctyl; aryl groups such as phenyl, 1-naphthyl, 2-naphthyl; heteroaryl groups such as 2-pyridyl, 2-thienyl, 2-furyl; Aralkyl groups such as benzyl, 2-phenylethyl, and p-methoxybenzyl, and the like.

Among these, in view of industrial availability, the carbon number is preferably 1 ~ 6 alkyl. In this case, the carbon number is preferably 2 or more from the viewpoint of being easily hydrolyzed in the synthesis to easily generate a carboxylic acid, and the low-boiling point produced by transesterification with a dihydroxy compound is preferred. From the viewpoint that alcohols can be removed and polyesters and polyester carbonates can be efficiently synthesized, the number of carbons is preferably 4 or less, and more preferably 2 or less. A particularly preferred substituent is ethyl.

On the other hand, in the case of an aryl group having 6 to 8 carbon atoms, the transesterification reaction easily proceeds. Therefore, the aryl ester compound, the dihydroxy compound, and the carbonic acid diester can be added to the reactor at one time, and the In the first stage, polyester carbonate, which is a preferable polymer, is synthesized, and therefore, it is preferable. In particular, the molecular weight is relatively small, and the phenyl group which can be distilled off as phenol after the synthesis of polyester carbonate is particularly preferable. In the case of an aryl group, from the viewpoint of reactivity at the time of polymerization, it is preferable to use the following diaryl carbonates as the carbonic acid diester, and from the viewpoint of easily removing by-products, More preferably, the aryl group in the ester group is the same as the aryl group in the diaryl carbonates.

In addition, the ester group can be converted into an alcohol useful as a raw material of polycarbonate or polyester by reduction.

The specific structure of the "fluorenylamino group" in X is not particularly limited, and examples include: (i) a fluorenylamino group having two hydrogen atoms at the nitrogen atom, and (ii) a hydrogen atom and a carbon number of 1 to the nitrogen atom. A secondary amido group of the organic substituent of 10, and (iii) a tertiary amido group having two organic substituents having 1 to 10 carbon atoms independently at the nitrogen atom. As the organic substituent having 1 to 10 carbon atoms, those exemplified as the organic substituent having 1 to 10 carbon atoms in the "ester group" can be preferably used.

The amido group can be reduced to become an "amine group" and made into a raw material of polyamido or polyimide. Among these, from the standpoint of ease of reduction and the reactivity of the amine group after reduction, a primary fluorene amino group and a secondary fluorene amino group are preferred, and a primary fluorene amino group is more preferred.

As X, from the viewpoint of being directly usable as a raw material of polyester or polyester carbonate, among these, an ester group or a carboxyl group is preferred, and a methyl ester group, an ethyl ester group, and a phenyl group are more preferred. Ester or carboxyl.

<1.4 Specific Structure>

As the oligomeric fluorene A1 of the present invention, specifically, those represented by the following general formula (1) can be preferably used.

In the formula (1), R ^{3 is} 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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in 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 alkyl group having 1 to 10 carbon atoms which can be substituted, an aryl group having 4 to 10 carbon atoms which can be substituted or an aralkyl group having 6 to 10 carbon atoms which can be substituted X is an ester group, amidino group, a carboxyl group, a cyano group, or a nitro group.

n represents an integer value from 1 to 5.

In the above formula (1), R ³ and R ⁴ to R ⁹ can be preferably used as exemplified in the bases of the above-mentioned "Invention 1".

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

Specific examples of the oligomeric fluorene A1 of the present invention include a structure shown in the following [E] group.

[Chem 89]

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

The physical property value of the oligomeric fluorene A1 of the present invention is not particularly limited, and it is preferably one that satisfies the physical property values exemplified below.

Regarding the chlorine content ratio in the oligomeric fluorene A1 of the present invention, it is preferably 100 mass ppm or less in terms of Cl conversion mass. It is more preferably 10 mass ppm or less. When the content of the chlorine component is large, there is a possibility that the monomer containing the oligomeric fluorene A1 as a raw material also contains a large amount of the chlorine component, and the catalyst used in the polymerization reaction is deactivated, thereby polymerizing. It no longer progresses to the desired molecular weight, or the reaction becomes unstable and the productivity deteriorates. Again There is a concern that the chlorine component also remains in the obtained polymer, thereby reducing the thermal stability of the polymer.

In the oligomeric fluorene A1 of the present invention, there is a long-period type periodic table Group 1 metal such as sodium or calcium, which contains a step derived from the step of reacting fluorenes with formaldehydes in the presence of a base, such as sodium or potassium. The possibility of Group 2 metals is preferably 500 mass ppm or less, more preferably 200 mass ppm or less, still more preferably 50 mass ppm or less, and even more preferably 10 mass ppm or less. If there are many metal components, the monomer may be contained in a large amount in the monomer obtained as oligomeric fluorene A1, and the polymer may be easily colored during polymerization or processing of the resin. In addition, there is a possibility that the contained metal component exhibits a catalyst effect or a catalyst deactivation effect, and polymerization becomes unstable.

In the oligomeric fluorene A1, especially oligomeric fluorene monoaryl esters of the present invention, there are titanium, copper, and titanium which contain a step derived from the transesterification by the action of a diaryl carbonate in the presence of a transesterification reaction catalyst. The possibility of transition metals such as iron, or Group 1 of the long-period periodic table such as sodium or potassium, or Group 2 metals such as magnesium and calcium, or Group 12 metals such as zinc or cadmium, or Group 14 metals such as tin, The content ratio of these is preferably 500 mass ppm or less, more preferably 200 mass ppm or less, still more preferably 50 mass ppm or less, and even more preferably 10 mass ppm or less. If there are many metal components, there may be a large amount of metal components contained in the monomer obtained as an oligomeric fluorene, and the polymer may be likely to be colored when the polymerization reaction or the resin is processed. In addition, there is a possibility that the metal component contained in the catalyst exhibits a catalyst action or a catalyst deactivation action, and polymerization becomes unstable.

The color tone of the 10% by mass tetrahydrofuran solution of the oligomeric fluorene A1 of the present invention is preferably 50 or less. It is more preferably 10 or less. Oligomeric A1 has the following properties: the absorption end is extended to a region near visible light, and it is easy to be colored when exposed to high temperature due to polymerization or resin processing. In order to obtain a polymer with a good hue, the monomer used in the polymerization reaction is preferably as small as possible. From this viewpoint, the oligomeric fluorene A1 as the monomer raw material is preferably as small as possible. Since the hue is proportional to the density, it can also be measured at different concentrations and A value obtained by normalizing to a concentration of 10% by mass. Here, the color tone (APHA value) of oligomeric fluorene A1 can be prepared by diluting a color standard solution (1000 degrees) manufactured by Kishida Chemical Co., Ltd. in accordance with JIS-K0071-1 (1998) and oligomeric fluorene A1 was measured in a colorimetric tube with an inner diameter of 20 mm for comparison.

The 5% weight reduction temperature of the oligomeric fluorene A1 of the present invention under thermogravimetric measurement is preferably 230 ° C or higher, more preferably 250 ° C or higher. The temperature is more preferably 270 ° C or higher. Samarium is a very electron-rich structure, and the reactivity of the substituents bonded to the samarium ring is improved, and it becomes easy to cause thermal decomposition. If a monomer with a low thermal decomposition temperature is used in the polymerization reaction, there is a risk that the thermal decomposition will be caused during the polymerization and the polymerization will not proceed to the required molecular weight, or the obtained polymer will be colored, so it is oligomerized as a monomer raw material. Polyfluorene A1 is also preferably a higher thermal decomposition temperature.

<1.7 Production method of oligomeric fluorene A1 having one reactive functional group>

The manufacturing method of the oligomeric fluorene A1 of this invention is not specifically limited, For example, the method of making an oligomeric fluorene represented by the following formula (3) in the presence of a base, and having the following formula (4) is mentioned. The olefin having the electron-withdrawing group represented is reacted to produce an oligomeric fluorene A1 represented by the following formula (1).

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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in 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 alkyl group having 1 to 10 carbon atoms which can be substituted, an aryl group having 4 to 10 carbon atoms which can be substituted or an aralkyl group having 6 to 10 carbon atoms which can be substituted X is an ester group, amidino group, a carboxyl group, a cyano group, or a nitro group.

n represents an integer value from 1 to 5.

The above-described formula (3) and (4), examples of ^{R 3 ~ R 9, R a} ~ R c, X , and n, may be preferably used the above-described formula (1) as ^{R 3 ~ R 9, R a} ~ R ^c , X, and n.

<1.7.1 Alkenes 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, and 2-hydroxyethyl acrylate. Acrylates such as 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, methyl methacrylate, ethyl methacrylate, phenyl methacrylate, allyl methacrylate, Methacrylic esters such as glycidyl methacrylate, 2-hydroxyethyl methacrylate, methyl 2-ethylacrylate, methyl 2-phenylacrylate, etc. α-substituted unsaturated esters, β-substituted unsaturated esters such as methyl cinnamate, ethyl cinnamate, methyl butenoate, ethyl butenoate, and conjugated nitroolefins such as β-nitrostyrene Α, β-unsaturated nitriles such as acrylonitrile and acrylonitrile, α, β-unsaturated aldehydes such as acrolein, methacrylaldehyde, 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 directly introduced is preferred.

[Chemical 91]

(In the formula, R ^c is the same as R ^c in Formula (4), and R ^g represents an organic substituent having 1 to 10 carbon atoms). Here, as the organic substituent having 1 to 10 carbon atoms in ^Rg , those exemplified as the organic substituent having 1 to 10 carbon atoms in the "ester group" can be preferably used.

Among the unsaturated carboxylic acids represented by the general formula (4-1), acrylates, methacrylates, or α-substituted unsaturated esters are more preferred. From the viewpoint of reaction speed and reaction selectivity, Acrylates or methacrylates in which R ^c is a hydrogen atom or a methyl group are preferred. The smaller R ^g is industrially cheap and easy to be distilled and refined, and has high reactivity. Therefore, it is particularly preferably methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate, or Phenyl methacrylate.

On the other hand, the unsaturated carboxylic acid ester represented by the formula (4-1) is a 2-hydroxyethyl acrylate group, a 4-hydroxybutyl acrylate group, and a 1,4-cyclohexanedimethanol monoacrylate group. In the case of hydroxyalkyl esters, polyester carbonates and polyester raw materials can be obtained in the first stage, which is particularly preferred.

Two or more kinds of olefins having an electron-withdrawing group may be used. In terms of simplicity of purification, one kind of olefins having an electron-withdrawing group is preferably used.

The use amount of the olefin having an electron-withdrawing group is not particularly limited. From the viewpoint of selectively obtaining a mole adduct, it is preferably 0.1 equivalent or more, more preferably 0.3 equivalent or more, and even more preferably 0.5 equivalent or more, particularly preferably 0.7 equivalent or more, and more preferably 2.0 equivalent or less, more preferably 1.8 equivalent or less, still more preferably 1.5 equivalent or less, and even more preferably 1.2 equivalent or less.

<1.7.2 Alkali>

As the base, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide; sodium carbonate; and hydrogen carbonate can be used. Carbonates of alkali metals such as sodium and potassium carbonate, carbonates of alkaline earth metals such as magnesium carbonate and calcium carbonate, alkali metal salts of phosphoric acid such as sodium phosphate, sodium phosphate sodium phosphate, and potassium phosphate, n-butyl lithium, third butyl lithium, etc. Organic lithium salts, sodium alkoxides of alkali metals such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide, alkali metal hydrides such as sodium hydride or potassium hydride, tertiary amines such as triethylamine and diazabicycloundecene , Tetramethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide and other quaternary ammonium hydroxide. These may be used individually by 1 type, and may use 2 or more types together.

When R ³ is a methylene group and other cases, there is a tendency that the reactivity of the oligomeric fluorene represented by formula (3) is greatly different. Therefore, the case where R ³ is methylene is described separately from the case other than R ³ .

When R ³ is a methylene group, the oligomeric fluorene represented by the formula (3) is in a solvent, and a decomposition reaction is easily performed in the presence of a base. Therefore, when a reaction is performed in a two-layer system of an organic layer and an aqueous layer, a water-soluble inorganic base is preferably used in terms of suppressing side reactions such as decomposition reactions. Among these, in terms of cost and reactivity, hydroxides of alkali metals are preferred, and sodium hydroxide or potassium hydroxide is more preferred.

Regarding the concentration of the aqueous solution, in the case of using a particularly preferred sodium hydroxide aqueous solution, if the concentration is thin, the reaction speed is significantly reduced. Therefore, it is particularly preferred to use 5wt / wt% or more, preferably 10wt / wt. % Or more, more preferably 25 wt / wt% or more of aqueous solution.

When R ³ is other than methylene, the reaction is also performed in the two-layer system of the organic layer and the water layer. However, when the reaction is performed using an organic base dissolved in the organic layer, the reaction tends to proceed quickly. Therefore, it is preferable to use an organic base. Among these, an alkali metal alkoxide having sufficient basicity in this reaction is preferable, and industrially inexpensive sodium methoxide or sodium ethoxide is more preferable. Here, the alkali metal alkoxide may be used in a powder form or in a liquid form such as an alcohol solution. Alternatively, it may be prepared by reacting an alkali metal with an alcohol.

In the case where R ³ is a methylene group, the upper limit of the amount of the base used is not particularly limited with respect to the oligomeric fluorene represented by the formula (3) as a raw material. When the refining load becomes large, when using a sodium hydroxide aqueous solution of 25 wt / wt% or more, which is a particularly preferred base, it is usually 20 times or less the volume of the oligomeric fluorene represented by formula (3). It is preferably 10 times or less the volume, and further preferably 5 times or less the volume. If the amount of the base is too small, the reaction rate is significantly reduced. Therefore, the base is usually 0.2 times the volume of the oligomeric fluorene represented by the formula (3) as a raw material. The volume is preferably 0.5 times or more, and more preferably 1 time or more.

When R ³ is other than methylene, the upper limit of the amount of base used is not particularly limited relative to the oligomeric fluorene represented by formula (3) as a raw material. If the amount of use is too large, there may be stirring or reaction. In the case where the subsequent refining load becomes large, when using sodium methoxide or sodium ethoxide, which is a particularly good base, it is usually 5 times less than the oligomeric fluorene represented by the formula (3), preferably It is preferably 2 times or less, more preferably 1 time or less, and particularly preferably 0.5 time or less. If the amount of the base is too small, the reaction rate is significantly reduced. Therefore, the base is usually 0.005 times mole or more relative to the oligomeric fluorene represented by the formula (3) as a raw material. It is preferably at least 0.01 times the mole, more preferably at least 0.05 times the mole, and even more preferably at least 0.1 times the mole.

<1.7.3 Interphase Transfer Catalyst>

When the reaction is performed in a two-layer system of an organic layer and an aqueous layer, in order to increase the reaction speed, 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, Halides (except fluorine) of quaternary ammonium salts such as trioctylmethylammonium chloride, tetrabutylammonium iodide, acetamyltrimethylammonium bromide, benzyltriethylammonium chloride, etc., N chloride , N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl-N-formyl chloride Halides (except fluorine) of quaternary pyrrolidinium salts such as methylpyrrolidinium, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholinium bromide, iodine N-butyl-N-methylmorpholinium, N-allyl-N-methylmorpholinium bromide halides (except fluorine), N-methyl chloride -N-benzylpiperidinium, N-methyl-N-benzylpiperidinium bromide, iodinated Halides of quaternary piperidinium salts such as N, N-dimethylpiperidinium, N-methyl-N-butylpiperidinium acetate, N-methyl-N-ethylpiperidinium iodide, etc. (Except fluorine), crown ethers, etc. A quaternary ammonium salt is preferable, and tetrabutylammonium bromide, benzyltrimethylammonium chloride, or benzyltriethylammonium chloride is more preferable. These may be used individually by 1 type, and may use 2 or more types together.

Regarding the use amount of the phase transfer catalyst, if it is too much relative to the oligomeric fluorene represented by the formula (3) as a raw material, there is a tendency that side reactions such as hydrolysis of the ester or sequential Michael reaction become obvious, and, From the viewpoint of cost, it is usually 5 times or less, preferably 2 times or less, and more preferably 1 time or less relative to the oligomeric fluorene represented by the formula (3). If the amount of the interphase transfer catalyst used is too small, the reaction speed tends to be significantly reduced. Therefore, the amount of the interphase transfer catalyst used is usually 0.01 times more than the oligomeric fluorene of the raw material. It is preferably at least 0.1 times mole, more preferably at least 0.5 times mole.

<1.7.4 Solvents>

The reaction of the olefin having the electron-withdrawing group represented by the formula (4) is preferably performed using a solvent.

Specific solvents that can be used include acetonitrile and propionitrile as the alkyl nitrile solvent, and acetone, methyl ethyl ketone, and methyl isobutyl ketone as the ketone solvent. As the ester solvent, Examples include methyl acetate, ethyl acetate, propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, methyl 3-methoxypropionate, 3- Linear esters such as methyl methoxypropionate, methyl lactate, ethyl lactate; cyclic esters such as γ-butyrolactone, caprolactone; ethylene glycol monomethyl ether acetate, ethylene glycol Ether esters such as alcohol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol-1-monomethyl ether acetate, propylene glycol-1-monoethyl ether acetate, and the like, and examples thereof include ether solvents Diethyl ether, tetrahydrofuran, 1,4-bis Alkane, methylcyclopentyl ether, third butyl methyl ether, and the like. Examples of the halogen-based solvent include 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane. Examples of the halogen-based aromatic hydrocarbon include chlorobenzene and 1,2-dichlorobenzene. Examples of the fluorene-based solvent include N, N-dimethylformamide and N, N, -dimethyl. Acetylamine and the like include fluorene-based solvents such as dimethyl fluorene and cyclobutane. Examples of the cyclic aliphatic hydrocarbon include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. And other monocyclic aliphatic hydrocarbons; its derivatives are methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1 , 3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, third butylcyclohexane, n-butylcyclohexane, Isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; polycyclic aliphatic hydrocarbons such as decahydronaphthalene; n-pentane, Non-cyclic aliphatics such as n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Examples of the hydrocarbon include toluene, para-xylene, o-xylene, and meta-xylene. Examples of the aromatic heterocyclic ring include pyridine. Examples of the alcohol-based solvent include methanol, ethanol, isopropyl alcohol, and the like. N-butanol, tertiary butanol, hexanol, octanol, cyclohexanol and the like.

When R ³ is a methylene group, it is known that by using a solvent separated from the water phase, side reactions such as the decomposition reaction of the oligomeric fluorene represented by the formula (3) can be suppressed. Furthermore, in the case where a solvent that sufficiently dissolves the oligomeric fluorene represented by the formula (3) is used as a raw material, it is preferable to use the formula (3) as a raw material because the reaction tends to proceed well. The solvent having an solubility of oligomeric fluorene represented by 0.5% by mass or more, more preferably a solvent having a solubility of 1.0% by mass or more, and particularly preferably a solvent having a solubility of 1.5% by mass or more. Specifically, a halogen-based aliphatic hydrocarbon, a halogen-based aromatic hydrocarbon, an aromatic hydrocarbon, or an ether-based solvent is preferred, and dichloromethane, chlorobenzene, chloroform, 1,2-dichlorobenzene, tetrahydrofuran, 1,4-two Alkane, or methylcyclopentyl ether.

On the other hand, when R ³ is a group other than methylene, it is known that the solubility of the organic base and the oligomeric fluorene represented by the formula (3) has a large influence on the reaction rate. To ensure its solubility, it is ideal to use a solvent with a dielectric constant above a certain value. As the solvent for sufficiently dissolving the organic base and the oligomeric fluorene represented by the formula (3), an aromatic heterocyclic ring, an alkyl nitrile-based solvent, a fluorene-based solvent, and a fluorene-based solvent are preferred, and pyridine and acetonitrile are particularly preferred , N, N-dimethylformamide, N, N, -dimethylacetamide, dimethylmethane, cyclobutane.

These solvents may be used alone or in combination of two or more.

With regard to the amount of solvent used, the upper limit is not particularly limited. If the production efficiency of the target substance in each reactor is considered, a volume of 20 times the volume of the oligomeric fluorene represented by formula (3) as a raw material is generally used. It is preferably an amount of 15 times the volume, and more preferably an amount of 10 times the volume. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent becomes poor and the stirring becomes difficult, and the progress of the reaction becomes slow. Therefore, as a lower limit, an oligomer represented by formula (3) as a raw material is generally used. The amount of 1 volume is preferably 2 volumes, more preferably 4 volumes.

<1.7.5 Reaction Form>

The form of the reaction may be a batch reaction, a flow-through reaction, or a combination of these, and the form is not particularly limited.

Regarding the method of feeding the reaction reagent into the reactor in the case of batch type, when an olefin having an electron-withdrawing group is added at a time at the start of the reaction, the olefin having an electron-withdrawing group is present at a high concentration, and therefore a side reaction occurs. The polymerization reaction is easy to proceed. Therefore, it is preferable to add an olefin having an electron-withdrawing group one by one in small amounts multiple times after adding the oligomeric fluorene, the phase transfer catalyst, the solvent, and the base represented by formula (3) as raw materials.

<1.7.6 Reaction conditions>

If the temperature is too low, a sufficient reaction rate cannot be obtained. On the other hand, if the temperature is too high, the polymerization reaction of an olefin having an electron-withdrawing group tends to proceed easily. Therefore, temperature management is extremely important. Therefore, as the reaction temperature, the lower limit is usually 0 ° C, preferably 10 ° C, and more preferably 15 ° C. On the other hand, the upper limit is usually 40 ° C, preferably 30 ° C, and more preferably 20 ° C.

As for the usual reaction time, the lower limit is usually 2 hours, preferably 4 hours, and further preferably 6 hours, and the upper limit is not particularly limited, but is usually 30 hours, preferably 20 hours, and further preferably 10 hours.

<1.7.7 Separation and Refining of Targets>

After completion of the reaction, the oligomeric fluorene A1 represented by the above formula (1) as a target substance can be removed from the reaction solution by filtering the metal halide by-produced and the residual inorganic base, and then concentrating the solvent by using The oligomeric fluorene A1 represented by the above formula (1) as a target is precipitated by a method such as a method of adding a poor solvent of the target or the like.

In addition, after the reaction is completed, acid water and an oligomeric fluorene A1 soluble solvent represented by the above formula (1) as a target substance may be added to the reaction solution to perform extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent.

The solvent that can be used in the extraction is not particularly limited as long as it is an oligomeric fluorene A1 represented by the above formula (1) as a target, and aromatic hydrocarbon compounds such as toluene and xylene can be preferably used , Methylene chloride, chloroform, and other halogen-based solvents, such as one or two or more.

In the case where X is an ester group in the oligomeric fluorene A1 represented by the formula (1) obtained here, it can be used as a precursor of a polyester or polyester carbonate raw material monomer, and can also be used after purification . As the purification method, ordinary purification methods such as recrystallization, reprecipitation, extraction purification, and column chromatography can be used without limitation. Alternatively, oligomeric fluorene A1 may be dissolved in an appropriate solvent and treated with activated carbon. The solvent that can be used at this time is the same as the solvent that can be used during extraction.

When X in the oligomeric fluorene A1 represented by the formula (1) obtained here is a carboxyl group, it can be used directly as a precursor of a polyester or a polyester carbonate raw material monomer. In addition, it can be converted to an oligomeric fluorene in which X is an ester group by an esterification reaction.

In the case where X in the oligomeric fluorene A1 represented by formula (1) obtained here is nitro or cyano, hydrogenation using a method such as palladium on carbon under a hydrogen environment, or using a reducing agent such as lithium aluminum hydride By hydrogenation reduction, oligomeric fluorenes having amine groups can be produced. When X is a cyano group, it can be determined by the specification of U.S. Patent No. 3280169 and U.S. Patent No. 3324084. To oligomeric amidines in which X is an ester group by methods such as the specification.

<2 Oligomeric amidine compound A2 having 2 different reactive functional groups>

The oligomeric fluorene having two different reactive functional groups according to the present invention (hereinafter, referred to as "oligomeric fluorene A2") is an oligomeric fluorene, which is characterized in that it contains 2 which may have a substituent. The 9 or more carbon atoms of the fluorene unit a are chain-bonded to each other via an alkylene group which may have a substituent, an alkylene group which may have a substituent, or an alkylene group which may have a substituent. The oligomeric fluorene structural unit a, and the carbon atom at the 9th position of the fluorene unit a on either end of the oligomeric fluorene structural unit a has a reactive functional group represented by the following formula (A), The 9-position carbon atom of the terminal fluorene unit a has an arbitrary reactive functional group different from the reactive functional group.

In formula (A), R ^a to R ^c are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or 6 carbon atoms that can be substituted Aralkyl of ~ 10, X is ester, amido, carboxy, cyano, or nitro. * Is a bond to a carbon atom at position 9 of the a unit of fluorene.

As the alkylene, arylene, and aralkyl groups of the fluorene unit a, respectively, those exemplified in <1.1 aralkylene, arylene, and aralkylene> can be preferably used.

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

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

<2.1 any reactive functional group>

As described above, the oligomeric fluorene A2 of the present invention is such that the carbon atom at the 9 position of the fluorene unit a at any terminal has a reactive functional group represented by the above formula (A), and the fluorene at the other terminal The carbon atom at the 9-position of the unit a has an arbitrary reactive functional group different from the reactive functional group.

The above-mentioned arbitrary reactive functional group is not particularly limited, and may be one that does not satisfy the requirements of formula (A), or may be one that satisfies the requirements of formula (A) but is different from one reactive functional group. .

As described above, since one oligofluorene has two different reactive functional groups, there is a tendency that specific physical properties derived from the two reactive functional groups can be easily imparted to the resin.

Specific structures of any of the reactive functional groups mentioned above are listed below, but are not limited thereto, and examples include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, hydroxybutyl, and 2,2-dimethyl Methyl-3-hydroxypropyl, 2-methoxymethyl-2-methylphenyl, 4-hydroxyphenyl, 4-hydroxy-3-methylphenyl, 4- (2-hydroxyethoxy ) Hydroxyl groups such as phenyl, (4- (hydroxymethyl) cyclohexane-1-yl) methyl; methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, ethoxycarbonylmethyl, 2- ( (Ethoxycarbonyl) ethyl, 2- (methoxycarbonyl) ethyl, 2- (phenoxycarbonyl) ethyl, 2-methyl-2- (ethoxycarbonyl) ethyl, 2-methyl Esters such as 2- (methoxycarbonyl) ethyl, 2-methyl-2- (phenoxycarbonyl) ethyl, 2- (methoxycarbonyl) propyl; 2-hydroxyethoxycarbonyl, 2- (2-hydroxyethoxy) carbonylethyl, 2-methyl-2- (2-hydroxyethoxy) carbonylethyl, 2- (2-hydroxyethoxy) carbonylpropyl, 2- ( 4-hydroxybutoxy) carbonylethyl, 2-methyl-2- (4-hydroxybutoxy) carbonylethyl, 2-[[4- (hydroxymethyl) cyclohexane-1-yl] methyl Oxy] carbonylethyl, 2-methyl-2-[[4- (hydroxymethyl) cyclohexane-1-yl] Oxy] hydroxy ester groups such as carbonylethyl; carboxyl groups such as carboxyl, carboxymethyl, 2-carboxyethyl, 2-methyl-2-carboxyethyl; aminomethyl, 2-aminoethyl, 3- Amino groups such as aminopropyl; propylene methoxymethyl, methacryl methoxymethyl, 2- (propylene fluorenyloxy) ethyl, 2- (methacryl methoxy) ethyl, 3- (Propenyloxy) propyl, 3- (methacryloxy) propyl, and other propenyl groups; 2,3-epoxy Epoxy groups such as propyl, 2,3-epoxypropoxymethyl, 2- (2,3-epoxypropoxy) ethyl, and the like.

Furthermore, the oligomeric fluorene A2 of the present invention can be used as a raw material of a polymer having a divalent oligomeric fluorene as a repeating unit, and the reactive functional group is preferably only two, and is preferably not included in the production Under various polymerization conditions, various resin compositions serve as a substituent that functions as a polymerization-reactive group.

Among these, regarding a preferable combination of the reactive functional group represented by the formula (A) and another reactive functional group, in terms of producing a polyester from one oligomeric fluorene compound, the formula (A) ) Is an ester group and another reactive functional group is a hydroxy group, formula (A) is a carboxyl group and another reactive functional group is a hydroxy group, and formula (A) is an ester group and the other reactive functional group is A combination of hydroxyester groups. The ester group, the hydroxyl group, the carboxyl group, and the hydroxyl ester group in this paragraph have the same meanings as the ester group, the hydroxyl group, the carboxyl group, and the hydroxyl ester group of the specific structure as the reactive functional group illustrated in the above paragraph.

<2.2 Specific Structure>

As the oligomeric fluorene A2 of the present invention, specifically, those represented by the following general formula (2) can be preferably used.

In formula (2), 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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl, fluorenyloxy having 1 to 10 carbons which may have a substituent, alkoxyl having 1 to 10 carbons which may have a substituent, aryloxy having 1 to 10 carbons which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in R ⁴ to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ is a direct bond, an alkylene group having 1 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, or an alkylene group having 6 to 10 carbon atoms that can be substituted, Or selected from the group consisting of an alkylene group having 1 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, and an alkylene group having 6 to 10 carbon atoms that can be substituted The two or more groups are a group bonded by an oxygen atom, a sulfur atom that may be substituted, a nitrogen atom that may be substituted, or a carbonyl group.

R ^a to R ^c are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which can be substituted, an aryl group having 4 to 10 carbon atoms which can be substituted or an aralkyl group having 6 to 10 carbon atoms which can be substituted X is an ester group, amidino group, a carboxyl group, a cyano group, or a nitro group.

A is a hydroxyl group, an amine group, an ester group, a sulfonylamino group, a carboxyl group, a cyano group, or a nitro group.

n represents an integer value from 1 to 5.

The above-described formula (2), examples of R ^3, may be preferably used as (1) R in the above Formula ³ are exemplified.

Further, as R ⁴ ~ R ^9, may preferably be used as R (1) In the above formula ⁴ ~ R ⁹ are illustrated.

Further, as R ^a ~ R ^c and X, may preferably be used as in the above-described formula ^(A) R ^a ~ R ^c and X are exemplified.

As R ¹⁰ , those exemplified as the substituents α ¹ and α ² in the following <4.1 divalent oligomeric fluorene> can be preferably used.

The "ester group and fluorenylamino group" in A can be preferably exemplified as the "ester group and sulfonylamino group" of X in the formula (A).

The specific structure of the "amine group" in A is not particularly limited, and examples thereof include (i) a first-order amine group having two hydrogen atoms in a nitrogen atom, and (ii) a hydrogen atom and a carbon number of 1 to a nitrogen atom. The secondary amine group of the organic substituent of 10, (iii) the tertiary amine group of the organic atom having two carbon substituents of 1 to 10 each independently on the nitrogen atom. As the organic substituent having 1 to 10 carbon atoms, those exemplified as the organic substituent having 1 to 10 carbon atoms in the "ester group" of X in the formula (A) can be preferably used.

Among these, in terms of being able to produce polyester or polyamine by using one of the oligomeric amidines A2 of the present invention, A is preferably a hydroxyl group or an amine group, and in terms of ease of production, A is more Preferred is hydroxyl.

<2.3 Specific examples of oligomeric fluorene A2 having two different reactive functional groups>

Specific examples of the oligomeric fluorene A2 of the present invention include a structure shown in the following [F] group.

[Chemical 94]

[Chem 95]

<2.4 Physical properties of oligomeric fluorene A2 having two different reactive functional groups>

It is the same as that described in the item <1.6 Physical properties of oligomeric fluorene A1 having one reactive functional group>.

<2.5 Manufacturing method of oligomeric fluorene A2 having two different reactive functional groups>

The method for producing the oligomeric fluorene A2 of the present invention is not particularly limited, and examples thereof include a method in which the oligomeric fluorene represented by the above formula (1) is reacted with an electrophilic compound to produce the oligomeric fluorene. The oligomeric fluorene A2 represented by the above formula (2).

Hereinafter, the manufacturing method of the oligomeric fluorene A2 represented by the said Formula (2) is divided into manufacturing method A, manufacturing method B, manufacturing method C, and manufacturing method D by the type of the electrophilic compound, and is described.

<2.5.1 Manufacturing method A: Manufacturing method using addition of formaldehyde>

The oligomeric fluorene represented by the following formula (2a) having a methylol group as a reactive functional group can be obtained from the oligomeric fluorene represented by the following formula (1) in the presence of a base in accordance with the reaction represented by the production method A. A1 and formaldehyde.

In the formula ^{(2a), R 3 ~ R} 9, R a ~ R c, X and n have the above-described system and the formula (1).

<2.5.1.1 Formaldehydes>

The formaldehyde used in the production method A is not particularly limited as long as it can supply formaldehyde to the reaction system. Examples include gaseous formaldehyde, aqueous formaldehyde solution, paraformaldehyde polymerized by formaldehyde, and Alkanes, etc. Among these, the use of paraformaldehyde is particularly preferable from the viewpoint of being industrially inexpensive, easy to handle and accurate weighing due to the powder form.

Regarding the amount of formaldehyde used, the upper limit is not particularly limited with respect to oligomeric fluorene A1 as a raw material. If the amount of use is too large, the refining load after the reaction tends to increase, which is usually 10 times that of oligomeric fluorene A1. It is preferably 5 times or less, more preferably 3 times or less. The lower limit is 1 mole of the theoretical amount relative to the raw material, and therefore is usually 1 mole or more. In order to make the reaction proceed faster, the starting materials or intermediates are not left, but formaldehydes may be used in an excessive amount relative to the oligomeric A1 of the starting materials. Regarding the preferred amount of formaldehyde used at this time, it is 1.1 times or more, and more preferably 1.2 times or more, relative to the oligomeric fluorene A1 of the raw material.

<2.5.1.2 Alkali>

As the base, 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 alkali metals such as sodium carbonate, sodium bicarbonate, and potassium carbonate can be used. Carbonate, magnesium carbonate, calcium carbonate and other alkaline earth metal carbonates, sodium phosphate, sodium phosphate sodium phosphate, potassium phosphate and other phosphoric acid alkali metal salts, organic lithium salts such as n-butyl lithium, third butyl lithium, sodium methoxide, Alkoxides of alkali metals such as sodium ethoxide, potassium tert-butoxide, etc., alkali metal hydrides such as sodium hydride or potassium hydride, tertiary amines such as triethylamine, diazabicycloundecene, and tetramethylammonium hydroxide , Tetrabutylammonium hydroxide, etc. These may be used individually by 1 type, and may use 2 or more types together.

Among these, an alkali metal alkoxide having sufficient basicity in this reaction is preferable, and industrially inexpensive sodium methoxide or sodium ethoxide is more preferable. Here, the alkali metal alkoxide may be used in a powder form or in a liquid form such as an alcohol solution. Alternatively, it may be prepared by reacting an alkali metal with an alcohol.

The upper limit of the amount of alkali used is not particularly limited. If the amount is too large, the refining load after the reaction tends to increase. It may be less than 1 mole, and preferably 0.5 times mole, relative to oligomeric A1. Hereinafter, it is more preferably 0.2 times mole or less. On the other hand, if the amount of alkali used is too small, the progress of the reaction is slowed. Therefore, as the lower limit, the oligomeric fluorene A1 of the raw material is usually 0.01 times mole or more, and preferably 0.05 times mole or more.

<2.5.1.3 Solvent>

Production method A is preferably performed using a solvent.

Specific solvents that can be used include acetonitrile and propionitrile as the alkyl nitrile solvent, and acetone, methyl ethyl ketone, and methyl isobutyl ketone as the ketone solvent. As the ester solvent, Examples include methyl acetate, ethyl acetate, propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, methyl 3-methoxypropionate, 3- Linear esters such as methyl ethoxypropionate, methyl lactate, ethyl lactate; cyclic esters such as γ-butyrolactone, caprolactone; ethylene glycol monomethyl ether acetate, ethylene glycol Ether esters such as alcohol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol-1-monomethyl ether acetate, propylene glycol-1-monoethyl ether acetate, and the like, and examples thereof include ether solvents Diethyl ether, tetrahydrofuran, 1,4-bis Alkane, methylcyclopentyl ether, third butyl methyl ether, and the like. Examples of the halogen-based solvent include 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane. Examples of the halogen-based aromatic hydrocarbon include chlorobenzene and 1,2-dichlorobenzene. Examples of the fluorene-based solvent include N, N-dimethylformamide and N, N, -dimethyl. Acetylamine and the like include fluorene-based solvents such as dimethyl fluorene and cyclobutane. Examples of the cyclic aliphatic hydrocarbon include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. And other monocyclic aliphatic hydrocarbons; its derivatives are methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1 , 3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, third butylcyclohexane, n-butylcyclohexane, Isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; polycyclic aliphatic hydrocarbons such as decahydronaphthalene; n-pentane, Non-cyclic aliphatics such as n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Examples of the hydrocarbon include toluene, para-xylene, o-xylene, and meta-xylene. Examples of the aromatic heterocyclic ring include pyridine. Examples of the alcohol-based solvent include methanol, ethanol, isopropyl alcohol, and the like. N-butanol, tertiary butanol, hexanol, octanol, cyclohexanol and the like.

Among them, in terms of the high solubility of anions generated from oligomeric fluorene A1 and the tendency of the reaction to proceed well, a fluorene-based solvent or a fluorene-based solvent is preferred, and N is particularly preferred. , N-dimethylformamide.

These solvents may be used alone or in combination of two or more. With regard to the amount of solvent used, the upper limit is not particularly limited. If the production efficiency of the target substance in each reactor is considered, 10 times the volume, preferably 7 times the volume of oligomeric A1, which is the raw material, is usually used. It is more preferably an amount of 4 times the volume. On the other hand, if the amount of the solvent used is too small, stirring tends to be difficult and the progress of the reaction tends to be slow. Therefore, as the lower limit, the volume of the oligomeric A1, which is the raw material, is usually 1 times the volume, preferably 2 times. Volume, feed It is preferably an amount of 3 times the volume.

<2.5.1.4 Reaction form>

When the manufacturing method A is carried out, the reaction may be performed in a batch manner, a flow-through reaction, or a combination of these, and the form is not particularly limited.

Regarding the method of adding the reaction reagent to the reactor in the case of batch type, it can be seen that when the base is added once at the beginning of the reaction, the decomposition reaction is easy to proceed. Therefore, it is preferable to add oligomeric A1 and formaldehyde as raw materials. After adding solvents and solvents, a small amount of alkali is added successively.

<2.5.1.5 Reaction conditions>

With regard to the manufacturing method A, it is found that if the temperature is too low, a sufficient reaction rate cannot be obtained, while if the temperature is too high, the decomposition reaction proceeds, and it is desirable to perform temperature management. Therefore, when using N, N-dimethylformamidine as an optimal solvent and sodium ethoxide as an optimal base, it is usually carried out at a lower limit of -50 ° C and an upper limit of 30 ° C. Specifically, when R ³ is a methylene group, the upper limit of the reaction temperature is preferably performed at 20 ° C, more preferably 10 ° C. On the other hand, the lower limit is implemented at a temperature of preferably -20 ° C, more preferably 0 ° C or higher. In the case where R ³ is ethylene, the upper limit of the reaction temperature is preferably 25 ° C., and more preferably 20 ° C. The lower limit is preferably implemented at 0 ° C, more preferably 10 ° C or higher.

<2.5.1.6 Separation and purification of target>

After the completion of the reaction, the oligomeric fluorene represented by the formula (2a) as the target can be added to the reaction solution by adding the reaction solution to acidic water such as dilute hydrochloric acid, or the reaction solution to add the reaction solution to the target solution. The oligomeric tritium represented by the formula (2a) is precipitated and separated.

After completion of the reaction, an oligomeric fluorene-soluble solvent and water represented by the formula (2a) as a target substance may be added to the reaction solution to perform extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent.

The obtained oligomeric fluorene represented by the formula (2a) can be directly used as a polymer raw material for polymerization. It can also be polymerized after purification. As the purification method, ordinary purification methods such as recrystallization or reprecipitation, extraction purification, and column chromatography can be used without limitation.

The presence of metal components is often a problem in the polymerization reaction. Regarding the long-period periodic table, the proportion of metals in Group 1 and Group 2 in the monomer can be 500 mass ppm or less, and more preferably 200 mass. ppm or less, more preferably 50 mass ppm or less, and even more preferably 10 mass ppm or less. In order to remove metal components, the liquid separation operation is usually very effective. The oligomeric fluorene represented by the formula (2a) as a target substance tends to dissolve only in highly polar solvents such as N, N-dimethylformamide or tetrahydrofuran. In many cases, the liquid separation operation in the two-layer system is very difficult. On the other hand, even if the precipitates after the reaction is stopped are subjected to ordinary purification treatments such as water washing and hot suspension washing with an arbitrary solvent, it is difficult to sufficiently remove the mixed metal components, and some 100 mass ppm remain in the precipitates. The situation of the left and right metal components. As a good refining method for removing metal components, a simple and effective inorganic salt removal method is preferred, even if the reaction precipitate containing impurities is dissolved in N, N-dimethylformamide, tetrahydrofuran, etc. A method in which a high solvent is added to water for precipitation.

<2.5.2 Manufacturing method B: Manufacturing method using addition reaction of olefin having electron withdrawing group>

The oligomeric fluorene represented by the following formula (2b) may be different from the oligomeric fluorene A1 represented by the following formula (1) according to the reaction represented by the manufacturing method B in the presence of a base, according to the reaction represented by the manufacturing method B: The olefin (4-2) having an electron-drawing group is produced.

In the formula ^{(2b), R 3 ~ R} 9, R a ~ R c, X and n have the above-described system and the formula (1). In addition, R ^a2 to R ^c2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or an aromatic group having 6 to 10 carbon atoms that can be substituted. Alkyl, Xa is ester, amido, carboxy, cyano, or nitro. Among them, R ^a to R ^c and X are different from at least one of R ^a2 to R ^c2 and Xa.

As R ^a2 ~ R ^c2 and Xa, may preferably be employed as in the formula ^(A) R ^a ~ R ^c and X are exemplified by, in R ^a ~ R ^c and X, and R ^a2 ~ R ^c2 and Xa in You must make at least one of them different. In particular, from the viewpoint of simply imparting specific physical properties derived from different reactive functional groups to the resin, it is preferable that X and Xa are different from each other in the formula (2b).

The oligomeric fluorene represented by the formula (2b) can be produced according to the method for producing the oligomeric fluorene A1 represented by the above formula (1). In this case, after the oligomeric fluorene A1 is produced, it may be isolated, refined, and then manufactured. The oligomeric fluorene represented by formula (3) and the olefin having an electron-withdrawing group represented by formula (4) may also be used. After the reaction, the reaction is further performed with an olefin having an electron-withdrawing group represented by the formula (4-2).

<2.5.3 Manufacturing Method C: Manufacturing method of oligomeric fluorene represented by formula (2c) using alkylation and hydrolysis reaction of oligomeric fluorene A1)>

The oligomeric fluorene represented by the following formula (2c) can be synthesized by using an alkylation reaction between the oligomeric fluorene A1 and the alkylating agent represented by the formula (8) to have a detachment represented by the formula (2c-1). The oligomeric fluorene step (step (ia)) and the subsequent hydrolysis reaction (step (ia)) can be produced, and can also be expressed by oligomeric fluorene A1 and formula (9) A method (step (ib)) for synthesizing an oligomeric fluorene having a protecting group represented by formula (2c-2), an alkylation reaction of an alkylating agent, and a method for subsequent hydrolysis reaction (step (iib)) And manufacture.

[Chemical 99]

In the ^{formula, R 3 ~ R 9, R} a ~ R c, X , and n lines of the above formula (1). R ¹⁰ is the same as R ^{10 in} the formula (2).

Xb and Xc represent a radical. Examples of the leaving group include a halogen atom (excluding fluorine), a methanesulfonyl group, or a tosylsulfonyl group.

T represents a protecting group. Examples of the protecting group include a methoxymethyl group, a 2-methoxyethoxymethyl group, a tetrahydropiperanyl group or a third butoxycarbonyl group, a benzyloxycarbonyl group, a trimethylsilyl group, Or the third butyldimethylsilyl group.

The alkylation reaction of amidines is well known. For example, 9,9-bis (bromohexyl) fluorene or 9,9-bis (iodohexyl) fluorene and other 9,9-bis (haloalkyl) fluorene (J. Org. Chem., 2010, 75, 2714.). Based on these findings, an oligomeric fluorene having a leaving group can be synthesized by using oligomeric fluorene A as a raw material. Further, there are many reported examples of hydrolysis of halogens (Bull. Korean Chem. Soc., 2008, 29.2491.), And the oligomeric fluorene represented by the formula (2c) can be synthesized through this route.

Examples of the alkylating agent used in step (ia) include diiodomethane, 1,2-diiodoethane, 1,3-diiodopropane, 1,4-diiodobutane, and 1,5- Diiodopentane, 1,6-diiodohexane, dibromomethane, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane Alkane, 1,6-dibromohexane, dichloromethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, Linear alkyl dihalides (excluding fluorine atoms) such as 1,6-dichlorohexane and 1-bromo-3-chloropropane, 2,2-dimethyl-1,3-dichloropropane, etc. Aryl dihalides containing side chains (excluding fluorine atoms), 1,4-bis (bromomethyl) benzene, 1,3-bis (bromomethyl) benzene, etc. (Except), glycols such as ethylene glycol dimethylsulfonate, ethylene glycol di-p-toluenesulfonate, propylene glycol dimethylsulfonate, tetramethylene glycol dimethylsulfonate, etc. Disulfonate, etc.

Examples of the alkylating agent used in step (ib) include protection of haloalkanols such as 3-bromopropanol, 2-bromopropanol, and 3-chloro-2,2-dimethyl-1-propanol.化 体 etc.

<2.5.4. Manufacturing method D: Manufacturing method using oligomeric fluorene represented by formula (2d) using alkylation of oligomeric fluorene A1)>

The oligomeric fluorene represented by the formula (2d) can be produced by an alkylation reaction between the oligomeric fluorene A1 and the alkylating agent represented by the formula (10).

In the formula (10), Xb and R ¹⁰ are the same as those in the formula (8). R ²¹ is the same as R ^g .

In the formula ^{(2d), R 3 ~ R} 9, R a ~ R c, X and n have the above-described system and the formula (1).

It is an oligomeric fluorene of formula (2d), and R ¹⁰ is other than a direct bond. The method described in step (ia) or (iib) in <2.5.3 Manufacturing Method C> can be used in the presence of a base. In the same manner, oligomeric fluorene A1 is produced by subjecting an alkylating agent represented by formula (10) to an alkylation reaction.

Examples of the alkylating agent used in Production Method D include methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, n-butyl chloroacetate, third butyl chloroacetate, methyl bromoacetate, and ethyl bromoacetate. Ester, tert-butyl bromoacetate, methyl iodoacetate, ethyl iodoacetate, tert-butyl iodoacetate, methyl chloropropionate, ethyl chloropropionate, tert-butyl chloropropionate, methyl bromopropionate Esters, ethyl bromopropionate, third butyl bromopropionate, methyl iodopropionate, ethyl iodopropionate, third butyl iodopropionate, and other alkyl halides, 4-chloromethylbenzoic acid Methyl ester, methyl 4-bromomethylbenzoate, ethyl 4-chloromethylbenzoate, ethyl 4-bromomethylbenzoate, methyl 3-chloromethylbenzoate, 3-bromomethylbenzoate Haloalkyl benzoates, such as methyl esters, and the like.

<3 oligomeric fluorene composition>

The oligomeric fluorene composition of the present invention comprises oligomeric fluorene A1 (oligomeric fluorene compound having 1 reactive functional group) and / or oligomeric fluorene A2 (oligomeric fluorene compound having 2 different reactive functional groups) (Hereinafter, these may be summarized and abbreviated as "oligomeric fluorene A.") and the following oligomeric fluorene B having a chemical structure different from the oligomeric fluorene A. Especially from the viewpoint of controlling the polymerization rate and molecular weight of the resin, it is preferable to include oligomeric fluorene A1. On the other hand, from the viewpoint of simply obtaining the physical properties of the resin due to two or more reactive functional groups, etc. In terms of oligomeric fluorene A2, it is preferred.

<3.1 Oligomeric B>

The oligomeric fluorene B includes an oligomeric fluorene structural unit (hereinafter referred to as an oligomeric fluorene structural unit b), which is a carbon atom at the 9 position of the fluorene unit b which may have two or more substituents, and may have a substituent through each other. An alkylene group which may have a substituent, or an aralkyl group which may have a substituent, which is chain-bonded, and is a fluorene unit b at both ends of the oligomeric fluorene structure unit b The 9-position carbon atom has the same reactive functional group represented by the following formula (B).

In formula (B), R ^d to R ^f are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or 6 carbon atoms that can be substituted Aralkyl of ~ 10, X is ester, amido, carboxy, cyano, or nitro. * It is bonded to the carbon atom at position 9 of the fluorene unit b.

As the alkylene group, alkylene group, and alkylene group of bonded fluorene unit b, those exemplified in <1.1 alkylene group, alkylene group, alkylene group, and the like can be preferably used, respectively. The group of the bonded fluorene unit b may be the same as or different from the group of the bonded fluorene unit a in the oligomeric fluorene. Together with From the viewpoint of simultaneous production, it is preferably the same as the base of the bond-binding unit a in the oligomeric fluorene.

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

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 used, respectively. Moreover, 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 oligomeric fluorene. From the viewpoint of simultaneous production, it is preferably the same as R ^a to R ^c and X of the formula (A) in the oligomeric fluorene.

<3.2 Specific Structure of Oligomeric B>

As the oligomeric fluorene B of the present invention, specifically, those represented by the following general formula (7) can be preferably used.

In formula (7), R ^{13 is} each independently a direct bond and an alkyl group having 1 to 4 carbon atoms which may have a substituent, and R ¹⁴ to R ¹⁹ are each independently a hydrogen atom and 1 to 10 carbon atoms which may have a substituent. An alkyl group, an aryl group having 4 to 10 carbon atoms which may have a substituent, a fluorenyl group having 1 to 10 carbon atoms which may have a substituent, a fluorenyl group having 1 to 10 carbon atoms which may have a substituent, may have a substituent Alkoxy groups having 1 to 10 carbon atoms, aryloxy groups having 1 to 10 carbon atoms which may have substituents, amine groups having substituents, vinyl groups having 1 to 10 carbon atoms which may have substituents, may have The acetylene group having 1 to 10 carbon atoms of the substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. Among them, at least two adjacent groups in 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 alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted or an aralkyl group that can be substituted with 6 to 10 carbon atoms X ¹ is an ester group, amidino group, a carboxyl group, a cyano group, or a nitro group.

n represents an integer value from 1 to 5.

As R ¹³ in formula (7), those exemplified as R ³ in formula (1) can be preferably used. Similarly, as R ¹⁴ to R ¹⁹ in the formula (7), those exemplified as R ⁴ to R ⁹ in the formula (1) can be preferably used. In addition, as R ^d to R ^f in the formula (7), those exemplified as R ^a to R ^c in the formula (1) can be preferably used. Furthermore, as X ¹ in the formula (7), those exemplified as X in the formula (1) can be preferably used. As n in the formula (7), those exemplified as n in the formula (1) can be preferably used.

<3.3 Specific Examples of Oligomeric B>

Specific examples of the oligomeric fluorene B of the present invention include a structure shown in the following [G] group.

[Chem. 105]

<3.4 content>

The content of the oligomeric fluorene A in the oligomeric fluorene composition of the present invention is not particularly limited, and from the viewpoint of controlling the molecular weight of the polymer, it is preferably 0.1% by mass or more, more preferably 0.5% by mass Above, still more preferably 1% by mass or more, still more preferably 60% by mass or less, still more preferably 50% by mass or less, still more preferably 40% by mass or less.

The content of the oligomeric fluorene B in the oligomeric fluorene composition of the present invention is not particularly limited. From the viewpoint of improving the polymerization degree of the polymer, it is preferably 5% by mass or more, and more preferably 10% by mass. % Or more, and more preferably 15% by mass or more. The content is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

The content ratio of oligomeric A and oligomeric B included in the oligomeric fluorene composition is not particularly limited. From the viewpoint of controlling the molecular weight of the polymer, the oligomeric fluorene included in the composition is not limited. The molar ratio of A to oligomeric fluorene B (molar number of oligomeric fluorene A / mollar number of oligomeric fluorene B) is preferably 0.001 or more, more preferably 0.005 or more, and still more preferably 0.01 or more. From the viewpoint of improving the polymerization degree of the polymer, it is preferably 0.05 or less, more preferably 0.03 or less, and even more preferably 0.02 or less.

The mole number of the oligomeric fluorene A or the oligomeric fluorene B contained in the oligomeric fluorene composition can be estimated, for example, by using a calibration curve from the area% analyzed by HPLC.

<4 resin composition>

A resin composition can be produced by using the oligomeric fluorene of the present invention.

When oligomeric fluorene A is used as the oligomeric fluorene, for example, a resin composition made of a polymer having a structure represented by the following formula (5) at the end or a resin composition containing the polymer can be obtained.

In formula (5), R ^{3 is} independently a direct bond and an alkylene group having 1 to 4 carbon atoms that may have a substituent, and R ⁴ to R ⁹ are each independently a hydrogen atom and 1 to 10 carbon atoms that may have a substituent. An alkyl group, an aryl group having 4 to 10 carbons which may have a substituent, a fluorenyl group having t to 10 carbons which may have a substituent, a fluorenyl group having 1 to 10 carbons which may have a substituent, may have a substituent Alkoxy groups having 1 to 10 carbon atoms, aryloxy groups having 1 to 10 carbon atoms that may have substituents, amine groups that may have substituents, vinyl groups having 1 to 10 carbon atoms that may have substituents, may An ethynyl group having 1 to 10 carbon atoms having a substituent, a sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group. Among them, at least two adjacent groups in 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 alkyl group having 1 to 10 carbon atoms which can be substituted, an aryl group having 4 to 10 carbon atoms which can be substituted or an aralkyl group having 6 to 10 carbon atoms which can be substituted .

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

n represents an integer value from 1 to 5.

＊ Bound with the bond of the linker.

As R ³ to R ⁹ , R ^a to R ^c, and n in the formula (5), those exemplified as R ³ to R ⁹ , R ^a to R ^c, and n in the formula (1) can be preferably used.

<4.1 Divalent Oligomers>

The polymer of the resin composition of the present invention is preferably a divalent oligofluorene as a repeating unit.

In this case, the resin composition of the present invention may contain, in addition to a polymer having a divalent oligomeric fluorene as a repeating unit, other polymers described below, and may also contain additives.

The method for obtaining a polymer having a divalent oligomeric fluorene as a repeating unit is not particularly limited. For example, when an oligomeric fluorene compound A2 is used as the oligomeric fluorene, 2 having a reactive functional group-derived 2 can be obtained. A polymer having more than one linking group and having a divalent oligomeric fluorene as a repeating unit. Moreover, it is also possible to obtain a polymer having a divalent oligomeric fluorene as a repeating unit by using oligomeric fluorene B.

The divalent oligomeric fluorene includes two or more fluorene units which may have a substituent, and the carbon atoms at the 9th position of the fluorene unit are mutually via an alkylene group which may have a substituent, an arylene group which may have a substituent, Or, an aralkyl group which may have a substituent and is chain-bonded.

As the fluorene unit, those exemplified as the fluorene unit a of the oligomeric fluorene A, or those exemplified as the fluorene unit b of the oligomeric fluorene B can be preferably used.

Similarly, as the alkylene group of the bonded fluorene unit, those exemplified as the alkylene group of the bonded oligomer A of the oligomer A, or as the bonded unit oligomer B of the oligomer B Exemplified by alkylene.

In addition, as the extended aryl group of the bonded fluorene unit, those exemplified as the extended aryl group of the bonded oligomeric unit A of the oligomeric fluorene A, or as the extended fluorene unit b of the oligomeric fluorene B Fang Base instantiator.

Furthermore, as the extended aralkyl group of the bonded fluorene unit, the exemplified as the extended aralkyl group of the bonded fluorene unit A of the oligomeric fluorene A, or the bonded fluorene unit b of the oligomeric fluorene B can be preferably used. Exemplified by aralkyl.

Regarding the divalent oligomeric fluorene described above, in the two or more fluorene units, the substituents α ¹ and α ² are respectively bonded to the carbon atom at the 9th position of the fluorene unit at both ends, and the substituent α ¹ and α ^{2 are} set to a divalent basis. In this case, α ¹ and α ² may be the same or different. In addition, the substituents α ¹ and α ² may include a direct bond, and the 9-position carbon atom of the fluorene unit may be a divalent group.

The substituents α ¹ and α ^{2 are} not particularly limited, and examples thereof include a direct bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, an arylene group having 4 to 10 carbon atoms which may be substituted, or Substituted aralkyl groups having 6 to 10 carbons, or selected from substitutable carbon groups of 1 to 10 carbons, substitutable arylene groups of 4 to 10 carbons, and substitutable carbons Two or more groups in the group consisting of 6-10 aralkyl groups are bonded by an oxygen atom, a sulfur atom that may be substituted, a nitrogen atom that may be substituted, or a carbonyl group.

As the "alkylene group having 1 to 10 carbon atoms which may be substituted", examples exemplified as the alkylene group of the bonded fluorene unit a can be preferably used. In this case, it is preferable to use a carbon number of 2 or more from the viewpoint of exhibiting inverse wavelength dispersion. On the other hand, it is preferable to set the number of carbons to 1 from the viewpoint of showing planar dispersibility. Furthermore, when the inverse wavelength dispersion property is exhibited, the number of carbons is preferably 5 or less, and more preferably 4 in view of the fact that the orientation of the ring is easily fixed to the main chain and the inverse wavelength dispersion characteristics are efficiently obtained. Hereinafter, it is more preferably 3 or less, and even more preferably 2 or less. On the other hand, from the viewpoint of imparting flexibility to the resin composition, the number of carbons is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.

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

"Selected from the group consisting of an alkylene group having 1 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, and an alkylene group having 6 to 10 carbon atoms that can be substituted The specific structure in which two or more groups are bonded by an oxygen atom, a sulfur atom that may be substituted, a nitrogen atom that may be substituted, or a carbonyl group "is listed below, and is not limited to these, and may be listed as follows Let us describe the divalent basis shown by the [H] group.

Among these, it is preferable that two or more groups selected from the group consisting of an alkylene group, an alkylene group, or an alkylene group to be imparted with flexibility while maintaining transparency and stability of the resin composition are connected by an oxygen atom. The formed group is more preferably a group in which an alkylene group represented by the following [I] group is bonded to an oxygen atom while imparting flexibility and increasing the glass transition temperature of the resin composition.

From the viewpoint of increasing the ratio of radon, in the case of using these connected bases, it is preferable to set the number of carbons to 2 or more, and more preferably to 6 or less. It is set to 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 a carbon number of 2 or more, the fluorene ring (fluorene unit) is roughly Since it is vertically aligned with the main chain, even if the proportion of the divalent oligomeric fluorene in the resin composition is small, the anti-wavelength dispersion property tends to develop. In the latter case, from the same viewpoint, it is preferable that both α ¹ and α ² have a carbon number of 2 or more. On the other hand, in a case where both of the substituents α ¹ and α ² are set to one carbon number (that is, a methylene group which may be substituted), the fluorene ring (fluorene unit) is not aligned substantially vertically to the main chain but Orientation is performed with a large inclination, so there is a tendency that even if the ratio of the divalent oligomeric fluorene in the resin composition is changed in a wide range, it is easy to be a plane with a small difference in phase difference in wide bands. Dispersion.

Among these, a direct bond, an alkylene group having 1 to 10 carbon atoms which can be substituted, an arylene group having 4 to 10 carbon atoms which can be substituted, or a group selected from the group consisting of 1 to 10 carbon atoms which can be substituted 2 or more of the group consisting of an alkylene group that can be substituted, an alkylene group that has 4 to 10 carbon atoms, and an alkylene group that can be substituted with 6 to 10 carbon atoms are composed of an oxygen atom, Substituted sulfur atom, a group which may be connected by a substituted nitrogen atom or a carbonyl group.

More preferred are a straight bond, a straight chain alkylene group, a side chain-containing alkylene group, and a linear or side chain-type alkylene group at any two positions of the alicyclic structure shown in the above [A] group. Alicyclic alkylene, phenylene, or selected from the group consisting of an alkylene group having 1 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, and a substituted one In the group consisting of 6 to 10 carbonized aralkyl groups, two or more groups are connected by oxygen atoms.

Further preferred are direct bonds, methylene, ethylidene, n-propylidene, n-butylidene, and methylmethylene, which have a tendency to achieve a lower photoelastic coefficient required for optical films because they do not have an aromatic ring. , 1-Methylethene, 2-Methylethene, 2,2-Dimethylpropane, 2-methoxymethyl-2-methylpropane or the following [J] group The alicyclic alkylene shown.

(The substitution positions of the two bonding bonds in each ring structure shown in the above [J] group are arbitrary, and Two bonds may be bonded to the same carbon and substituted).

Furthermore, it is more preferably a direct bond, methylene, ethylidene, n-propylidene, n-butylidene, methylmethylene, 1-methylidene, 2-methylidene, or 2,2- Dimethylpropane. Especially preferred are methylene, ethyl, or n-propyl.

If the chain length is longer, the glass transition temperature tends to be lower. Therefore, a shorter chain-like base such as a base having 2 or less carbon atoms is preferred. Furthermore, since the molecular structure becomes smaller, the concentration of the fluorene ring (fluorene ratio) in the repeating unit tends to be high, so that the required optical physical properties can be developed efficiently. Moreover, it is preferable that even if it is contained in an arbitrary mass with respect to the entire mass of the resin composition, it may be a plane dispersion having a small phase dispersion and a small wavelength dispersion, and it may be introduced in a short stage and industrially inexpensively. The advantage of methylene.

On the other hand, in order to improve the mechanical strength or reliability at high temperature of the obtained film, it is preferred that the aryl group having a carbon number of 4 to 10 which can increase the glass transition temperature of the resin composition, or selected from the group consisting of An alkylene group having 1 to 10 carbon atoms and an arylene group having 4 to 10 carbon atoms that can be substituted. Two or more groups are connected by oxygen atoms, and more preferably 1,4- A phenylene group, a 1,5-naphthyl group, a 2,6-naphthyl group, or a divalent group represented by the following [H2] group.

When applying to a retardation film having inverse wavelength dispersion, it is important to appropriately select the substituents α ¹ and α ² . For example, a base of carbon number 1 represented by methylene has an unexpected tendency to have low inverse wavelength dispersion. Therefore, R ¹ and R ^{2 are} preferably a direct bond, or at least one of them is a base of carbon number 2 or more. .

More preferably, it is a direct bond, an alkylene group having 2 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, or an alkylene group having 1 to 10 carbon atoms that can be substituted. Available 2 or more of the group consisting of an arylene group having 4 to 10 carbon atoms and an aralkyl group having 6 to 10 carbon atoms that can be substituted include an oxygen atom, a sulfur atom that can be substituted, and Substituted nitrogen atom or carbonyl group.

Further, a straight bond, a linear alkylene group, a linear alkylene group including a side chain, and any two of the alicyclic structures shown in the above-mentioned [A] group are preferably linear or side chain alkylene groups. Alicyclic alkylene, phenylene, or selected from the group consisting of an alkylene group having 1 to 10 carbon atoms that can be substituted, an alkylene group having 4 to 10 carbon atoms that can be substituted, and In the group consisting of substituted aralkyl groups having 6 to 10 carbon atoms, two or more groups are connected by oxygen atoms.

More preferred are direct bonds, ethylidene, n-propylidene, n-butylidene, methylmethylene, 1-methylethylidene, which do not have aromatic rings and can achieve the lower photoelastic coefficient required by optical films. , 2-methyl butyral, 2,2-dimethyl butyral, 2-methoxymethyl-2-methyl butyral or alicyclic butane as shown in the above [J] group Or 1,4-phenylene which can increase the glass transition temperature of the resin composition, selected from the group consisting of an alkylene group having 1 to 10 carbon atoms that can be substituted and an alkylene group having 4 to 10 carbon atoms that can be substituted Two or more of the groups in the group are formed by connecting oxygen atoms.

Especially preferred are direct bond, ethyl, n-propyl, n-butyl, methylmethylene, 1-methylethyl, 2-methylethyl, or 2,2-dimethylene base.

Ethyl or propyl is preferred. If the chain length is longer, the glass transition temperature tends to be lower. Therefore, a shorter chain-like base such as a base having 3 or less carbon atoms is preferred. Furthermore, since the molecular structure becomes smaller, the concentration (fluorene ratio) of the fluorene ring in the repeating unit can be increased, and thus the required optical physical properties can be developed efficiently.

The same substituents α ¹ and α ² are preferred because they facilitate production.

As described above, the resin composition of the present invention tends to be formed by a polymer having a repeating unit in which two or more carbon atoms at the 9-position of the fluorene unit b are connected to each other by a specific carbon-carbon bond. It can form or contain the polymer, so that the optical properties derived from the fluorene ring can be obtained more effectively.

As the divalent oligomeric fluorene, specifically, those represented by the following general formula (11) can be preferably used.

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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl, fluorenyloxy having 1 to 1b carbon having a substituent, alkoxyl having 1 to 10 carbons having a substituent, aryloxy having 1 to 10 carbons having a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in R ⁴ to R ⁹ may be bonded to each other to form a ring.

n represents an integer value from 1 to 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, as R ³ to R ⁹ and n in the above formula (11), those exemplified as R ³ to R ⁹ and n in the above formula (1) can be preferably used, respectively.

<4.2 Polymer>

The polymer contained in the resin composition of the present invention has a divalent oligofluorene as a repeating unit. Examples include divalent oligomeric polymers in which oligomeric fluorenes are linked to each other by an arbitrary linking group. The polymer may have any repeating unit other than a divalent oligomeric fluorene. Of copolymers.

<4.3 link base>

It is the same as that described in the item "3.4 Linker" of "Invention 2" above.

<4.4 copolymer>

The polymer having a divalent oligomeric fluorene as a repeating unit may be a copolymer further containing an arbitrary divalent organic group (except for a divalent oligomeric fluorene) as a repeating unit. In this case, the repeating units are preferably formed by connecting the above-mentioned linking groups.

In the copolymer, an arbitrary divalent organic group that can be used in combination with a divalent oligomeric fluorene is the same as that described in the item <3.5 Copolymer> of the aforementioned "Invention 2".

<4.5 copolymerization composition>

It is the same as that described in the item <3.7 Copolymerization Composition> of the aforementioned "Invention 2".

<4.6 Composition of Resin Composition>

It is the same as that described in the item <3.9 Resin Composition Composition> in the above-mentioned "Invention 2".

"Invention 4"

Hereinafter, the manufacturing method of the oligomeric fluorene diester of this invention 4 and the resin composition using it is explained in full detail.

In addition, the following (general) formulae (1), (1a), (1b), (1a-I), (1a-II), (10e), (I) to (V), (IIa) (IIb) and (VI-1) are those who explain each structure in the fourth aspect of the present invention.

<1 oligomeric diester A>

The oligomeric fluorene diester of the present invention (hereinafter referred to as "oligomeric fluorene diester A") includes two or more fluorene units which may have a substituent, and the carbon atoms at the 9-position of the fluorene unit are directly bonded to each other. Or a chain via an alkylene group which may have a substituent, an alkylene group which may have a substituent, or an alkylene group which may have a substituent, and the metal content ratio is 500 Mass ppm or less.

<1.1 Specific Structure>

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

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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in 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 from 1 to 5.

In the above formula (1), as R ¹ and R ² , those exemplified in the related groups of R ¹ and R ² in the above-mentioned "Invention 1" can be preferably used, respectively.

Similarly, as R ³ , those exemplified in the related base of R ³ in the above-mentioned "Invention 1" can be preferably used.

As R ⁴ to R ⁹ , those exemplified in the related groups of R ⁴ to R ⁹ in the above-mentioned "Invention 1" can be preferably used.

In addition, as R ¹⁰ , those exemplified as the organic substituent in the <1.3 ester group> of the above-mentioned "Invention 2" can be preferably used.

<1.2 metal content>

The content of the above metal is preferably 400 mass ppm or less, more preferably 200 mass ppm or less, and further preferably 100 in terms of reducing the thermal stability of the oligomeric fluorene diester A and causing coloration. Mass ppm or less, more preferably 50 mass ppm or less, even more preferably 10 ppm or less, and most preferably 5 mass ppm or less.

There is no particular limitation on the type of the above-mentioned metals. Since there is a possibility that metal used as a catalyst may be mixed in the production of oligomeric fluorene diesters, it can be considered to be selected from Groups 1 and 2 of the long-period periodic table. , Group 12, Group 14 and at least one metal of a transition metal. Specifically, examples of the Group 1 metal include lithium, sodium, potassium, and cesium. Examples of the Group 2 metal include magnesium, calcium, and barium. Examples of the Group 12 metal include zinc and cadmium. Examples of the metal include aluminum, and examples of the Group 14 metal include tin and lead, and examples of the transition metal include iron, copper, titanium, zirconium, manganese, cobalt, and vanadium. Regarding the oligomeric fluorene diester of the present invention, a catalyst and the like at the time of production remain, and usually contain a metal.

In the oligomeric fluorene diester of the present invention, there is a long-period periodic table Group 1 metal such as sodium or potassium and a second group containing calcium derived from the step of methylolating the formaldehydes in the presence of a base. Group metal possibilities. In addition, there are transition metals such as titanium, copper, iron, and the like, which are derived from a step of transesterifying a diaryl carbonate in the presence of a transesterification reaction catalyst, or a long-period periodic table such as sodium and potassium Or a Group 2 metal such as magnesium or calcium, or a Group 12 metal such as zinc or cadmium, or a Group 14 metal such as tin.

Among these, from the viewpoint of the reactivity of the transesterification catalyst, a transition metal is preferred, titanium or zirconium is more preferred, and titanium is more preferred.

Examples of the method for measuring the metal content include an ICP-QMS method.

As a method of making the amount of metal into the above range, for example, ordinary purification For example, recrystallization, reprecipitation, extraction purification, filter filtration and other filtration operations, and column chromatography. When the oligomeric fluorene diester A of the present invention is produced by a transesterification method, it is important to reduce the water or impurities in the raw material and the carboxylic acid component in advance.

<1.3 Production method of oligomeric fluorene diester A>

The manufacturing method of the oligomeric fluorene of this invention is not specifically limited, For example, it can manufacture by the manufacturing method A or manufacturing method B shown by following formula.

Here, in each structural 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 alkyl group having 1 to 10 carbons that may have a substituent, an aryl group having 4 to 10 carbons that may have a substituent, and 1 to 10 carbons that may have a substituent Fluorenyl group, fluorenyloxy group having 1 to 10 carbon atoms which may have a substituent, alkoxyl group having 1 to 10 carbon atoms which may have a substituent, aryloxy group having 1 to 10 carbon atoms which may have a substituent, may have Substituent amino group, vinyl group having 1 to 10 carbon atoms which may have a substituent, ethynyl group having 1 to 10 carbon atoms which may have a substituent, sulfur atom having a substituent, silicon atom having a substituent, halogen atom , Nitro, or cyano. Among them, at least two adjacent groups in R ⁴ to R ⁹ may be bonded to each other to form a ring.

n represents an integer value from 1 to 5.

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

<1.3.1 Manufacturing Method A>

Production method A uses Rhenium (I) as a raw material, converts it to 9-hydroxymethylhydrazone (IV), and reacts an olefin (V) synthesized by dehydration with a fluorenyl anion to produce R ³ Method for methylene oligomeric fluorene compound (II). Furthermore, unsubstituted 9-hydroxymethylfluorene can be purchased as a reagent. The oligomeric fluorene diester (1) can be prepared by introducing an ester group from the oligomeric fluorene compound (II) obtained here according to the following step (ii).

For example, a method for converting a mixture of 9-hydroxymethylfluorene to dibenzofulvene and an oligomeric fluorene by anionic polymerization is known (J. Am. Chem. Soc., 123, 2001, 9918- 9183.). The oligomeric fluorene compound (II) can be produced using these as a reference.

<1.3.2 Manufacturing Method B>

Production method B is to produce an oligomeric fluorene compound (II) by performing a cross-linking reaction (step (i)) of the fluorene type (I) as a raw material, and then introducing an ester group (step (ii)), thereby producing an oligosaccharide. Method for polyfluorene diester (1).

In each of the above formulae, R ¹ to R ¹⁰ are synonymous with R ¹ to R ¹⁰ in formula (1).

Hereinafter, the manufacturing method B is divided into the manufacturing method of step (i) oligomeric fluorene compound (II), and the manufacturing method of step (ii) oligomeric fluorene diester (1).

<1.3.3 Step (i): Method for producing oligomeric fluorene compound (II)>

In the above formulae, R ³ to R ⁹ and n are the same as R ³ to R ⁹ in the formula (1).

Hereinafter, the case where the manufacturing method of the oligomeric fluorene compound (II) in step (i) is divided into n and R ³ is described.

<1.3.3.1 In a case where n = 1 and R ³ is a direct bond: 9,9 ': 9', 9 "-Mitsumi's manufacturing method>

There are several known methods for synthesizing 9,9'-bisfluorene, which can be synthesized from fluorenone or 9-bromofluorene (J. Chem. Res., 2004,760; Tetrahedron Lett., 2007, 48, 6669.) . Furthermore, 9,9'-bipyrene can be purchased as a reagent.

<1.3.3.2 In the case where n = 2 and R ³ is a direct bond: 9,9 ': 9', 9 "-Mitsumi's manufacturing method>

Regarding the method of synthesizing 9,9 ': 9', 9 "-bispyrene, a plurality of kinds are known and can be synthesized from fluorenone (Eur, J. Org. Chem. 1999, 1979-1984.).

<1.3.3.3 Step (ia): Production method in a case where R ³ is methylene>

The oligomeric fluorene compound having a methylene cross-linking represented by the following general formula (IIa) can be produced from a fluorene (I) and formaldehyde in accordance with a reaction represented by the following formula in the presence of a base.

In the above formulas, the same as R ⁴ ~ R ⁹ and n lines of (1) R in the above formula ⁴ ~ R ⁹ and n meaning.

<1.3.3.3.1 Formaldehydes>

The so-called formaldehydes used in step (ia) are not particularly limited as long as they can supply formaldehyde to the reaction system. Examples include gaseous formaldehyde, aqueous formaldehyde solution, paraformaldehyde polymerized by formaldehyde, and Alkanes, etc. From the viewpoint that it is industrially inexpensive and easy to handle and can be accurately weighed due to the powder form, paraformaldehyde is more preferred. On the other hand, formaldehyde is more preferred from the viewpoint that it is industrially inexpensive and has less risk of exposure during addition due to liquid.

(Definition of theoretical quantity)

In the case of producing the target oligomeric fluorene compound (IIa), the theoretical amount (molar ratio) of formaldehydes relative to the fluorene type (I) of the raw material is represented by n / (n + 1).

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

When the formaldehydes are used in an amount exceeding the theoretical amount with respect to the amidine (I), the target oligomeric amidine compound (IIa) tends to generate an amidine crosslinked oligomeric amidine compound. It can be seen that as the number of fluorene rings of an oligomeric fluorene compound increases, the solubility decreases. Therefore, when there are four or more fluorene rings crosslinked oligomeric fluorene compounds in the target, the purification load tends to increase. Therefore, in general, the amount of formaldehydes used is preferably n / (n + 1) times the mole of the theoretical amount for the purpose.

(Why not better than the theoretical amount)

In addition, it can be seen that if the amount of formaldehydes used is significantly lower than the theoretical amount of n / (n + 1), there will be more than the target trifluorene compound (IIa), and the difluorene compound with a smaller number of crosslinks of the fluorene ring will become the main product The product (I) or the raw material (I) is left unreacted, so that the yield tends to decrease significantly.

Therefore, regarding the optimum amount of formaldehyde used, in the case of n = 1, it is usually 0.1 times or more, preferably 0.3 times or more, more It is preferably 0.38 times moles or more, usually 0.5 times moles or less, more preferably 0.46 times moles or less, and still more preferably 0.42 times moles or less.

In the case of n = 2, it is usually 0.5 times or more Molar, preferably 0.55 times or more Molar, further preferably 0.6 times or more Molar, and usually 0.66 times or less Molar, preferably 0.65 times or more Beam is less than or equal to 0.63, and is more preferably 0.63 or less. As mentioned above, it can be seen that depending on the amount of formaldehyde used, the ratio of the structure of the main product to the product greatly changes. By using under the condition that the amount of formaldehyde used is limited, the target n can be obtained in high yield. Number of oligomeric fluorene compounds (IIa).

<1.3.3.3.2 Alkali>

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; sodium carbonate, and carbonic acid. Carbonates of alkali metals such as sodium hydrogen and potassium carbonate, carbonates of alkaline earth metals such as magnesium carbonate and calcium carbonate, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate, and potassium phosphate, n-butyl lithium, and third butyl lithium And other organic lithium salts, sodium alkoxides of alkali metals such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide, alkali metal salts such as sodium hydride or potassium hydride, triethylamine, diazabicycloundecene, and other tertiary Tertiary ammonium hydroxide such as amine, tetramethylammonium hydroxide and tetrabutylammonium hydroxide. These may be used individually by 1 type, and may use 2 or more types together.

When the reaction is performed in a homogeneous system, among these, the alkali metal alkoxide having sufficient basicity in the reaction is preferred, and industrially inexpensive sodium methoxide or sodium ethoxide is more preferred. Here, the alkoxide of the alkali metal may be used in a powder form or in a liquid form such as an alkali solution. It is also possible to prepare by reacting an alkali metal with an alcohol.

On the other hand, when the reaction is performed in a two-layer system, among these, an aqueous solution of an alkali metal hydroxide having sufficient basicity in the reaction is preferable, and industrially inexpensive sodium hydroxide, Aqueous solution of potassium hydroxide.

In addition, regarding the concentration of the aqueous solution, in the case of using a particularly preferable sodium hydroxide aqueous solution, if the concentration is thin, the reaction speed is significantly reduced. Therefore, it is generally used at 10 wt / wt% or more, preferably 25 wt / wt% or more, More preferably, it is an aqueous solution of 40 wt / wt% or more.

When the reaction is carried out in a homogeneous system, the upper limit of the amount of alkali used is not particularly limited with respect to the amidine (I) as a raw material, but if the amount is too large, the purification load after stirring or reaction becomes large Therefore, it is usually 10 times or less, preferably 5 times or less, and more preferably 1 time or less. On the other hand, if the amount of alkali used is too small, the reaction tends to slow down. Therefore, as the lower limit, it is usually 0.01 times the mole or more, and preferably 0.1 times the mole or more, relative to the raw material (I). , And more preferably 0.2 times mole or more.

On the other hand, when the reaction is performed in a two-layer system, regarding the amount of alkali used, The upper limit is not particularly limited with respect to the stilbene (I) as a raw material, but if it is used in an excessive amount, the refining load after stirring or reaction tends to increase, so it is usually 10 times the mole of the stilbene (I). Hereinafter, it is preferably 5 times or less, more preferably 2 times or less. On the other hand, if the amount of alkali used is too small, the reaction tends to slow down. Therefore, as the lower limit, it is usually 0.1 times or more, and preferably 0.3 times or more, relative to the type (I) of the material. , And more preferably 0.4 times mole or more.

<1.3.3.3.3 Solvents>

Step (ia) is preferably performed using a solvent. Specific examples of usable solvents include acetonitrile and propionitrile as the alkyl nitrile solvent, and diethyl ether, tetrahydrofuran, and 1,4-dicarbonate as the ether solvent. Alkane, methylcyclopentyl ether, third butyl methyl ether, and the like. Examples of the halogen-based solvent include 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane. Examples of the halogen-based aromatic hydrocarbon include chlorobenzene and 1,2-dichlorobenzene. Examples of the fluorene-based solvent include N, N-dimethylformamide and N, N, -dimethyl. Acetylamine, N-methylpyrrolidone and the like. Examples of the fluorene-based solvents include dimethyl fluorene and cyclobutane. Examples of the cyclic aliphatic hydrocarbon include cyclopentane and cyclohexane. , Monocyclic aliphatic hydrocarbons such as cycloheptane, cyclooctane; methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2- Dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, third butylcyclohexane , N-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; polycyclic forms such as decalin Aliphatic hydrocarbons; n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Examples of the acyclic aliphatic hydrocarbon include toluene, para-xylene, o-xylene, and meta-xylene. Examples of the alcohol-based solvent include methanol, ethanol, isopropanol, n-butanol, and Tributanol, hexanol, octanol, cyclohexanol, etc.

Among the homogeneous reactions, the anion generated from the amidine (I) has high solubility, and the reaction proceeds well, and the ammonium system of a polar solvent is preferred. Solvent, or fluorene-based solvent. Among them, N, N-dimethylformamide is particularly preferred. The reason is that there is a tendency that the triamidine compound (IIa) has a low solubility in N, N-dimethylformamide, and the target substance precipitates rapidly after it is generated, and the progress of subsequent reactions is suppressed, and the target Material selectivity is improved.

In the two-layer reaction, two layers are formed with an alkaline aqueous solution. The anion generated from the amidine (I) has high solubility, and a polar solvent is preferred in terms of the tendency of the reaction to proceed well. An ether-based solvent or a halogen-based solvent. Among them, tetrahydrofuran is particularly preferred. The reason for this is that the trifluoride compound (IIa) has a low solubility in tetrahydrofuran, and the target substance is rapidly precipitated after it is generated, the subsequent reaction progress is suppressed, and the selectivity of the target substance is improved.

These solvents may be used alone or in combination of two or more.

As for the amount of the solvent to be used, an amount of 10 times the volume, preferably 7 times the volume, and more preferably 4 times the volume is used as the raw material (I). On the other hand, if the amount of the solvent used is too small, stirring tends to be difficult and the progress of the reaction tends to be slow. Therefore, as the lower limit, a volume of 1 times as much as the raw material (I) is preferably used, preferably 2 The volume-by-volume amount, and more preferably the volume-by-volume amount is 3 times.

<1.3.3.3.4 Reaction Form>

When performing step (ia), the reaction may take the form of a batch reaction, a flow-through reaction, or a combination of these, and the form is not particularly limited.

<1.3.3.3.5 Reaction conditions>

Regarding step (ia), in order to suppress the formation of a fluorene ring-crosslinked compound compared to the trifluorene compound (IIa), it is preferable to perform the reaction at a low temperature as much as possible. On the other hand, if the temperature is too low, a sufficient reaction rate may not be obtained.

Therefore, as a specific reaction temperature, the upper limit is usually 40 ° C, preferably 30 ° C, and more preferably 20 ° C. On the other hand, the lower limit is -50 ° C, preferably -20 ° C, and more preferably 0 ° C or higher.

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

<1.3.3.3.6 Separation and purification of target>

After completion of the reaction, the target oligomeric fluorene compound (IIa) can be added to the reaction solution by adding the reaction solution to acidic water such as dilute hydrochloric acid, or by adding acidic water such as dilute hydrochloric acid to the reaction solution to make the target oligomeric fluorene Compound (IIa) is precipitated and isolated.

After the reaction is completed, a solvent in which the oligomeric fluorene compound (IIa) as a target is soluble and water may be added to the reaction solution to perform extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent. Among them, the solubility of the oligomeric fluorene compound (IIa) in a solvent at room temperature tends to be very low, and therefore, a method of precipitating it by contacting with acidic water is generally preferred.

The obtained oligomeric fluorene compound (IIa) can also be used directly as a raw material in step (ii), but it can also be used in step (ii) after purification. As the purification method, ordinary purification methods such as recrystallization, reprecipitation, extraction purification, and column chromatography can be used without limitation.

<1.3.3.4 Step (ib): Manufacturing method in a case where R ³ is other than a direct bond>

The oligomeric fluorene compound represented by the following general formula (IIb) is produced by using a fluorene (I) as a raw material, in the presence of an alkylating agent (VIIIa) and a base, and reacting according to the formula (ib).

The oligomeric fluorene compound in the above formula is represented by structural formula (IIb).

In the above formulas, R ^3, and R ⁴ ~ R ⁹ and n lines (1) of the formula R ^3, the same as R ⁴ ~ R ⁹ and n meaning. X represents a radical. Examples of the leaving group include a halogen atom (except fluorine), a methanesulfonyl group, or a tosylsulfonyl group.

As a method for producing an oligomeric fluorene compound (IIb), a method is known in which n-butyllithium is used as a base to generate an anion of the fluorene (I) and then couple it with an alkylating agent (VIIIa). A manufacturing method in the case where ³ is an ethyl group or a case where R ³ is a propyl group (Organometallics, 2008, 27, 3924; J. Molec. Cat. A: Chem., 2004, 214, 187.) In addition to alkylene, there are also reports of cross-linking with xylylene (J. Am. Chem. Soc., 2007, 129, 8458.). However, in these methods using n-butyllithium, for industrial production, there is a tendency that it is very difficult both 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, and 1,5- Diiodopentane, 1,6-diiodohexane, dibromomethane, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane Alkane, 1,6-dibromohexane, dichloromethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, Linear alkyl dihalides (excluding fluorine atoms) such as 1,6-dichlorohexane and 1-bromo-3-chloropropane, 2,2-dimethyl-1,3-dichloropropane, etc. Aryl dihalides containing side chains (excluding fluorine atoms), 1,4-bis (bromomethyl) benzene, 1,3-bis (bromomethyl) benzene, etc. Excluding), ethylene glycol dimethyl sulfonate, ethylene glycol dimethyl sulfonate, propylene glycol dimethyl sulfonate, 1,4-butanediol dimethyl sulfonate and other diol disulfonates and the like.

<1.3.4 Production method of oligomeric fluorene diester (1)>

Hereinafter, the manufacturing method of the oligomeric fluorene diester (1) in the step (ii) represented by the following formula is classified and described by the types of R ¹ and R ² .

[Chemical 118]

In the above formulas, R ¹ ~ R ⁹ and n have the above-described formula based R (1) in the ¹ ~ R ⁹ and n have the same meaning. R _i , R _ii and R _iii represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted, an aryl group having 4 to 10 carbon atoms which may be substituted, or an aromatic group having 6 to 10 carbon atoms which may be substituted alkyl.

<1.3.4.1 Step (iia): Manufacturing method using Michael addition in general formula (1)>

The oligomeric fluorene diester represented by the following general formula (1a) is obtained from an oligomeric fluorene compound (II) and an α, β-unsaturated ester in the presence of a base according to the reaction represented by step (iia) below. (VI) Manufacturing.

In the above formulas, R ³ ~ R ¹⁰ and n lines and n ³ ~ R ¹⁰ and the formula R (1) in the same meaning. R _i , R _ii and R _iii each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or 6 to 10 carbon atoms that can be substituted Of aralkyl.

<1.3.4.1.1 α, β-unsaturated ester>

The α, β-unsaturated ester system 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 each independently represent a hydrogen atom and a carbon number. An alkyl group of 1 to 10, an aryl group of 4 to 10 carbons that can be substituted, or an aralkyl group of 6 to 10 carbons that can be substituted. Specific examples include: methyl, ethyl, n-propyl, isopropyl, cyclohexyl, etc. (which may be straight or side chain) alkyl, phenyl, 1-naphthyl, 2-naphthyl , Aryl such as 2-thienyl, aralkyl such as benzyl, 2-phenylethyl, and p-methoxybenzyl.

Examples of the α, β-unsaturated ester (VI) include methyl acrylate, ethyl acrylate, phenyl acrylate, allyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. Acrylates such as 1,4-cyclohexanedimethanol monoacrylate, methyl methacrylate, ethyl methacrylate, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, Methacrylic esters such as 2-hydroxyethyl methacrylate, α-substituted unsaturated esters such as methyl 2-ethylacrylate and methyl 2-phenylacrylate, methyl cinnamate, ethyl cinnamate, butyl Β-substituted unsaturated esters such as methyl enoate and ethyl butenoate. Among these, an unsaturated carboxylic acid ester represented by the following general formula (VI-1) into which a polymerization-reactive group can be directly introduced is preferred.

(In the formula, R ¹⁰ represents an organic substituent having 1 to 10 carbon atoms, and R _iii represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be substituted, an aryl group having 4 to 10 carbon atoms that can be substituted, or Arylalkyl with 6 to 10 carbon atoms that can be substituted). The acrylates, methacrylates, or α-substituted unsaturated esters contained therein are more preferable, and from the viewpoint of reaction speed and reaction selectivity, it is more preferable that R _iii is a hydrogen atom or a methyl group. Acrylates or methacrylates. The smaller R ¹⁰ is industrially cheap and easy to be distilled and purified, and the reactivity is also high. Therefore, it is more preferably methyl acrylate, ethyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate, Or phenyl methacrylate. Among these, ethyl acrylate and ethyl methacrylate are particularly preferred because carboxylic acids are difficult to hydrolyze and difficult to produce by-products.

On the other hand, the organic substituents in the ester group are esters having hydroxyalkyl groups such as 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate. In this case, it is particularly preferable because raw materials of polyester carbonate and polyester can be obtained in the first stage.

It is also possible to use two or more different α, β-unsaturated esters (VI). In terms of simplicity of purification, it is preferable to use one type of α, β-unsaturated ester (VI).

The polymerization activity of α, β-unsaturated ester (VI) is relatively high. Therefore, if it is present at a high concentration, it tends to be easily polymerized due to external stimuli such as light, heat, acid, and alkali. At this time, there is a case where it becomes very dangerous due to a large heat release. Therefore, the use amount of the α, β-unsaturated ester (VI) is preferably not excessively used from the viewpoint of safety. It is usually 10 times or less, preferably 5 times or less, and more preferably 3 times or less relative to the oligomeric fluorene compound (II) as a raw material. The lower limit is 2 times the mole in terms of the theoretical amount of the raw material, and therefore is usually 2 times the mole or more. In order to speed up the reaction without leaving raw materials or intermediates, the amount of α, β-unsaturated ester (VI) used is 2.2 times more than the mole of the oligomeric fluorene compound (II) of the raw materials, which is It is preferably 2.5 times more than Mohr.

<1.3.4.1.2 alkali>

As the base, 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 alkali metals such as sodium carbonate, sodium bicarbonate, and potassium carbonate can be used. Carbonate, magnesium carbonate, calcium carbonate and other alkaline earth metal carbonates, sodium phosphate, sodium hydrogen phosphate, potassium phosphate and other phosphoric acid alkali metal salts, organic lithium salts such as n-butyl lithium, third butyl lithium, sodium methoxide, Alkoxides of alkali metals such as sodium ethoxide, potassium tert-butoxide, etc., alkali metal hydrides such as sodium hydride or potassium hydride, tertiary amines such as triethylamine, diazabicycloundecene, and tetramethylammonium hydroxide , Tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and other tertiary ammonium hydroxide. These may be used individually by 1 type, and may use 2 or more types together.

When R ³ is a methylene group and other cases, there is a tendency that the reactivity of the oligomeric fluorene compound (II) is greatly different. Therefore, the case where R ³ is methylene is described separately from the case other than R ³ .

When R ³ is a methylene group, the oligomeric fluorene compound (II) is in a solvent, and a decomposition reaction is easily performed in the presence of a base. Therefore, when a reaction is performed in a two-layer system of an organic layer and an aqueous layer, a water-soluble inorganic base is preferably used in terms of suppressing side reactions such as decomposition reactions. Among them, in terms of cost and reactivity, an aqueous solution of an alkali metal hydroxide, particularly an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is more preferable. In addition, regarding the concentration of the aqueous solution, in the case of using an especially preferred sodium hydroxide aqueous solution, if the concentration is relatively thin, the reaction rate tends to be significantly reduced. Therefore, it is particularly preferred to use 10wt / wt% or more, preferably An aqueous solution of 30 wt / wt% or more, more preferably 40 wt / wt% or more.

When R ³ is other than methylene, the reaction is also performed in the two-layer system of the organic layer and the water layer. However, when the reaction is performed using an organic base dissolved in the organic layer, the reaction proceeds quickly, so Preferably, an organic base is used. Among these, an alkali metal alkoxide having sufficient basicity in this reaction is preferable, and industrially inexpensive sodium methoxide or sodium ethoxide is more preferable. Here, the alkali metal alkoxide may be used in a powder form or in a liquid form such as an alcohol solution. Alternatively, it may be prepared by reacting an alkali metal with an alcohol.

In the case where R ³ is methylene, the upper limit of the amount of base used is not particularly limited relative to the oligomeric fluorene compound (II) as a raw material. If the amount is too large, there may be a purification load after stirring or reaction. When it becomes larger, when using an aqueous sodium hydroxide solution of 40 wt / wt% or more, which is a particularly preferred base, it is usually 10 times or less the volume of the oligomeric fluorene (II), preferably 5 times the volume. The amount is less than or equal to 2 times the volume amount. If the amount of the base is too small, the reaction rate is significantly reduced. Therefore, the amount of the base relative to the oligomeric fluorene compound (II) of the raw material is usually 0.1 times or more by volume. It is preferably at least 0.2 times the volume, more preferably at least 0.5 times the volume.

When R ³ is other than methylene, the upper limit of the amount of base used is not particularly limited relative to the oligomeric fluorene compound (II) as a raw material. If the amount is too large, there may be purification after stirring or reaction. When the load becomes large, when using sodium methoxide or sodium ethoxide, which is a particularly preferable base, it is usually 5 times or less, preferably 2 times or less, relative to the oligomeric fluorene compound (II). It is more preferably 1 time or less, more preferably 0.5 time or less. If the amount of alkali is too small, the reaction rate tends to decrease significantly. Therefore, the oligomeric fluorene (II) of the alkali relative to the raw material is usually 0.005 times mole or more. It is preferably at least 0.01 times the mole, more preferably at least 0.05 times the mole, and even more preferably at least 0.1 times the mole.

<1.3.4.1.3 Phase-to-phase transfer catalyst>

In the case where the reaction is performed in a two-layer system of an organic layer and an aqueous layer in step (iia), in order to increase the reaction speed, 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, Halides (except fluorine) of quaternary ammonium salts such as trioctylmethylammonium chloride, tetrabutylammonium iodide, acetamyltrimethylammonium bromide, benzyltriethylammonium chloride, etc. , N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl-N-formyl chloride Halides (except fluorine) of quaternary pyrrolidinium salts such as methylpyrrolidinium, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholinium bromide, iodine Tertiary morpholinium salts such as N-butyl-N-methylmorpholinium, N-allyl-N-methylmorpholinium bromide (except fluorine), N-methyl chloride -N-benzylpiperidinium, N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide, N-methyl-N-butylpiperidinium acetic acid Halides (except fluorine) of quaternary piperidinium salts such as salts, iodized N-methyl-N-ethylpiperidinium, and crown ethers. A quaternary ammonium salt is preferable, and tetrabutylammonium bromide, benzyltrimethylammonium chloride, or benzyltriethylammonium chloride is more preferable.

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

Regarding the amount of the phase-transfer catalyst used, if the amount of the oligomeric fluorene compound (II) is too much as a raw material, side reactions such as hydrolysis of esters or successive Michael reactions tend to become apparent, and from the viewpoint of cost Generally speaking, it is 5 times more than oligomeric fluorene compound (II). Below the ear, it is preferably 2 times the mole or less, and further preferably below 1 time the mole. If the amount of the interphase transfer catalyst used is too small, the reaction rate tends to decrease significantly. Therefore, the amount of the interphase transfer catalyst used is usually 0.01 times or more moles relative to the oligomeric fluorene compound (II) of the raw material. It is preferably at least 0.1 times mole, more preferably at least 0.5 times mole.

<1.3.4.1.4 Solvent>

Step (iia) is preferably performed using a solvent.

Specific solvents that can be used include acetonitrile and propionitrile as the alkyl nitrile solvent, and acetone, methyl ethyl ketone, and methyl isobutyl ketone as the ketone solvent. As the ester solvent, Examples include methyl acetate, ethyl acetate, propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, methyl 3-methoxypropionate, 3- Linear esters such as methyl methoxypropionate, methyl lactate, ethyl lactate; cyclic esters such as γ-butyrolactone, caprolactone; ethylene glycol monomethyl ether acetate, ethylene glycol Ether esters such as alcohol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol-1-monomethyl ether acetate, propylene glycol-1-monoethyl ether acetate, and the like, and examples thereof include ether solvents Diethyl ether, tetrahydrofuran, 1,4-bis Alkane, methylcyclopentyl ether, third butyl methyl ether, and the like. Examples of the halogen-based solvent include 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane. Examples of the halogen-based aromatic hydrocarbon include chlorobenzene and 1,2-dichlorobenzene. Examples of the fluorene-based solvent include N, N-dimethylformamide and N, N, -dimethyl. Acetylamine and the like include fluorene-based solvents such as dimethyl fluorene and cyclobutane, and examples of cyclic aliphatic hydrocarbons include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Monocyclic aliphatic hydrocarbons; methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1, 2 3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, third butylcyclohexane, n-butylcyclohexane, isopropyl Butylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; Polycyclic aliphatic hydrocarbons such as decalin; n-pentane, n-hexane Non-cyclic aliphatic hydrocarbons such as alkane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Examples of the aromatic hydrocarbon include toluene, para-xylene, o-xylene, and meta-xylene. Examples of the aromatic heterocyclic ring include pyridine. Examples of the alcohol-based solvent include methanol, ethanol, isopropyl alcohol, N-butanol, tertiary butanol, hexanol, octanol, cyclohexanol and the like.

When R ³ is a methylene group, it is known that by using a solvent separated from the water phase, side reactions such as a decomposition reaction of the oligomeric fluorene compound (II) can be suppressed. Furthermore, when a solvent that sufficiently dissolves the oligomeric fluorene compound (II) of the raw material is used, the reaction tends to proceed well. Therefore, the solubility of the oligomeric fluorene compound (II) using the raw material is preferably 0.5% by mass or more. The solvent is more preferably a solvent having a solubility of 1.0% by mass or more, and particularly preferably a solvent having a solubility of 1.5% by mass or more. Specifically, a halogen-based aliphatic hydrocarbon, a halogen-based aromatic hydrocarbon, an aromatic hydrocarbon, or an ether-based solvent is preferred, and dichloromethane, chlorobenzene, chloroform, 1,2-dichlorobenzene, tetrahydrofuran, 1,4-two Alkane, or methylcyclopentyl ether.

These solvents may be used alone or in combination of two or more.

The upper limit of the amount of the solvent used is not particularly limited. If the production efficiency of the target substance in each reactor is considered, the volume of the oligomeric fluorene compound (II), such as the raw material, is usually 20 times the volume, preferably 15 times. The volume amount is more preferably an amount of 10 times the volume amount. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent becomes worse, the stirring becomes difficult, and the progress of the reaction tends to be slow. Therefore, as the lower limit, an oligomeric fluorene compound (II) as a raw material is usually used. The amount is 1 times the volume, preferably 2 times the volume, and more preferably 4 times the volume.

When R ³ is other than methylene, it is known that the solubility of the organic base and the oligomeric fluorene compound (II) has a large influence on the reaction rate. In order to ensure the solubility, it is more preferably used. Solvents with a dielectric constant above a certain value. As a solvent for sufficiently dissolving the organic base and the oligomeric fluorene compound (II), an aromatic heterocyclic ring, an alkyl nitrile-based solvent, a fluorene-based solvent, and a fluorene-based solvent are preferred, and pyridine, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylmethane, cyclobutane.

These solvents may be used alone or in combination of two or more.

With regard to the amount of solvent used, the upper limit is not particularly limited. If the production efficiency of the target substance in each reactor is considered, 20 times the volume, preferably 15 times the volume of the oligomeric fluorene (II) used as the raw material is usually used. The amount is more preferably an amount of 10 times the volume. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent becomes worse, the stirring becomes difficult, and the progress of the reaction tends to be slow. Therefore, as the lower limit, an oligomeric osmium (II) used as a raw material is usually used. An amount of 1 volume, preferably an amount of 2 volume, and further preferably an amount of 4 volume.

<1.3.4.1.5 Reaction Form>

When the step (iia) is performed, the form of the reaction may be a batch reaction, a flow-through reaction, or a combination of these, and the form is not particularly limited.

Regarding the method of feeding the reaction reagent into the reactor in the case of batch type, when α, β-unsaturated ester (VI) is added at one time at the start of the reaction, α, β-unsaturated ester (VI) is higher The concentration is present, so that the polymerization reaction of side reactions easily proceeds. Therefore, it is preferable to add the α, β-unsaturated ester (VI) one after another in small amounts and multiple times after adding the oligomeric fluorene compound (II), the interphase transfer catalyst, the solvent, and the base.

<1.3.4.1.6 Reaction conditions>

In step (iia), if the temperature is too low, a sufficient reaction rate cannot be obtained; otherwise, if the temperature is too high, the polymerization reaction of α, β-unsaturated ester (VI) proceeds or is easily generated due to hydrolysis. The oligomeric fluorene monoester monocarboxylic acid represented by the following general formula (1a-I) and the oligomeric fluorene dicarboxylic acid represented by (1a-II) have a tendency to be preferably temperature-controlled. Therefore, as the reaction temperature, the lower limit is usually 0 ° C, preferably 10 ° C, and more preferably 15 ° C. On the other hand, the upper limit is usually 40 ° C, preferably 30 ° C, and more preferably 20 ° C.

[Chemical 121]

In the above ^{formulas, n, R 3 ~ R 10} , R i, R ii , and R _iii lines as in the above-described formula ^{(1a) n, R 3 ~} R 10, R i, R ii , and R _iii same meaning.

Regarding the usual reaction time in step (iia), the lower limit is usually 30 minutes, preferably 1 hour, and more preferably 2 hours. If the reaction time is longer, the oligomeric fluorene diester (1a) is generated. The possibility of generating a carboxylic acid by hydrolysis is usually 10 hours, preferably 5 hours, and even more preferably 2 hours.

<1.3.4.1.7 Separation and purification of target>

After the reaction, the target oligomeric oligomeric diester (1a) can be removed from the reaction solution by filtering by-produced metal halides and residual inorganic bases, and then concentrating the solvent, or A method such as adding a poor solvent of the target substance, etc., separates the oligomeric fluorene diester (1a) as the target substance and separates it.

After the completion of the reaction, acidic water and a solvent soluble in the oligomeric fluorene diester (1a) as a target substance may be added to the reaction solution to perform extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent.

The solvent that can be used during extraction is not particularly limited as long as it dissolves the oligomeric diester (1a) as the target, and aromatic hydrocarbon compounds such as toluene and xylene, and dichloromethane can be preferably used. Or one or more halogen-based solvents such as chloroform and chloroform.

The oligomeric fluorene diester (1a) obtained here can be used directly as a raw material for polyester or polyester carbonate raw materials, or as a precursor for polycarbonate raw material monomers, but it can also be used after purification. In particular, when carboxylic acid components such as oligomeric fluorene monoester monocarboxylic acid (1a-I) and oligomeric fluorene dicarboxylic acid (1a-II) are contained as impurities, it can be seen that the oligomeric fluorene diaryl ester (2) When it is manufactured, it not only becomes the catalyst poison of the transesterification reaction catalyst, but also the gold contained in the oligomeric diaryl ester (2) Increasing the content of the metal leads to a decrease in thermal stability, so it is preferable to perform a refining operation. As the purification method, ordinary purification methods such as recrystallization, reprecipitation, extraction purification, and column chromatography can be used without limitation. Extraction purification is preferable because a carboxylic acid component can be removed as a carboxylic acid salt in an aqueous layer by using an alkaline aqueous solution. An aqueous solution of an inorganic base such as sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, or potassium hydroxide is more preferred, and an aqueous solution of a weak base such as sodium bicarbonate, sodium carbonate, or potassium carbonate, which is difficult to cause hydrolysis, is more preferred. . The oligomeric fluorene diester (1a) may be dissolved in an appropriate solvent and treated with activated carbon. The solvent that can be used at this time is the same as the solvent that can be used during extraction.

The oligomeric fluorene diester (1a) obtained here can be used directly as a raw material for polyester, polyester carbonate raw material monomer, or polycarbonate raw material monomer.

<1.3.4.2 Step (iib): Production method using alkylation reaction>

The oligomeric fluorene diester (1b) can be produced by a method in which an oligomeric fluorene compound (II) is alkylated with an alkylating agent (VIIIb) and (VIIIc).

In the above formulas, R ¹ ~ R ¹⁰ and n lines of the formula R (1) in the ¹ ~ R ¹⁰ and n have the same meaning. X represents a radical. Examples of the leaving group include a halogen atom (excluding fluorine), a methanesulfonyl group, or a tosylsulfonyl group.

The alkylation reaction of amidines is well known. For example, 9,9-bis (bromohexyl) fluorene or 9,9-bis (iodohexyl) fluorene and other 9,9-bis (haloalkyl) fluorene (J. Org. Chem., 2010, 75, 2714.). Based on these findings, an oligomeric fluorene diester (1b) can be synthesized by using an oligomeric fluorene compound (II) as a raw material.

Examples of the alkylating agent used in step (iib) include methyl chloroacetate and bromoacetic acid. Methyl ester, methyl iodoacetate, ethyl chloroacetate, ethyl bromoacetate, ethyl iodoacetate, propyl chloroacetate, n-butyl chloroacetate, third butyl chloroacetate, third butyl bromoacetate, iodoacetic acid Third butyl ester, methyl chloropropionate, methyl bromopropionate, methyl iodopropionate, ethyl chloropropionate, third butyl chloropropionate, third butyl bromopropionate, ethyl bromopropionate , Ethyl iodopropionate, methyl chlorobutyrate, methyl bromobutyrate, methyl iodobutyrate, ethyl chlorobutyrate, ethyl chlorobutyrate, ethyl iodobutyrate, third butyl iodopropionate Alkyl alkanoates, phenyl chloroacetate, phenyl bromoacetate, phenyl iodoacetate, etc. aryl alkanoates, such as methyl 4-chloromethylbenzoate, methyl 4-bromomethylbenzoate, 4 -Alkyl alkyl benzoates such as ethyl chloromethylbenzoate, ethyl 4-bromomethylbenzoate, methyl 3-chloromethylbenzoate, methyl 3-bromomethylbenzoate, and the like.

In addition, after the reaction in step (iib) is completed, it is preferable to separate and refine the oligomeric diester (1b) as a target. As a method of single isolation and purification, the method described in <1.3.4.1.7 Isolation and Refining of Targets> can be preferably used.

<1.3.4.3 Production method of oligomeric perylene diaryl ester of general formula (2) (production method of oligomeric perylene diaryl ester compound (2) using transesterification reaction)>

The oligomeric fluorene diaryl ester compound (2) can be produced by a method (step (iic)) of an oligomeric fluorene diester compound (1) and a transesterification reaction step with a diaryl carbonate (11a).

In the above formulas, R ¹ ~ R ¹⁰ and n lines of the formula R (1) in the ¹ ~ R ¹⁰ and n have the same meaning. Ar ¹ represents an aryl group having 4 to 10 carbon atoms which may be substituted.

<1.3.4.3.1 Production method of oligomeric perylene diaryl ester of general formula (2) (production method of oligomeric perylene diaryl ester compound (2) using transesterification reaction)>

Ar ¹ is an oligomeric fluorene diarylate compound (2) which can be substituted with an aryl group having 4 to 10 carbon atoms. In the presence of a transesterification catalyst, according to the reaction represented by step (iic), the An ester compound (1) and a diaryl carbonate (11a) are produced.

<1.3.4.3.1.1 Oligomeric fluorene diester compound (1)>

If the content of carboxylic acid in the oligomeric fluorene diester compound (1) is large, there is a tendency that the carboxylic acid becomes a catalyst poison of the transesterification reaction catalyst, and a large amount of the transesterification reaction catalyst must be used. Therefore, if the content of carboxylic acid is large, the metal content contained in the oligomeric fluorene diaryl ester compound (2) tends to increase. From the viewpoint of reducing the amount of metal contained in the oligomeric fluorene diaryl ester (2), the content of the carboxylic acid in the oligomeric fluorene diester compound (1) is preferably 5% by mass or less, and more preferably 3% by mass. Hereinafter, it is more preferably 2% by mass or less, and still more preferably 1% by mass or less. In addition, the smaller the carboxylic acid content is, the better it is. However, if it is set to 0% by mass, there is a concern that there is a significant increase in cost or a decrease in production efficiency for the purpose of preventing the inclusion of impurities. The content of the carboxylic acid capable of maintaining productivity is usually 0.1% by mass or more.

Examples of the carboxylic acid contained in the oligomeric fluorene diester compound (1) include an oligomeric fluorene monoester monocarboxylic acid or an oligomeric fluorene dicarboxylic acid.

The mole number of the oligomeric fluorene monoester monocarboxylic acid or the oligomeric fluorene dicarboxylic acid contained in the oligomeric fluorene diester compound (1) can be estimated, for example, from the area% analyzed by HPLC using a calibration curve.

<1.3.4.3.1.2 Diaryl carbonates>

Examples of the diaryl carbonates used as a reaction reagent include diphenyl carbonate, xylyl carbonate, bis (chlorophenyl) carbonate, m-tolyl carbonate, dinaphthyl carbonate, and bis (biphenyl) carbonate. Wait. Among them, diphenyl carbonate, which is inexpensive and commercially available, is preferred.

These diaryl carbonates may be used singly or in combination of two or more kinds.

Regarding the amount of diaryl carbonate used, the upper limit is not particularly limited with respect to the oligomeric fluorene diester (1) as a raw material. If the amount used is too large, the refining load after the reaction tends to increase. Less than 20 times moles of oligomeric diester, preferably 10 times moles Hereinafter, it is more preferably 5 times or less.

On the other hand, if the amount of diaryl carbonate used is too small, there may be cases where the oligomeric fluorene diester (1) as a raw material or the oligomeric fluorene monoaryl ester (10e) remaining as an intermediate is left, Therefore, as the lower limit, the oligomeric fluorene diester (1) with respect to the raw material is generally 1 time or more, preferably 1.5 time or more, and more preferably 2 time or more.

In the above formulas, R ¹ ~ R ¹⁰ and n lines of the formula R (1) in the ¹ ~ R ¹⁰ and n have the same meaning. Ar ¹ represents an aryl group having 4 to 10 carbon atoms which may be substituted.

<1.3.4.3.1.3 Transesterification reaction catalyst>

Examples of the transesterification catalyst include tetrabutoxytitanium, tetraisobutoxytitanium, tetramethoxytitanium, tetraisopropoxytitanium, tetraethoxytitanium, and tetrakis (2-ethylhexyloxy). Titanium compounds such as titanium, tetrakis (octadecyloxy), titanium tetraphenoxy, titanium (IV) acetoacetone, titanium (IV) bis (ethylacetone) isopropoxy titanium; lithium carbonate, lithium Alkali metal compounds such as lithium butylamino, lithium acetoacetone, sodium phenoxide, potassium phenol; cadmium compounds such as cadmium acetoacetone, cadmium carbonate; zirconium compounds such as zirconium acetoacetone, zirconocene, etc. Lead compounds such as lead, lead, lead, carbonate, lead acetate, tetrabutyl lead, tetraphenyl lead, triphenyl lead, dimethoxy lead, diphenoxy lead, etc. Copper compounds such as copper acetone acetone, copper oleate, butyl copper, dimethoxy copper, and copper chloride; iron hydroxide, iron carbonate, triethoxy iron, trimethoxy iron, and triphenoxy iron Other iron compounds; zinc compounds such as zinc diacetamate acetone, zinc diethoxylate, dimethoxyzinc, diethoxyzinc, and diphenoxyzinc; di-n-butyltin oxide, diphenyltin oxide , Di-n-octyltin oxide, Di-n-butyltin dimethanol, Di-n-butyltin diacrylate, Di-n-butyltin dimethacrylate, Di-n-butyl dilaurate Organotin compounds such as tin, tetramethoxytin, tetraphenoxytin, tetrabutyl-1,3-diethylfluorenyldistanoxane; aluminum compounds such as aluminum acetate, aluminum methoxide, aluminum ethoxide, and aluminum phenolate ; Vanadium compounds such as vanadium dichloride, vanadium trichloride, vanadium tetrachloride, and vanadium sulfate; phosphonium salts such as tetraphenylphenol rhenium and the like. These may be used individually by 1 type, and may use 2 or more types together.

Among these, it is preferable to use a sulfonium salt, a lithium compound, a zirconium compound, an organotin compound, or a titanium compound from the viewpoint of being industrially inexpensive and having advantages in reaction operation. Among them, an organotin compound is particularly preferred. Or titanium compounds.

Regarding the amount of the transesterification reaction catalyst, the upper limit is not particularly limited with respect to the oligomeric fluorene diester (1) as a raw material. If the amount used is too large, the refining load after the reaction tends to increase, so it is usually It is preferably 20 mol% or less, preferably 10 mol% or less, and further preferably 5 mol% or less.

On the other hand, if the amount of transesterification catalyst used is too small, the reaction time may become too long. Therefore, as the lower limit, it is usually 0.1 mol% or more relative to the oligomeric oligo diester of the raw material. 0.5 mol% or more, more preferably 1 mol% or more.

<1.3.4.3.1.4 Solvent>

In step (iic), a reaction solvent may also be used, but it is preferred that the reaction is not performed using only the oligomeric fluorene diester (1), the diaryl carbonate, and the transesterification reaction catalyst. However, in the case where the oligomeric fluorene diester (1) and the diaryl carbonate of the raw materials are solid at normal temperature and it is difficult to stir, a reaction solvent may be used. In the case of using a reaction solvent, as long as it is a solvent capable of dissolving and / or dispersing the oligomeric fluorene diester (1), diaryl carbonates, and transesterification reaction catalysts of the above materials, Arbitrary.

Specific solvents that can be used include acetonitrile and propionitrile as the alkyl nitrile solvent, and acetone, methyl ethyl ketone, and methyl isobutyl ketone as the ketone solvent, and ether solvents as the ketone solvent. , Including diethyl ether, tetrahydrofuran, 1,4-di Alkane, methylcyclopentyl ether, third butyl methyl ether, and the like. Examples of the halogen-based solvent include 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane. Examples of the halogen-based aromatic hydrocarbon include chlorobenzene and 1,2-dichlorobenzene. Examples of the fluorene-based solvent include N, N-dimethylformamide and N, N, -dimethyl. Acetylamine and the like include fluorene-based solvents such as dimethyl fluorene and cyclobutane. Examples of the cyclic aliphatic hydrocarbon include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. And other monocyclic aliphatic hydrocarbons; its derivatives are methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1 , 3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, third butylcyclohexane, n-butylcyclohexane, Isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; polycyclic aliphatic hydrocarbons such as decahydronaphthalene; n-pentane, Non-cyclic fats such as n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Hydrocarbons, examples of aromatic hydrocarbons include toluene, para-xylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3 , 4-tetrahydronaphthalene, etc. Examples of the aromatic heterocyclic ring include pyridine.

This reaction is preferably carried out at a high temperature of generally 100 ° C or higher. Therefore, among the above solvents, solvents having a boiling point of 100 ° C or higher, that is, chlorobenzene, 1,2-dichlorobenzene, trichlorobenzene, toluene, p- Xylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, tetralin, decalin, N , N-dimethylformamide, N, N-dimethylacetamide, dimethylmethane, or cyclobutane, the oligomeric fluorene diester (10b) of the raw material can be better dissolved, From the viewpoint that the boiling point is 130 ° C or higher and the reaction can be performed at a higher temperature, 1,2-dichlorobenzene, xylene, 1,3,5-trimethylbenzene, 1,2,4- Trimethylbenzene, or tetralin or decalin.

These solvents may be used alone or in combination of two or more.

Regarding the amount of solvent used, the upper limit is not particularly limited. If the production efficiency of the target of each reactor is considered, 15 times the volume of the oligomeric diester (1) as the raw material is usually used, preferably 10 The volume-by-volume amount, and more preferably, the volume-by-volume amount is 5 times. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent becomes poor and the stirring becomes difficult, and the progress of the reaction tends to be slow. Therefore, as the lower limit, an oligomerization using a raw material is generally used. The concentration of the perylene diester (1) is 1 volume volume, preferably 2 volume volume, and more preferably 4 volume volume.

<1.3.4.3.1.5 Reaction Form>

When the step (iic) is performed, the form of the reaction may be a batch reaction, a flow-through reaction, or a combination of these, and the form is not particularly limited.

<1.3.4.3.1.6 Reaction conditions>

In the step (iic), if the temperature is too low, a sufficient reaction rate may not be obtained. Therefore, the lower limit is usually 50 ° C, preferably 70 ° C, and more preferably 100 ° C. On the other hand, the upper limit is implemented at usually 250 ° C, preferably 200 ° C, and more preferably 180 ° C.

Regarding the usual reaction time in step (iic), the lower limit is usually 1 hour, preferably 2 hours, and further preferably 3 hours, and the upper limit is not particularly limited, but is usually 30 hours, preferably 20 hours, and further It is preferably 10 hours.

In step (iic), in order to shift the equilibrium to the product side, the reaction may be performed while distilling off by-products under reduced pressure. The pressure in the case of reduced 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 degree of reduced pressure is too high, even diaryl carbonates used as reagents may also sublime. Therefore, it is usually performed at 0.1 kPa or more, preferably 0.5 kPa or more, and more preferably 1.0 kPa or more.

<1.3.4.3.1.7 Separation and purification of target>

After completion of the reaction, the oligomeric fluorene diaryl ester (2) as a target substance can be isolated by adding a poor solvent to the reaction solution to precipitate the oligomeric fluorene diaryl ester (2) as a target substance.

After the reaction is completed, a target oligomeric fluorene diaryl ester (2) -soluble solvent and water may be added to the reaction solution to perform extraction. The target substance extracted by the solvent may be a method using a difference in solubility caused by a temperature difference, a method of concentrating a solvent, or A method such as adding a poor solvent is used for single isolation.

The obtained oligomeric fluorene diaryl ester (2) can also be directly used for polymerization as a polycarbonate raw material containing polyester carbonate or a polyester raw material. As the purification method, ordinary purification methods such as recrystallization, reprecipitation, extraction purification, and column chromatography can be used without limitation.

When purification is performed by a refining method such as recrystallization or reprecipitation, solvents that can be specifically used as good solvents include acetonitrile, propionitrile, and the like as alkonitrile solvents, and acetone and formaldehyde as the ketone solvents. Ethyl ethyl ketone, methyl isobutyl ketone and the like. Examples of ether solvents include diethyl ether, tetrahydrofuran, 1,4-di Alkane, methylcyclopentyl ether, third butyl methyl ether, and the like. Examples of the halogen-based solvent include 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane. Examples of the halogen-based aromatic hydrocarbon include chlorobenzene and 1,2-dichlorobenzene. Examples of the fluorene-based solvent include N, N-dimethylformamide and N, N-dimethylethyl. Examples of fluorene-based solvents include dimethyl sulfene and cyclobutane. Examples of aromatic hydrocarbons include toluene, para-xylene, o-xylene, m-xylene, and 1,3,5-. Trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-tetrahydronaphthalene, etc. Examples of the aromatic heterocyclic ring include pyridine.

The oligomeric arylene diaryl ester (2) has a large difference in solubility depending on the temperature, so methyl isobutyl ketone and 1,4-dimethyl ketone having a boiling point of 100 ° C or higher are preferred. Alkane, methylcyclopentyl ether, third butyl methyl ether, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamidamine, dimethylmethylene sulfene, cyclobutane, toluene, paraxylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2, 4-trimethylbenzene, 1,2,3,4-tetrahydronaphthalene, pyridine. Of these, toluene, para-xylene, o-xylene, m-xylene, aromatic hydrocarbons which are stable at high temperatures and have a small environmental load under non-halogen systems even in the presence of transesterification catalysts, 1,3,5-trimethylbenzene, 1,2.4-trimethylbenzene.

These good solvents can be used alone or in combination of two or more.

Regarding the amount of solvent used, the upper limit is not particularly limited. If the purification efficiency of the target of each reactor is considered, it is usually used as 15 times the mass of the oligomeric diaryl ester (2). The amount is preferably 10 times the mass amount, and more preferably 5 times the mass amount. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent becomes poor and the stirring becomes difficult, and the progress of the reaction becomes slow. Therefore, as the lower limit, a concentration meter such as an oligomeric diaryl ester (2) is usually used The amount is 0.3 times the mass, preferably 0.5 times the mass, and more preferably 1 time.

When purification is performed by a refining method such as recrystallization or reprecipitation, crystallization can be performed using only a good solvent by using a solubility difference according to temperature, but in order to improve the recovery rate, it is preferable to use a poor solvent. As a specific example of a poor solvent that can be used, examples of the cyclic aliphatic hydrocarbon include monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; Methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-bis Methylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, third butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethyl Cyclohexane, 1,3,5-trimethylcyclohexane, etc .; Polycyclic aliphatic hydrocarbons such as decahydronaphthalene; n-pentane, n-hexane, n-heptane, n-octane, isooctane, Non-cyclic aliphatic hydrocarbons such as n-nonane, n-decane, n-dodecane, and n-tetradecane. Examples of the alcohol-based solvent include methanol, ethanol, isopropanol, n-butanol, third butanol, Hexanol, octanol, cyclohexanol, etc.

Highly polar impurities can be removed. Therefore, as the poor solvent, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, tertiary butanol, hexanol, octanol, and cyclohexanol are more preferred. Methanol and ethanol with shorter carbon chains.

The oligomeric fluorene diaryl esters (2) exist in stable and quasi-stable polymorphs. In the case where a good solvent is used and the crystals are precipitated due to the difference in temperature solubility, the crystals precipitated in a quasi-stable form tend to be brittle and tend to be micronized when changing to a stable form. The micronized crystal may have poor fluidity when used industrially as a resin raw material, which may cause poor addition. On the other hand, toluene, para-xylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2, Aromatic hydrocarbons such as 3,4-tetrahydronaphthalene, and methanol, ethanol, isopropanol, n-butanol, tertiary butanol, hexanol, octanol as poor solvents When an alcohol-based solvent such as an alcohol or cyclohexanol is combined, it is preferable to obtain an initially stable crystal without causing micronization.

When combining an aromatic hydrocarbon as a good solvent and an alcoholic solvent as a poor solvent, if the temperature of the alcoholic solvent is low, quasi-stable crystals will precipitate before the addition of the alcoholic solvent. Increasing tendency. Therefore, the addition temperature of the alcohol-based solvent is usually 20 ° C or higher, preferably 30 ° C or higher, more preferably 40 ° C or higher, and even more preferably 50 ° C or higher.

Regarding the quasi-stable crystals of oligomeric perylene diaryl ester (2), if the powder X-ray diffraction measurement device (XRD) is used for analysis, it will be at 2θ = 5.6 °, 8.5 °, 11.0 °, 12.5 °, 12.9 ° The characteristic peaks were observed at 14.9 °, 16.3 °, 19.1 ° (θ = ± 0.2 °). The quasi-stable crystal is relatively brittle and easily causes phase transfer. Therefore, by continuously stirring during crystallization, micronization is performed, which causes poor extraction from the reactor or deteriorates filterability. In addition, quasi-stable crystals cannot withstand impact or avoid poor addition due to reduced powder fluidity. Therefore, it is preferred that the crystals do not include peaks of these angles of incidence.

If the amount of the good solvent used for crystallization of the oligomeric fluorene diaryl ester (2) is too small, it becomes difficult to dissolve the oligomeric fluorene diaryl ester (2), and the purification efficiency is also reduced. The lower limit is usually 0.3 times the mass, preferably 0.5 times the mass, more preferably 0.7 times the mass, and even more preferably 0.9 times the mass relative to the oligomeric fluorene diaryl ester (2). In addition, if the amount of the good solvent is too large, the loss of the oligomeric fluorene diaryl ester (2) to the filtrate increases, and the yield is reduced. Therefore, the upper limit of the amount of the good solvent is relative to the oligomeric fluorene diaryl ester (2). Usually 5 times the mass, preferably 4 times the mass, more preferably 3 times the mass, and even more preferably 2 times the mass.

If the amount of the poor solvent used in the crystallization of the oligomeric arylene diaryl ester (2) is too small, the loss of the oligomeric arylene diaryl ester (2) to the filtrate increases, and the yield is reduced. About the lower limit of the amount of the poor solvent Compared with the oligomeric fluorene diaryl ester (2), it is usually 2 times the mass, preferably 3 times the mass, more preferably 3.5 times the mass, and even more preferably 4 times the mass. In addition, if the amount of the poor solvent is too large, the purification efficiency is also reduced, and the efficiency of the kettle is reduced, and the productivity is reduced. The upper limit of the amount of the poor solvent is usually 10 times the mass, preferably 9 times the mass, more preferably 8 times the mass, and even more preferably 7 times the mass relative to the oligomeric fluorene diaryl ester (2). .

If a large amount of a poor solvent is added at one time in order to obtain crystals from the initial stable shape, the solubility is rapidly reduced, and the crystals are precipitated at one time, so it is difficult to increase the size of the crystals. Regarding the oligomeric fluorene diaryl ester (2), if a small amount of a specific poor solvent is added to a specific good solvent, the solubility tends to increase. By using this property, a specific poor solvent is added separately, or a specific poor solvent is intermittently supplied, and the crystal size tends to become larger. As a specific good solvent, toluene, para-xylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3 are preferable. Aromatic hydrocarbons such as 1,4-tetrahydronaphthalene are preferably toluene, para-xylene, o-xylene, and m-xylene which are inexpensive and easily available in industry. As the specific poor solvent, alcohol-based solvents such as methanol, ethanol, isopropanol, n-butanol, tertiary butanol, hexanol, octanol, and cyclohexanol are preferred, and industrially inexpensive and easily available Isopropanol, methanol, ethanol. Particularly preferred is a combination of o-xylene as a specific good solvent and methanol as a specific poor solvent.

In the case where a specific poor solvent is added in two times, if the proportion of the specific poor solvent added first is too high, the influence of the poor solvent becomes strong, and the effect of improving solubility is not exhibited. Therefore, it is usually 40% by mass. Hereinafter, it is preferably 30% by mass or less, and more preferably 20% by mass or less. On the other hand, if the proportion of the specific poor solvent added first is too low, the effect of adding a poor solvent is not exhibited, so it is usually 5 mass% or more, preferably 10 mass% or more, and more preferably 15 mass% or more.

In the case of adding a specific poor solvent in two times, due to the combination of the specific good solvent and the specific poor solvent, the optimal addition temperature must be adjusted. In the case of particularly preferred o-xylene and methanol, If the addition temperature of methanol is low, the quasi-stable crystals precipitate before the addition of methanol, and the proportion thereof tends to increase. Therefore, the temperature of the initial addition of methanol is usually 45 ° C or higher, preferably 50 ° C or higher, more preferably 55 ° C or higher, and even more preferably 60 ° C or higher. The lower limit of the temperature of the next methanol to be added is usually 0. Above 5 ° C, preferably above 5 ° C, more preferably above 10 ° C. On the other hand, the upper limit of the temperature of the methanol to be added next is usually 42 ° C or lower, preferably 40 ° C or lower, and more preferably 38 ° C or lower.

The oligomeric fluorene diaryl ester (2) largely varies in particle size depending on crystallization conditions. If the particle size of the particles is too small, it tends to become easy to cause clogging of the filter cloth during the crystallization filtration step, and the filtration time becomes longer, or the liquid content becomes higher and the oligomeric arylene diaryl ester (2) Reduced purity. In addition, when used as a resin raw material, powder flowability may be deteriorated, which may cause poor addition. Therefore, the lower limit of the average particle size of the particles of the oligomeric fluorene diaryl 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, and even more preferably 170 μm or more. . If the average particle diameter of the oligomeric fluorene diaryl ester (2) is too large, the filter may be clogged when used as a resin raw material. Therefore, the upper limit of the average particle diameter of the oligomeric fluorene diaryl ester (2) is usually 2 cm or less, preferably 1 cm or less, more preferably 0.5 cm or less, and even more preferably 0.3 cm or less.

The oligomeric fluorene diaryl ester (2) largely varies in particle size depending on crystallization conditions. If the particle size of the particles is too small, it tends to become easy to cause clogging of the filter cloth in the crystallization filtration step, and the filtration time becomes longer, or the liquid content becomes higher and the oligomeric diaryl diaryl ester (2) Reduced purity. In addition, when used as a resin raw material, powder flowability may be deteriorated, which may cause poor addition. Therefore, the particle size of the particles of the oligomeric fluorene diaryl ester (2) is 50% or more of the cumulative%, usually 50% or more is 50% or more, preferably 60% or more, more preferably 70% or more, and even more preferably Above 80%, particularly preferably above 90%.

The particle size of the primary crystals or aggregates aggregated by the primary crystals obtained by crystallization depends on various conditions such as the shape of the reactor or the stirring blade, the stirring speed, and the material of the reactor. Generally, as the scale becomes larger, the shearing force tends to increase and the particles tend to be crushed, and the particle size tends to become smaller. However, according to the crystallization conditions described above, even if a reactor having a size of 1 m ³ or more is used, for example, an oligomeric fluorene diaryl ester (2) having a preferable particle diameter can be obtained.

The metal content can be reduced by repeated crystallization operations. At this time, the lower the crystallization temperature, the higher the recovery amount of the target oligomeric diaryl ester (2), but the metal purification efficiency tends to decrease.

In the case where a Ti compound, which is a particularly good transesterification catalyst, is used as the catalyst, there is a case where the removal of Ti in the oligomeric diaryl ester (2) is difficult and the residue of Ti becomes a problem. In the above case, it is preferred to add water to the reaction solution after the reaction or the solution obtained by dissolving the temporarily isolated oligomeric fluorene diaryl ester (2) in the above-mentioned solvent to deactivate the Ti compound. After converting to insoluble titanium residue, the titanium residue is removed in a filtration step. At this time, when water is added to the reaction liquid after the reaction is completed, the amount of the refined titanium residue is large, and a large load is applied to the filtration step. Therefore, the filterability tends to deteriorate. Therefore, it is preferred to temporarily add a poor solvent to the reaction completion liquid, remove most of the Ti compounds, and then re-dissolve the oligomeric arylene diaryl ester (2) that has been isolated, and then perform the filtration step after deactivation with water.

The particle size of the titanium residue is very small. If the pore size is large, the titanium residue may be mixed into the product without removing the titanium residue. Therefore, the pore diameter of the filter material used in the filtration step is usually 10 μm or less, preferably 5 μm or less, and more preferably 1 μm or less. On the other hand, if the pore diameter of the filter material is too small, there is a possibility that the filtration speed is reduced and the step time may be delayed. Therefore, the pore diameter of the filter material used in the filtration step is usually 0.01 μm or more, preferably 0.05 μm or more, and more preferably 0.1 μm or more. In addition, if the filter surface of the filter material used in the filtration step is flat, titanium residue accumulates on the filter surface and blocks the filter surface. Therefore, in order to shorten the filtration time, an excessive filtration area is required. On the other hand, if the shape of the filter material used in the filtering step is a cylindrical shape that seals the bottom surface of the filter bag, the titanium residue is accumulated on the bottom surface and can be filtered from the side, so the risk of clogging can be reduced. good. The material of the filter material used in the filtration step is preferably made of polypropylene, cotton, and polyester from the viewpoint of being inexpensive and easily available industrially, and more preferably from the viewpoint of higher heat resistance. Made of polyester, cotton and Teflon, more preferably cheap cotton and polyester with high heat resistance Made of filter media. Examples of the filtration steps include suction filtration, centrifuge filtration, and pressure filtration. Among them, the filtration speed of the pressure filtration is fast, so it is preferable. Regarding the pressure of the pressure filtration, in order to increase the filtration speed, it is usually 0.11 MPa or more, preferably 0.15 MPa or more, and more preferably 0.20 MPa or more. Although the upper limit of the pressure filtration depends on the equipment, it is usually 5.0 MPa or less, preferably 3.0 MPa or less, and more preferably 1.0 MPa or less in order to avoid causing a large load on the equipment.

In the filtration step, a filtering aid may also be used. Examples of the filtering aids include diatomaceous earth, powdered cellulose, magnesium sulfate, sodium sulfate, silica gel, activated alumina, activated carbon, activated clay, pole iron, glass fiber, and glass beads.

Among these, diatomaceous earth, powdered cellulose, and puleoirite having a larger filtration area and less adsorption loss are preferred.

<2 oligomeric diester B>

The oligomeric fluorene diester of the present invention (hereinafter referred to as "oligomeric fluorene diester B") includes two or more fluorene units which may have a substituent, and the carbon atoms at the 9-position of the fluorene unit are directly bonded to each other. Or a chain via an alkylene group which may have a substituent, an alkylene group which may have a substituent, or an alkylene group which may have a substituent, and the content ratio of the carboxylic acid is 5% by mass or less .

As the alkylene, alkylene, and alkylene, those exemplified in <1.1 alkylene, alkylene, and alkylene> can be preferably used.

Similarly, as the fluorene unit, those exemplified in <1.2 substituents which a fluorene unit may have> can be preferably used.

The oligomeric fluorene diester B of the present invention can be set as follows, even if the substituents α ¹ and α ² are respectively bonded to the carbon atom at the 9th position of the fluorene unit at both ends, and the substituents α ¹ and α ^{2 is} bonded to an ester group. In this case, α ¹ and α ² may be the same or different. The substituents α ¹ and α ² may also include a direct bond, that is, an ester group is directly bonded to a carbon atom at the 9-position of the fluorene unit.

As the ester group, the <1.3 ester group> in the above-mentioned "Invention 2" can be preferably used. Instantiator. In particular, the ester group is preferably a linear alkyl group, and more preferably a methyl group or an ethyl group, in terms of a tendency to increase resistance to hydrolysis.

As the substituents α ¹ and α ² , those exemplified in <1.4 Substituents α ¹ and α ² > of the aforementioned “Invention 2” can be preferably used.

As a specific structure of the oligomeric fluorene diester B, those represented by the general formula (1) can be preferably used. Moreover, as a specific example, the structure shown by the said [H] group is mentioned.

<2.1 Physical properties of oligomeric diester B>

As described above, the content ratio of the carboxylic acid of the oligomeric fluorene diester of the present invention is 10% by mass or less. By setting the content of the carboxylic acid to a specific range as described above, when the diaryl ester is produced using the oligomeric fluorene diester as a raw material, the amount of metal contained in the diaryl ester can be reduced to a specific value. The tendency of the scope.

The content of the carboxylic acid is preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less, from the viewpoint of reducing the amount of metal contained in the diaryl ester. It is 3% by mass or less, particularly preferably 2% by mass or less, and most preferably 1% by mass or less. In addition, the smaller the carboxylic acid content, the better. However, if it is set to 0% by mass, there is a concern that there is a significant increase in cost or a decrease in production efficiency for the purpose of preventing the inclusion of impurities. The content of the carboxylic acid capable of maintaining productivity is usually 0.1% by mass or more.

It is considered that the carboxylic acid is by-produced by hydrolysis during the production of an oligomeric fluorene diester. The type of the carboxylic acid is not particularly limited, and examples thereof include oligomeric fluorene monoester monocarboxylic acid (in which an ester group is substituted with a carboxylic acid in an oligomeric fluorene diester), and oligomeric fluorene dicarboxylic acid (In the oligomeric fluorene diester, two ester groups are substituted with a carboxylic acid).

Examples of a method for measuring the content of a carboxylic acid include a method of quantifying an isolated carboxylic acid by high performance liquid chromatography.

Examples of the method for adjusting the amount of carboxylic acid to the above range include ordinary purification methods such as filtration operations such as washing with alkaline water, recrystallization, reprecipitation, extraction purification, filter filtration, and column chromatography. . In addition, the present invention is produced by a two-layer reaction. In the case of oligomeric fluorene diester B, it is important to suppress the hydrolysis reaction by lowering the reaction temperature and shortening the reaction time.

In addition, other physical property values of the oligomeric fluorene diester B of the present invention are not particularly limited, and it is preferable to satisfy the item <1.6 Physical properties of the oligomeric fluorene A1 having one reactive functional group> of the above-mentioned "Invention 3" Exemplified physical property values.

<2.2 Production method of oligomeric fluorene diester B>

The manufacturing method of the oligomeric fluorene B of this invention is not specifically limited, For example, it can manufacture by the method similar to the method described in <1.3.4 Manufacturing method of an oligomeric fluorene diester (1)>.

Examples

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. The present invention is not limited to the following examples as long as it does not exceed the gist thereof.

<< Examples 1-1 ~ 1-6, Comparative Examples 1-1 ~ 1-17 >>

The quality evaluation of the oligomeric fluorene monomer and the characteristics evaluation of the resin and the transparent film of the present invention were performed by the following methods. In addition, the characteristic evaluation method is not limited to the following methods, and the operator can select appropriately.

<Evaluation of monomers and resins>

(1) Aluminum and sodium content in actinide monomers

The aluminum and sodium content ratios in the monomer containing a fluorene ring (hereinafter, may be referred to as a fluorene-based monomer) were measured as follows. After the analysis sample was subjected to a wet decomposition treatment, ICP-AES (ULTIMA 2C manufactured by HORIBA Jobin Yvon) was used to quantify the aluminum content rate and the sodium content rate. The sodium content rate was also analyzed by an atomic absorption method (Spectr AA-220P manufactured by VARIAN) based on the analysis sample.

(2) Chlorine content in actinide monomers

The chlorine content rate in the actinic monomer was measured as follows. The combustion device AQF-2100M manufactured by Mitsubishi Chemical Corporation is used to burn the analysis sample and absorb pure water. Of gas. Thereafter, the pure water having absorbed the gas was introduced into an ion chromatograph DX-500 manufactured by Japan Dionex Co., Ltd., and the chlorine content was quantified.

(3) Thermal decomposition temperature of actinide monomer

The glass transition temperature of the actinic monomer was measured using a differential thermal-thermogravimetric analyzer TG-DTA6300 manufactured by SII NanoTechnology. About 4 mg of stilbene-based monomer was placed in an aluminum pan manufactured by the same company and sealed. Under a nitrogen flow of 200 mL / min, the temperature was raised from room temperature (20 to 30 ° C) to 600 ° C at a heating rate of 10 ° C / min. According to the obtained TG data (thermogravimetric data), the temperature at which the sample weight was reduced by 5 wt% was set to the 5 wt% weight reduction temperature. Regarding the monomer containing a solvent, the weight of the solvent estimated from ¹ H-NMR was reduced from the weight at the start of the measurement, and the weight at the time point when the weight change disappeared was set as the initial weight. Reduce the temperature by 5 wt%. In addition, based on the obtained TG data (thermogravimetric data), the peak top of which no decrease in weight was observed and a steep endothermic peak was observed was set as the melting point of the sample.

(4) Absorption maximum wavelength of actinide monomer in ultraviolet-visible region (UV-Vis)

The absorption maximum wavelength of the actinide monomer in the ultraviolet-visible region (UV-Vis: 280 to 800 nm) was measured using an ultraviolet-visible absorption spectrophotometer UV-1650PC manufactured by Shimadzu Corporation. The measurement solution was prepared precisely using tetrahydrofuran as a solvent so that the concentration of the pyrene ring became 10 μM. The measurement unit is a 1 cm square quartz unit, and the measurement is 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 to 800 nm, and the maximum absorption was set as the absorption maximum wavelength (λ _max ).

(5) Resin viscosity of resin

The resin was dissolved in dichloromethane to prepare a resin solution having a concentration of 0.6 g / dL. Using a U-shaped viscosity tube manufactured by Morito Rika Chemical Industries, the temperature was measured at 20.0 ° C ± 0.1 ° C, and the passage time t ₀ of the solvent and the passage time t of the solution were measured. Using the obtained values of t ₀ and t, the relative viscosity η _rel is obtained by the following formula (I), and the specific viscosity η _sp is obtained 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)

Thereafter, the obtained specific viscosity ηs _{p is} divided by the concentration c (g / dL) to obtain the reduced viscosity η _sp / c. The higher the value, the larger the molecular weight.

(6) Melt viscosity of resin

The particulate resin was dried under vacuum at 90 ° C for more than 5 hours. The dried particles were used for measurement using a capillary rheometer manufactured by Toyo Seiki Co., Ltd. Measuring a temperature of 240 deg.] C is set, at a shear rate of the melt viscosity was measured between 9.12 ~ 1824sec ^-1, the value of the melt viscosity under the 91.2sec ^-1. Furthermore, the damping hole system uses a mold diameter of 1mm, length is 10mm.

(7) Glass transition temperature (Tg) of resin

The glass transition temperature of the resin was measured using a differential scanning calorimeter DSC 6220 manufactured by SII NanoTechnology. About 10 mg of the resin was put into an aluminum pan manufactured by the same 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 flow of 50mL / min. After holding the temperature for 3 minutes, it was cooled to 30 ° C at a rate of 20 ° C / min. The temperature was maintained at 30 ° C for 3 minutes, and the temperature was again raised to 200 ° C at a rate of 20 ° C / min. Based on the DSC data obtained during the second temperature increase, the extrapolated glass transition starting temperature is calculated, that is, the slope of the curve extending from the low-temperature side reference line to the high-temperature side and the curve of the step-shaped change in the glass transition The temperature at the intersection of the tangent line drawn by the maximum point was set as the glass transition temperature. Those having a glass transition temperature of 125 ° C. or higher were evaluated as those having excellent heat resistance.

<Evaluation of unstretched film>

(8) Film formation

The unstretched film is produced by the following two methods.

In the following Examples 1-1 and Comparative Examples 1-1 to 1-12, the following procedures were used Press forming is performed to produce an unstretched film. About 4g of resin particles dried under vacuum for more than 5 hours at 90 ℃, using spacers with a length of 14cm, a width of 14cm, and a thickness of 0.1mm, covering the sample with a polyimide film, at a temperature of 200 ~ 230 ℃ Preheat for 3 minutes, press for 5 minutes under the condition of pressure of 40 MPa, take out the spacer together with the separator, and cool it to make a film. In this method, the thickness accuracy of the film cannot be set to 5% or less. In addition, in this specification, thickness accuracy is calculated using the following formula. That is, the thickness accuracy refers to the ratio of the difference between the maximum value or minimum value of the fluctuation range and the set value to the average value when the thickness of each position of the film is measured.

Thickness accuracy [%] = ｜ Maximum or minimum thickness-Set value ｜ / Average × 100

In addition, in the following Examples 1-2 to 1-6 and Comparative Examples 1-13 to 1-17, a long unstretched film was produced by a melt extrusion method. The melt extrusion method is performed as follows. Using a uniaxial extruder (screw diameter 25mm, cylinder set temperature: 220 ° C ~ 240 ° C) manufactured by ISUZU Chemical Machinery Co., Ltd., the resin particles will be vacuum dried at 90 ° C for more than 5 hours from the T-die Head (width 200mm, set temperature: 200 ~ 240 ° C) extrusion. The extruded film was cooled by a cooling roll (setting temperature: 120 to 150 ° C.) and formed into a roll shape by a winding machine to produce a long unstretched film. Moreover, in the above method, the thickness accuracy of the film below 5% can be achieved by adjusting the opening width of the T-die or the temperature of the cooling roll, the distance between the T-die and the cooling roll, and the like.

(9) Measurement of refractive index

A rectangular test piece having a length of 40 mm and a width of 8 mm was cut from the unstretched film produced by the above-mentioned hot pressing method or melt extrusion method to prepare a measurement sample. Using an interference filter of 589 nm (D line), the refractive index n _D was measured by a multi-wavelength Abbe refractometer DR-M4 / 1550 manufactured by Atago. The measurement was performed at 20 ° C using monobromonaphthalene as the interface liquid.

(10) Measurement of total light transmittance

An unstretched film having a film thickness of about 100 μm is prepared by the above-mentioned melt extrusion method, and used The turbidimeter COH400 manufactured by Nippon Denshoku Industries Co., Ltd. measures total light transmittance.

(11) Photoelastic coefficient

A device combining a birefringence measuring device made of a He-Ne laser, a polarizing element, a compensation plate, a light analyzing element, and a light detector and a vibration-type viscoelasticity measuring device (DVE-3 manufactured by Rheology) Determination. (For details, refer to the Journal of the Rheological Society of Japan Vol.19, p93-97 (1991)).

From the unstretched film produced by any of the methods described above, a 5 mm wide and 20 mm long sample was cut and fixed to a viscoelasticity measuring device. At room temperature of 25 ° C, the modulus of storage elasticity E was measured at a frequency of 96 Hz. 'Perform the measurement. At the same time, the emitted laser light is sequentially passed through the polarizing element, the sample, the compensation plate, and the light analyzing element, and is picked up by a photodetector (photodiode), and the waveform of the angular frequency ω or 2ω is obtained through a lock-in amplifier The phase difference with respect to the amplitude and the distortion is obtained, and the strain optical coefficient O ′ is obtained. At this time, the directions of the polarizing element and the light analyzing element are orthogonal, and they are adjusted so that they each form an angle of π / 4 with the direction of elongation of the sample. The photoelastic coefficient C is obtained from the following formula using a storage elastic modulus E 'and a strain optical coefficient O'.

C = O '/ E'

Those with this photoelastic coefficient of 20 or less were evaluated as those with excellent photoelastic characteristics.

(12) Elastic modulus

A rectangular test piece having a width of 5 mm and a length of 50 mm was cut from the film obtained by the above method, and the storage elastic modulus (E ') and the loss elastic modulus (E ") were measured. The measurement was made by TA Instruments. The rheometer RSA-III, in tensile mode, under the conditions of a distance of 20mm between chucks, a heating rate of 3 ° C / min, a frequency of 1Hz, and a deformation of 0.1%, the temperature is from 0 ° C to the glass transition of each sample Above the temperature, the measurement is performed until the sample breaks. The storage elastic modulus in the present invention uses a storage elastic modulus at 30 ° C.

(13) Water absorption

An unstretched film having a thickness of 100 to 300 μm was prepared by any of the methods described above, and a square having a length of 100 mm and a width of 100 mm was cut to prepare a sample. Using this sample, the water absorption was measured in accordance with the "Test method for water absorption and boiling water absorption of plastics" described in JIS K7209.

(14) Toughness of the film (bending test)

An unstretched film having a thickness of 100 to 200 μm is 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 is produced from the film. The interval between the left and right joint surfaces of the vise was opened to 40 mm, and both ends of the test piece were fixed in the joint surface. Then, the interval between the left and right joining surfaces is narrowed at a speed of 2 mm / sec or less. While the film does not protrude from the joining surface of the vise, the entire film bent into a substantially U-shape is compressed within the joining surface. The case where the test piece was fractured into two pieces (or three or more pieces) at the bending portion before the full contact between the joint surfaces was set as "fractured", and the case where the test piece was not broken and was bent even if the joint surfaces were completely tightly connected. Set to "Unbroken". For the same kind of film, the test was performed and repeated 5 times. Among them, those with “breaking” 4 or more times were marked as “×: brittle fracture”, and those with “breaking” less than 3 times were “○: not brittle”. "Break", and the non-brittle failure was evaluated as the one with excellent toughness.

<Evaluation of retardation film>

(15) Extension of the film

According to the above-mentioned method for producing an unstretched film, a retardation film is produced by the following two methods.

The unstretched film produced by the hot pressing method was stretched by the following method. Cut the film with a width of 50mm and a length of 125mm from the unstretched film. Use a batch-type biaxial stretching device (biaxial stretching device BIX-277-AL manufactured by Island industry), and use the glass transition temperature of resin + 15 ° C. The stretching temperature, the stretching speed of 300% / min, and the stretching ratio of 1.5 times were performed for uniaxial stretching of the free end of the above-mentioned film to obtain an extended film.

For unstretched films made by melt extrusion, set to 300% / min stretch Speed, 2 times the stretching ratio, stretching at the glass transition temperature of the resin + 10 ° C stretching temperature, after the stretch film is obtained without breaking, the stretching temperature is lowered by 1 ° C and 1 ° C, and the temperature is reduced during stretching until the film breaks . The stretched film obtained at a stretching temperature 1 ° C higher than the breaking temperature was used for the following evaluations.

(16) Phase difference, wavelength dispersion, and birefringence of stretched film

The central portion of the stretched film obtained by the above method was cut into a width of 4 cm and a length of 4 cm, and a phase difference measuring device KOBRA-WPR manufactured by Oji Measurement Co., Ltd. was used at a measurement wavelength of 450, 500, 550, 590, and 630 nm The phase difference was measured, and the wavelength dispersion was measured. Wavelength dispersion is expressed as the ratio of the phase difference R450 to R550 (R450 / R550) measured at 450nm and 550nm. If R450 / R550 is greater than 1, the wavelength dispersion is positive, and if R450 / R550 is less than 1, it is inverse wavelength dispersion. 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 dividing the value obtained by subtracting the value of R450 / R550 from 1 by the mole ratio of the actinide monomer is set as the visibility of the inverse wavelength dispersion, the value of 0.01 or more is evaluated as the inverse wavelength. Excellent dispersion visibility.

Furthermore, the value of B (R450 / R550) of the formulae (1) to (3) of the present invention 1 can be used for evaluation of stretched films obtained from unstretched films produced by the above-mentioned hot-pressing method The measured wavelength dispersion value.

The birefringence Δn was obtained from the following formula using a retardation R550 of 550 nm and the thickness of the stretched film.

Birefringence = R550 [nm] / (film thickness [mm] × 10 ⁶ )

The larger the value of birefringence, the higher the degree of alignment of the polymer. Also, the larger the value of the birefringence, the thinner the thickness of the film that can be used to obtain the required retardation value.

<Comprehensive evaluation>

Those who did not evaluate as poor among the various evaluations described above were evaluated as those with excellent balance of various characteristics.

<Synthesis example of monomer>

Hereinafter, a method for synthesizing a monomer used for resin production will be described.

[Synthesis Example 1] Synthesis of bis (fluoren-9-yl) methane (compound 1)

Rhenium (120 g, 722 mmol) and N, N-dimethylformamidine (480 ml) were added to a 1 L four-necked flask, followed by nitrogen substitution, and then cooled to 5 ° C or lower. Sodium ethoxide (24.6 g, 361 mmol) was added, and paraformaldehyde (8.7 g, 289 mmol) was added in small amounts several times so as not to exceed 10 ° C., and stirred. After 2 hours, 1N hydrochloric acid (440 ml) was added dropwise to stop the reaction. The obtained suspension solution was suction-filtered, and spray-washed with demineralized water (240 ml). Thereafter, the obtained crude product was dispersed in desalted water (240 ml) and stirred for 1 hour. This suspension was suction-filtered, and then spray-washed with demineralized water (120 ml). The obtained crude product was dispersed in toluene (480 ml), and then dehydrated using a Dean-Stark apparatus under heating and refluxing conditions. After returning to room temperature (20 ° C), suction filtration was performed, and the solution was dried under reduced pressure at 80 ° C to a constant amount, thereby obtaining 84.0 g of bis (fluoren-9-yl) methane (compound 1) as a white solid (product Yield: 84.5%, HPLC purity: 94.0%). The chemical shift in the ¹ H-NMR spectrum of Compound 1 is as follows.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.83 (d, J = 7.6Hz, 4H), 7.56 (dd, J1 = 7.6Hz, J2 = 0.8Hz, 4H), 7.41 (t, J = 7.3Hz, 4H ), 7.29 (dt, J1 = 7.3Hz, J2 = 1.3Hz, 4H), 4.42 (t, J = 7.6Hz, 2H), 2.24 (d, J = 7.6Hz, 2H).

[Synthesis Example 2] Synthesis of bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] methane (Compound 2)

[Chem. 126]

To a 1 L three-necked flask was added the 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 mmol) and dichloromethane (400 ml). After nitrogen substitution, the temperature was controlled to 15 ° C. to 20 ° C. in a water bath, and a 50% aqueous sodium hydroxide solution (64 ml) was added. As a result, the color of the solution became light red. Thereafter, ethyl acrylate (50.5 ml, 465 mmol) was added dropwise over 5 minutes. After 1 hour, ethyl acrylate (25.3 ml, 232 mmol) was further added, and the reaction was stirred for 9 hours while the reaction was followed by HPLC. After confirming that the single adduct was 5% or less by HPLC, the solution was cooled in an ice bath, and 3N hydrochloric acid (293 ml) was added dropwise under temperature equilibrium, followed by quenching. After the organic layer was washed with water until the liquidity became neutral, it was dried with 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 and refluxed for 30 minutes to perform thermal suspension washing. Thereafter, the temperature was returned to room temperature (20 ° C), and suction filtration was performed, followed by drying under reduced pressure at 80 ° C to a constant amount, thereby obtaining bis [9- (2-ethoxycarbonylethyl) as a white solid.茀 -9-yl] methane (compound 2) 96.1 g (yield: 75.9%, HPLC purity: 96.0%). The chemical shift in the ¹ H-NMR spectrum of Compound 2 is as follows.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.03 (d, J = 7.6Hz, 4H), 6.97 (dt, J1 = 7.6Hz, J2 = 1.5Hz, 4H), 6.82 (dt, J1 = 7.6Hz, J2 = 1.3Hz, 4H), 6.77 (d, J = 7.6Hz, 4H), 3.88 (q, J = 7.1Hz, 4H), 3.12 (s, 2H), 2.23 (m, 4H), 1.13 (m, 4H ), 1.02 (t, J = 7.1Hz, 6H).

The 5 wt% weight reduction temperature of Compound 2 (under a nitrogen environment) was 295 ° C, and the melting point was 141 ° C.

[Synthesis Example 3] Synthesis of bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (Compound 3)

To a 1 L four-necked flask was added the bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] methane (Compound 2, 50.0 g, 91.80 mmol), diphenyl carbonate (98.3 g, 459 mmol), tetraisopropyl orthotitanate (1.3 mL, 4.59 mmol), the degree of reduced pressure was adjusted to 3 kPa, the by-products were distilled off and stirred for 6 hours at a temperature range of 145 ° C to 150 ° C. After cooling to 90 ° C and confirming the completion of the reaction by HPLC, toluene (100 ml) was added and the mixture was cooled to 50 ° C. Methanol (250 ml) was added here, and after cooling to 5 ° C, suction filtration was performed. The obtained white solid was dispersed in toluene (100 ml) and heated under reflux for 30 minutes. After cooling to 50 ° C, methanol (200 ml) was added. After cooling to room temperature (20 ° C), suction filtration was performed, and the solution was dried under reduced pressure at 100 ° C to a constant amount, thereby obtaining bis [9- (2-phenoxycarbonylethyl) 乙基 -9 as a white solid. -Yl] methane (compound 3) 50 g (yield: 85%, HPLC purity: 98.1%). The chemical shift in the ¹ H-NMR spectrum of Compound 3 is as follows.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.23-7.28 (m, 4H), 7.07-7.16 (m, 6H), 7.03 (dt, J1 = 6.9Hz, J2 = 2.0, 4H), 6.78-6.90 (m , 12H), 3.20 (s, 2H), 2.37 (t, J = 8.3Hz, 4H), 1.40 (t, J = 8.3Hz, 4H).

The 5 wt% weight reduction temperature of Compound 3 (under a nitrogen atmosphere) was 336 ° C, and the melting point was 176 ° C.

[Synthesis Example 4] Synthesis of 1,2-bis (fluoren-9-yl) ethane (Compound 4)

Rhenium (2.0 g, 12 mmol) and tetrahydrofuran (35 ml) were added to a 100-ml four-necked flask, followed by nitrogen substitution, and then 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 in small amounts multiple times so as not to exceed -40 ° C and stirred. Then, it heated up to 10 degreeC, and after stirring for 1 hour, 1, 2- dibromoethane (0.55 ml, 6.4 ml) was added, and it stirred for 2 hours. Thereafter, 1N hydrochloric acid (0.5 ml) was added dropwise, and the resulting suspension solution was suction-filtered, washed with water, and then dried under reduced pressure at 80 ° C to a constant amount, thereby obtaining 1,2-bis as a white solid. 0.63 g of (fluoren-9-yl) ethane (compound 4) (yield: 29.2%, HPLC purity: 98.0%). The solvent of the filtrate was distilled off under reduced pressure, and ethanol (25 ml) was added and stirred for 30 minutes. The suspension was suction-filtered and dried under reduced pressure at 80 ° C. to a constant amount, thereby obtaining 0.44 g of 1,2-bis (fluoren-9-yl) ethane (compound 4) as a white solid (yield). : 20.5%, HPLC purity: 84.0%). When combined with the obtained white solid, it was 1.07 g (yield: 49.7%). The chemical shift in the ¹ H-NMR spectrum of Compound 4 is as follows.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.75 (d, J = 7.6Hz, 4H), 7.37 (dt, J1 = 7.6Hz, J2 = 0.5Hz, 4H), 7.27-7.34 (m, 8H), 3.85 (s, 2H), 1.74 (t, J = 2.3Hz, 4H).

[Synthesis Example 5] Synthesis of 1,2-bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] ethane (Compound 5)

In a 1 L four-necked flask, 1,2-bis (fluoren-9-yl) ethane (Compound 4, 85 g, 237 mmol), tetrahydrofuran (725 ml), and N, N-dimethylformamide were obtained. (85 ml), after replacing with nitrogen, sodium ethoxide (3.23 g, 47.5 mmol) was added, the temperature was raised to room temperature (20 ° C), and the mixture was stirred for 30 minutes. Ethyl acrylate (59.3 ml, 545 mmol) was added dropwise over 2.5 hours. After confirming the disappearance of the raw materials 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 liquidity became neutral, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was dispersed in methanol (400 ml), and heated and refluxed for 1 hour to perform thermal suspension washing. Thereafter, the temperature was returned to room temperature (20 ° C), and suction filtration was performed, followed by drying under reduced pressure at 80 ° C to a constant amount, thereby obtaining 1,2-bis [9- (2-ethoxy) as a white solid. 101 g of carbonylethyl) fluoren-9-yl] ethane (compound 5) (yield: 76.1%, HPLC purity: 98.6%). The chemical shift in the ¹ H-NMR spectrum of Compound 5 is as follows.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.72 (d, J = 7.6Hz, 4H), 7.36 (t, J = 7.6Hz, 4H), 7.27 (t, J = 7.3Hz, 4H), 6.97 (d , J = 7.3Hz, 4H), 3.80 (q, J = 7.1Hz, 4H), 1.93 (t, J = 8.6Hz, 4H), 1.33 (t, J = 8.6Hz, 4H), 1.23 (s, 4H ), 1.01 (t, J = 7.1Hz, 6H).

The 5 wt% weight reduction temperature of Compound 5 (under a nitrogen environment) was 306 ° C, and the melting point was 150 ° C.

[Synthesis Example 6] Synthesis of 1,2-bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] ethane (Compound 6)

To a 1 L four-necked flask, 1,2-bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] ethane (compound 5, 100.0 g, 179 mmol), carbonic acid obtained by the above method was added. After diphenyl ester (115 g, 537 mmol) and tetraisopropyl orthotitanate (2.62 ml, 8.95 mmol) were replaced with nitrogen, the temperature was raised to 135 ° C. and stirred for 24 hours. On the way, diphenyl carbonate (38.3 g, 179 mmol) was added in small amounts at a time point of 12 hours and a time point of 20 hours. After confirming the completion of the reaction by HPLC, toluene (400 ml) was added, and the mixture was heated under reflux for 1 hour. After cooling to room temperature (20 ° C), suction filtration was performed. The obtained white solid was dispersed in toluene (300 ml) and heated under reflux for 1 hour. After cooling to room temperature (20 ° C), suction filtration was performed, and the solution was dried under reduced pressure at 80 ° C until a constant amount was obtained, thereby obtaining 1,2-bis [9- (2-phenoxycarbonylethyl) as a white solid. ) 82 g of fluoren-9-yl] ethane (compound 6) (yield: 70.0%, HPLC purity: 98.0%). The chemical shift in the ¹ H-NMR spectrum of compound 6 is as follows.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.76 (d, J = 7.6, 4H), 7.41 (dt, J1 = 7.3, J2 = 1.0, 4H), 7.32 (dt, J1 = 7.3, J2 = 1.0, 4H ), 7.22 (t, J = 8.3, 4H), 7, 11 (t, J = 7.6, 2H), 7.03 (d, J = 7.6, 4H), 6.78 (d, J = 8.6, 4H), 2.06 ( t, J = 8.1,4H), 1.60 (t, J = 8.1,4H), 1.29 (s, 4H).

The 5 wt% weight reduction temperature of Compound 6 (under a nitrogen environment) was 337 ° C, and the melting point was 232 ° C.

[Synthesis Example 7] Synthesis of bis [9- (3-hydroxypropyl) -fluoren-9-yl] methane (Compound 7)

A 500 ml four-necked flask was charged with bis [9- (2-ethoxycarbonylethylfluoren-9-yl) methane (Compound 2, 50 g, 91.8 mmol) and toluene (250 ml) obtained in Synthesis Example 2 After the nitrogen substitution, the solution was cooled to 5 ° C or lower in an ice bath, kept at 10 ° C or lower, and a 65 wt% toluene solution (82.7 ml, 275 mmol) of sodium bis (2-methoxyethoxy) aluminum hydride was added dropwise, and stirred for 1 hour After confirming the disappearance of the raw materials by HPLC, ethyl acetate (9.9 ml) was added dropwise, and after stirring for 30 minutes, a 3.1N sodium hydroxide aqueous solution was further added dropwise, followed by stirring for 2 hours. The obtained suspension solution was evacuated It was filtered and spray-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, the spray-washing was performed until the liquidity became neutral. It was spray-washed with toluene (50 ml). The obtained crude product was dispersed in tetrahydrofuran (150 ml) and dissolved by heating. The tetrahydrofuran solution was returned to room temperature (20 ° C), and then passed through a short silicon gel. The channel (50g) was washed with tetrahydrofuran (350ml), and the obtained solution was used The solvent was removed by distillation under reduced pressure. The obtained crude product was dispersed in toluene (250 ml), and heated and refluxed for 30 minutes to perform thermal suspension washing. After returning to room temperature (20 ° C), suction filtration was performed. 35.5 g of bis [9- (3-hydroxypropyl) -fluorene-9-yl] methane (compound 7) was obtained as a white solid by drying under reduced pressure at 80 ° C under constant pressure (yield: 83.9% , HPLC purity: 99.8%). The sodium content and aluminum content in the solid were less than 1 ppm. The chemical shift in the ¹ H-NMR spectrum of compound 7 is as follows. ¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.05 (d, J = 7.6Hz, 4H), 6.97 (dt, J1 = 7.6Hz, J2 = 1.5Hz, 4H), 6.81 (dt, J1 = 7.6Hz, J2 = 1.3Hz, 4H), 6.77 (d , J = 7.6Hz, 4H), 3.19 (q, J = 6.3Hz, 4H), 3.08 (s, 2H), 1.94 (m, 4H), 0.77 (t, J = 5.8Hz, 2H), 0.47 (m , 4H).

The 5 wt% weight reduction temperature of Compound 7 (under a nitrogen environment) was 301 ° C, and the melting point was 214 ° C.

[Synthesis Example 8] Synthesis of 1,2-bis [9- (3-hydroxypropyl) -fluoren-9-yl] ethane (Compound 8)

In a 1 L four-necked flask, 1,2-bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] ethane (Compound 5, 100 g, 179 mmol) and tetrahydrofuran obtained in Synthesis Example 5 were added. (500 ml), after nitrogen substitution, cooled to 5 ° C or lower in an ice bath, kept at 15 ° C or lower, and a 65 wt% toluene solution of sodium bis (2-methoxyethoxy) aluminum hydride (161 ml, 537 mmol) was added dropwise. And stir for 1 hour. After confirming the disappearance of the raw materials by HPLC, ethyl acetate (32 ml) was added dropwise, and after stirring for 45 minutes, a 3.1 N sodium hydroxide aqueous solution (257 ml) was further added dropwise, followed by stirring for 1 hour. After the tetrahydrofuran was distilled off under reduced pressure, the obtained suspension solution was suction-filtered, and spray-washed with demineralized water (100 ml). Thereafter, the obtained crude product was dissolved in ethyl acetate (700 ml), and washed three times with demineralized water (100 ml). After the organic layer was dried with magnesium sulfate, it was rinsed with tetrahydrofuran (800 ml) through a short silica gel channel (50 g), and the obtained solution was distilled to remove the solvent under reduced pressure using an evaporator. The obtained crude product was dispersed in toluene (400 ml), and heated and refluxed for 30 minutes to perform thermal suspension washing. After returning to room temperature (20 ° C), suction filtration was performed, and then dried under reduced pressure at 100 ° C to a constant amount to obtain 1,2-bis [9- (3-hydroxypropyl) as a white solid. -Fluoren-9-yl] ethane (compound 8) 75.6 g (yield: 89.0%, HPLC purity: 98.7%). The content of sodium in the solid was 2 ppm, and the content of aluminum was less than 2 ppm. The chemical shift in the ¹ H-NMR spectrum of Compound 8 is as follows.

¹ H-NMR (400MHz, DMSO-d ₆ ) δ 7.81 (d, J = 7.3Hz, 4H), 7.35 (t, J = 7.3Hz, 4H), 7.29 (t, J = 7.3Hz, 4H), 7.02 (d, J = 7.3Hz, 4H), 4.02 (t, J = 5.0Hz, 2H), 2.93 (m, 4H), 1.59 (m, 4H), 1.19 (s, 4H), 0.45 (m, 4H) .

The 5 wt% weight reduction temperature of Compound 8 (under a nitrogen atmosphere) was 312 ° C, and the melting point was 253 ° C.

[Synthesis Example 9] Synthesis of bis (9-hydroxymethylfluorene-9-yl) methane (Compound 9)

[Chemical 133]

A 500 mL four-necked flask was added with bis (fluoren-9-yl) methane (Compound 1, 100 g, 290 mmol) and N, N-dimethylformamide (400 ml) obtained in Synthesis Example 1, and nitrogen substitution was performed. Add paraformaldehyde (18.3 g, 610 mmol). After cooling to 5 ° C or lower, sodium ethoxide (0.698 g, 13 mmol) was added, and the mixture was stirred so as not to exceed 10 ° C. After 1 hour and a half, 1N hydrochloric acid (32 ml) was added so as not to exceed 25 ° C to stop the reaction. Furthermore, water (300 ml) was added and stirred, and the obtained suspension solution was suction-filtered, and spray-washed with demineralized water (100 ml). The obtained crude product was dispersed in tetrahydrofuran (400 ml), and then heated under reflux for 1 hour. The temperature was returned to room temperature (20 ° C), and after suction filtration, the solution was dried under reduced pressure at 80 ° C to a constant amount to obtain 108 g of a white solid (yield: 91%, HPLC purity: 99.1%). 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 and refluxed for 1 hour, filtered and dried, and the sodium content in the obtained solid was measured. As a result, it was 390 ppm . Furthermore, the obtained white solid was dispersed in N, N-dimethylformamide (500 ml), heated to make a uniform solution, and then cooled to 40 ° C or lower, and then poured into 0.03N hydrochloric acid (1500 ml). Add slowly. The obtained suspension solution was suction-filtered and dispersed in desalted water (200 ml), and stirred for 1 hour. This suspension was suction-filtered, and then spray-washed with demineralized water (100 ml). The obtained product was dispersed in toluene (800 ml), and then azeotropically dehydrated under heating and refluxing. The temperature was returned to room temperature (20 ° C), and after suction filtration, the solution was dried under reduced pressure at 100 ° C to a constant amount to obtain bis (9-hydroxymethylfluorene-9-yl) methane (compound 9) as a white solid. 104 g (87% yield, HPLC purity: 99.8%). The content of sodium and chlorine in the solids did not reach 10 ppm respectively. The chemical shift in the ¹ H-NMR spectrum of Compound 9 is as follows.

¹ H-NMR (400MHz, DMSO-d ₆ ) δ 7.12 (d, J = 7.3Hz, 4H), 7.07- 6.93 (m, 8H), 6.77 (dt, J1 = 7.3Hz, J2 = 1.0Hz, 4H) , 4.97 (t, J = 4.6Hz, 2H), 3.31 (s, 2H), 3.23 (d, J = 4.3Hz, 4H).

The absorption maximum wavelength λ _max in the UV-Vis spectrum (solvent: THF) of Compound 9 exists at 263 nm, 292 nm, and 304 nm. The 5 wt% weight reduction temperature of Compound 9 (under a nitrogen environment) was 289 ° C, and the melting point was 226 ° C.

[Synthesis Example 10] Synthesis of 1,2-bis (9-hydroxymethylfluoren-9-yl) ethane (Compound 10)

In a 1 L four-necked flask, 1,2-bis (fluoren-9-yl) ethane (Compound 4, 100 g, 278.9 mmol), paraformaldehyde (17.6 g, 585.8 mmol), and N obtained in Synthesis Example 4 were added. N-dimethylformamidine (400 ml), after nitrogen substitution, and cooled to 10 ° C or lower. Sodium ethoxide (1.80 g, 27.9 mmol) was added, and the temperature was raised to room temperature (20 ° C) and stirred for 1 hour. After confirming the disappearance of the raw materials by HPLC, the reaction solution was added dropwise to 0.1N hydrochloric acid (440 ml) to stop the reaction. The obtained suspension solution was suction-filtered, and spray-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 to 0.005N hydrochloric acid (1000 ml), and after stirring for 30 minutes, suction filtration was performed. The obtained crude product was dispersed in demineralized water (500 ml) and stirred for 1 hour. This suspension was suction-filtered, and then spray-washed with demineralized water (200 ml). The obtained crude product was dispersed in toluene (500 ml), and then dehydrated using a Dean-Stark apparatus under heating and refluxing conditions. After returning to room temperature (20 ° C), suction filtration was performed, and the solution was dried under reduced pressure at 100 ° C until a constant amount was obtained, thereby obtaining 1,2-bis (9-hydroxymethylfluorene-9-yl) as a white solid. 112.4 g of ethane (compound 10) (yield: 96.3%, HPLC purity: 99.1%). The content of sodium in the solid was less than 1 ppm. The chemical shift in the ¹ H-NMR spectrum of Compound 10 is as follows.

¹ H-NMR (400MHz, DMSO-d ₆ ) δ 7.91 (d, J = 7.3Hz, 4H), 7.4 (dt, J1 = 7.6Hz, J2 = 1.0Hz, 4H), 7.35 (dt, J1 = 7.6Hz , J2 = 1.0Hz, 4H), 7.18 (d, J = 7.3Hz, 4H), 4.79 (t, J = 5.3Hz, 2H), 3.18 (d, J = 5.3Hz, 2H), 1.40 (s, 4H ).

The absorption maximum wavelength λ _max in the UV-Vis spectrum (solvent: THF) of Compound 10 exists at 264 nm, 291 nm, and 302 nm. The 5 wt% weight reduction temperature of Compound 10 (under a nitrogen atmosphere) was 301 ° C, and the melting point was 278 ° C.

[Synthesis Example 11] Synthesis of 1,2-bis (fluoren-9-yl) butane (Compound 11)

Sulfur (3.5 g, 21 mmol), 1,4-butanediol (4.9 g, 54 mmol), 85% KOH (1.52 g, 23 mmol), tetraethylene glycol dimethyl ether (4.9 g) Under a nitrogen environment, the reaction was performed at 250 ° C for 8 hours. After cooling, the contents were dispersed in tetrahydrofuran and water, and neutralized with dilute hydrochloric acid. The precipitated powder was filtered from the obtained suspension solution and washed with water to obtain 1.7 g of 1,4-bis (fluoren-9-yl) butane (Compound 11) as a white solid (yield: 41.9%, HPLC purity : 97.4%). The chemical shift in the ¹ H-NMR spectrum of Compound 11 is as follows.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.72 (d, J = 7.6Hz, 4H), 7.42 (m, 4H), 7.25-7.36 (m, 8H), 3.89 (t, J = 5.8Hz, 2H) , 1.96-1.86 (m, 4H), 1.15-1.05 (m, 4H).

[Synthesis Example 12] Synthesis of 1,2-bis (9-hydroxymethylfluoren-9-yl) butane (Compound 12)

[Chemical 136]

In a 500 mL four-necked flask, 1,2-bis (fluoren-9-yl) butane (compound 11, 37.0 g, 95.7 mmol), paraformaldehyde (6.03 g, 201 mmol), N, N obtained above were added. -Dimethylformamide (148 ml), after nitrogen substitution, and cooling to 10 ° C or lower. Sodium ethoxide (0.65 g, 9.6 mmol) was added, the temperature was raised to room temperature (20 ° C), and the mixture was stirred for 1 hour. After confirming the disappearance of the raw materials by HPLC, the reaction solution was added dropwise to 0.1N hydrochloric acid (162 ml) to stop the reaction. The obtained suspension solution was suction-filtered, and spray-washed with demineralized water (37 ml). The obtained crude product was dispersed in toluene (185 ml), and then dehydrated using a Dean-Stark apparatus under heating and refluxing conditions. After returning to room temperature (20 ° C), suction filtration was performed, and reduced pressure filtration was performed at 80 ° C until a constant amount was obtained, thereby obtaining 1,2-bis (9-hydroxymethylfluorene-9-yl) as a white solid. ) 39.8 g of butane (Compound 12) (yield: 93.1%, HPLC purity: 99.1%). The chemical shift in the ¹ H-NMR spectrum of Compound 12 is as follows.

¹ H-NMR (400MHz, DMSO-d ₆ ) δ 7.71-7.66 (m, 4H), 7.38-7.24 (m, 4H), 3.71 (d, J = 6.3Hz, 4H), 1.89-1.81 (m, 4H ), 1.22 (t, J = 6.3Hz, 2H), 0.51-0.44 (m, 4H).

The absorption maximum wavelength λ _max in the UV-Vis spectrum (solvent: THF) of Compound 12 exists at 291 nm and 302 nm. The 5 wt% weight reduction temperature of Compound 12 (under a nitrogen environment) was 314 ° C, and the melting point was 212 ° C.

[Synthesis Example 13] Synthesis of α, α'-bis- (9-hydroxymethylfluoren-9-yl) -1,4-xylene (Compound 13)

[Chemical 137]

Add α, α'-bis- (fluoren-9-yl) -1,4-xylene (130 g, 0.3 mol), paraformaldehyde (18.9 g, 0.63 mol), N, N to a 1 L four-neck eggplant-shaped flask -Dimethylformamide (520 ml), after replacing with nitrogen, 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 desalted water and 1 N hydrochloric acid (45 ml) were added to a 1 L beaker, and the reaction solution was added while stirring to quench the reaction. The obtained crystals were suction-filtered, and spray-washed with demineralized water (100 ml). The obtained crude product was dispersed in demineralized water (500 ml), and then subjected to suction filtration, and spray-washed with demineralized water (100 ml). The obtained crude product was dispersed in toluene (500 ml), and then dehydrated using a Dean-Stark apparatus under heating and refluxing conditions. After returning to room temperature (20 ° C), suction filtration and drying under reduced pressure at 70 ° C to a constant amount were performed to obtain 130 g of a white solid (Compound 13) (yield: 87%, HPLC purity: 97.6%). The chemical shift in the ¹ H-NMR spectrum of Compound 13 is as follows.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.62 (d, J = 7.6Hz, 4H), 7.33 (t, J = 8.0Hz, 4H), 7.25 (t, J = 60Hz, 4H), 7.19 (br, 4H), 6.45 (s, 4H), 3.80 (d, J = 6.4Hz, 4H), 3.12 (s, 4H), 1.42 (t, J = 6.4Hz, 2H).

The 5 wt% weight reduction temperature of Compound 13 (under a nitrogen atmosphere) was 327 ° C, and the melting point was 198 ° C.

[Synthesis Example 14] Synthesis of 1,2-bis (9-hydroxyfluorene-9-yl) ethane (Compound 14)

To a 1 L four-necked flask, 1,2-bis (fluoren-9-yl) ethane (compound 4, 20 g, 59 mmol), N, N-dimethylformamide ( 200ml), tributyl phosphite (37.9ml, 140mmol) was added, and after nitrogen substitution, benzyltrimethylammonium hydroxide (40% methanol solution) (25ml) was added, and air (100ml / min) and nitrogen ( 300ml / min) mixed gas is circulated in 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 1 hour. 1N hydrochloric acid (200 ml) was added to stop the reaction, and ethyl acetate (400 ml) was added to perform a liquid separation operation. Furthermore, the organic layer was washed three times with saturated saline (100 ml). The organic layer was dried with magnesium sulfate, and then filtered, and the organic solvent was distilled off under reduced pressure. Toluene (100 ml) and hexane (200 ml) were added to the obtained suspension solution, and after stirring for 30 minutes, the mixture was suction-filtered and dried under reduced pressure at 80 ° C to a constant amount to obtain 1,2 as a white solid. -13.9 g of bis (9-hydroxyfluorene-9-yl) ethane (Compound 14) (yield: 63.8%, HPLC purity: 92.5%). The chemical shift in the ¹ H-NMR spectrum of Compound 14 is as follows.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.73 (d, J = 7.3Hz, 4H), 7.35 (dt, J1 = 7.6Hz, J2 = 1.0, 6H), 7.26 (dt, J1 = 7.6Hz, J2 = 1.0, 4H), 7.11 (d, J = 7.3Hz, 4H), 5.35 (s, 2H), 1.40 (s, 4H).

[Synthesis Example 15] Synthesis of bis-{[4- (2-hydroxyethoxy) phenyl] fluorene-9-yl} ethane (Compound 15)

A 300 mL four-necked flask was charged with 1,2-bis (fluoren-9-yl) ethane (compound 14, 17 g, 45 mmol, phenoxyethanol (37 g, 267 mmol)) obtained by the method described above, and then replaced with nitrogen. And cooled to below 10 ° C. Boron trifluoride-diethyl ether complex (5.6ml, 45mmol) was added, and after stirring at room temperature (20 ° C) for 3 hours, boron trifluoride-diethyl was further added. Ether complex (5.6 ml, 45 mmol) and chloroform (35 ml) were stirred at 40 ° C. for 4 hours and 60 ° C. for 2 hours. Furthermore, boron trifluoride-diethyl ether complex (5.6 ml) was added. , 45 mmol), refluxed for 2 hours. After cooling to room temperature (20 ° C), neutralization was performed using a saturated aqueous sodium hydrogen carbonate solution, and insoluble matter was removed by suction filtration. Ethyl acetate (120 ml) was added. The organic layer was washed twice with saturated saline, and once with demineralized saline. The organic layer was dried with magnesium sulfate, filtered, and the organic solvent was distilled off under reduced pressure. It was dissolved again in ethyl acetate (150 ml). ), Added activated carbon (Japan Norit Co., Ltd., SXPLUS, pH = 7, 2.5g), stirred for 1 hour, and then filtered through diatomaceous earth The organic solvent was distilled off under reduced pressure. Methanol (100 ml) was added, and the mixture was stirred for 1 hour, followed by suction filtration, and dried under reduced pressure at 80 ° C. to a constant amount, thereby obtaining bis-{[4- (2- Hydroxyethoxy) phenyl] fluorene-9-yl} ethane (compound 15) 15.8 g (yield: 56.1%, HPLC purity: 86%). The chemical shift in the ¹ H-NMR spectrum of compound 15 is as follows As described.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.77 (d, J = 7.3Hz, 4H), 7.36 (dt, J1 = 7.6Hz, J2 = 1.0, 4H), 7.22 (dt, J1 = Hz, J2 = 1.0 , 4H), 6.92 (d, J = 7.6Hz, 4H), 6.73 (d, J = 9.1Hz, 4H), 6.59 (d, J = 9.1Hz, 4H), 3.91-3.93 (m, 4H), 3.83 -3.87 (m, 4H), 1.92 (t, J = 6.3Hz, 2H), 1.82 (s, 4H),

[Synthesis Example 16] Synthesis of 茀 -9,9-diethanol (Compound 16)

Synthesis was performed according to the method described in Japanese Patent Laid-Open No. 2010-261008.

<Resin Synthesis Examples and Characteristics Evaluation>

The abbreviations and the like 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 Chemicals)

‧BCF: 9,9-bis (4-hydroxy-3-methylphenyl) -fluorene (manufactured by Osaka Gas Chemicals)

‧DPC: Diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation)

‧ISB: Isosorbide (manufactured by Roquette Freres, trade name: POLYSORB)

‧CHDM: 1,4-cyclohexanedimethanol (cis, trans mixture, manufactured by SK Chemicals)

‧TCDDM: Tricyclodecane dimethanol (manufactured by OXEA)

‧SPG: Spirodiol (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

‧BPA: 2,2-bis [4-hydroxyphenyl 7 propane (manufactured by Mitsubishi Chemical Corporation)

‧PEG: Number average molecular weight of polyethylene glycol: 1000 (manufactured by Sanyo Kasei Co., Ltd.)

‧CHDA: 1,4-cyclohexanedicarboxylic acid (cis, trans mixture, manufactured by Eastman Chemical)

‧DMT: Dimethyl terephthalate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Example 1-1]

Bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (compound 3) 38.06 parts by mass (0.059 mol), ISB 53.73 parts by mass (0.368 mol), CHDM 9.64 parts by mass (0.067 mol ), 81.28 parts by mass (0.379 mol) of DPC, and 3.83 × 10 ^-4 parts by mass (2.17 × 10 ^-6 mol) of calcium acetate monohydrate as a catalyst were put into a reaction vessel, and the inside of the reaction apparatus was replaced with reduced-pressure nitrogen. Under a nitrogen atmosphere, the raw materials were stirred at 150 ° C. for about 10 minutes. In the step of the first stage of the reaction, the temperature was raised to 220 ° C over 30 minutes, and the reaction was carried out under normal pressure for 60 minutes. Then, the pressure was reduced from normal pressure to 13.3 kPa over 90 minutes, and the pressure was maintained at 13.3 kPa for 30 minutes. The generated phenol was extracted out of the reaction system. Then, in the second step of the reaction, the temperature of the heating medium was raised to 240 ° C. over 15 minutes, and the pressure was reduced to less than 0.10 kPa over 15 minutes, and the generated phenol was extracted out of the reaction system. After reaching a specific stirring torque, the nitrogen was returned to normal pressure to stop the reaction, the produced polyester carbonate was extruded in water, and the strands were cut to obtain pellets. Using the obtained pellets of polyester carbonate, various evaluations described above were performed. The evaluation results are shown in Table 1.

Regarding the polyester carbonate of Example 1-1, the content of the oligomeric fluorene structural unit derived from Compound 3 was 27.0% by mass, which was a small amount, but the wavelength dispersion (R450 / R550) of the retardation film showed 0.835, and the reverse wavelength dispersion The visibility is 0.025, which can be understood as high. Furthermore, the polyester carbonate of Example 1-1 had a low photoelastic coefficient, a glass transition temperature of 143 ° C, and a value excellent in the balance between melt processability and heat resistance.

[Comparative Example 1-1]

1,2-bis [9- (2-phenoxycarbonylethyl) fluorene-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 Except for parts by mass (0.108 mol), DPC 72.36 parts by mass (0.338 mol), and calcium acetate monohydrate 3.55 × 10 ^-4 parts by mass (2.02 × 10 ^-6 mol), the same as Example 1-1 was used. Synthesis was carried out in this manner to obtain pellets of polyester carbonate. Using the obtained pellets of polyester carbonate, various evaluations described above were performed. The evaluation results are shown in Table 1.

The polyester carbonate of Comparative Example 1-1 also exhibited high reversibility of wavelength dispersion and had excellent mechanical properties, but its photoelastic properties were poor.

[Comparative Example 1-2]

Using 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), Except for DPC 95.85 parts by mass (0.447 mol) and calcium acetate monohydrate 3.90 × 10 ^-4 parts by mass (2.22 × 10 ^-6 mol), synthesis was performed in the same manner as in Example 1-1 to obtain a polymer. Carbonate particles.

Using the obtained polycarbonate pellets, various evaluations described above were performed. The evaluation results are shown in Table 1.

The polycarbonate of Comparative Example 1-2 also has relatively excellent characteristics, but the visibility of the inverse wavelength dispersion is poor.

[Comparative Example 1-3]

1,2-bis [9- (3-hydroxypropyl) -fluoren-9-yl] ethane (compound 8) 37.92 parts by mass (0.080 mol), ISB 42.45 parts by mass (0.290 mol), and CHDM 8.47 parts by mass Except for (0.059 mol), 92.84 parts by mass (0.433 mol) of DPC, 3.78 × 10 ^-4 parts by mass (2.15 × 10 ^-6 mol) of calcium acetate monohydrate, the same procedure as in Example 1-1 was performed Synthesis to obtain polycarbonate particles. Using the obtained polycarbonate pellets, various evaluations described above were performed. The evaluation results are shown in Table 1.

The polycarbonate of Comparative Examples 1-3 had poor visibility or photoelastic properties of inverse wavelength dispersion.

[Comparative Example 1-4]

28.19 parts by mass (0.070 mol) of bis (9-hydroxymethylhydrazone-9-yl) methane (Compound 9), 42.45 parts by mass (0.290 mol), 16.95 parts by mass (0.118 mol) of CHDM, 103.35 parts by mass of DPC ( Except for 0.482 mol) and calcium acetate monohydrate (1.68 × 10 ^-3 parts by mass (9.55 × 10 ^-6 mol)), polycarbonate particles were obtained in the same manner as in Example 1-1. Using the obtained polycarbonate pellets, various evaluations described above were performed. The evaluation results are shown in Table 1.

Compound 9 is a compound in which the same oligomeric fluorene structure unit as the fluorene monomer used in Example 1-1 or Comparative Examples 1-1 to 1-3 can be introduced. The polycarbonate using compound 9 is unexpected. Ground does not exhibit inverse wavelength dispersion. The reason is speculated that the fluorene ring of compound 9 is not aligned in a direction perpendicular to the extending direction.

[Comparative Example-5]

47.08 parts by mass (0.112 mol) of 1,2-bis (9-hydroxymethylfluoren-9-yl) ethane (Compound 10), 29.71 parts by mass (0.203 mol) of ISB, 12.71 parts by mass (0.088 mol) of CHDM, Except for DPC 87.40 parts by mass (0.408 mol) and calcium acetate monohydrate 7.12 × 10 ^-4 parts by mass (4.04 × 10 ^-6 mol), synthesis was performed in the same manner as in Example 1-1 to obtain a polycarbonate. Ester particles. Using the obtained polycarbonate pellets, various evaluations described above were performed. The evaluation results are shown in Table 1.

The resin system of this example did not exhibit reverse wavelength dispersion property similarly to Comparative Examples 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), Except for DPC 98.74 parts by mass (0.461 mol) and calcium acetate monohydrate 8.04 × 10 ^-4 parts by mass (4.56 × 10 ^-6 mol), synthesis was performed in the same manner as in Example 1-1 to obtain a polycarbonate. Ester particles. Using the obtained polycarbonate pellets, various evaluations described above were performed. The evaluation results are shown in Table 1.

The resin system of this example did not exhibit reverse wavelength dispersion property similarly to Comparative Examples 1-4.

[Comparative Example 1-7]

33.85 parts by mass (0.084 mol) of bis (9-hydroxymethylfluoren-9-yl) methane (Compound 9), 28.97 parts by mass (0.201 mol) of CHDM, 48.03 parts by mass (0.279 mol) of CHDA, and a catalyst Tetra-n-butyl titanate was synthesized in the same manner as in Examples 1-6, except for 9.49 × 10 ^-3 parts by mass (2.79 × 10 ^-5 mol), to obtain a pellet of polyester. Using the pellets of the obtained polyester, various evaluations described above were performed. The evaluation results are shown in Table 1.

In this example, a polyester was synthesized from Compound 9 used in the polycarbonates of Comparative Examples 1-4, However, the polyester does not exhibit reverse wavelength dispersion.

[Comparative Example 1-8]

Α, α'-bis- (9-hydroxymethylfluoren-9-yl) -1,4-xylene (Compound 13) 38.00 parts by mass (0.077 mol), 33.96 parts by mass (0.232 mol), CHDM 16.95 Except for parts by mass (0.118 mol), DPC 92.32 parts by mass (0.431 mol), calcium acetate monohydrate 7.52 × 10 ^-4 parts by mass (4.27 × 10 ^-6 mol), and the same as those in Example 1-1 Synthesis was performed to obtain polycarbonate particles. Using the obtained polycarbonate pellets, various evaluations described above were performed. The evaluation results are shown in Table 1.

The resin system of this example did not exhibit reverse wavelength dispersion property similarly to Comparative Examples 1-4. From the results of Comparative Examples 1-4 to 1-8, it can be 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 inverse wavelength dispersion. If the distance between the carbonyl group and the fluorene ring is too close, it is presumed that the fluorene ring cannot be aligned in a better direction due to the steric hindrance of the carbonyl group, and the anti-wavelength dispersion property is not developed.

[Comparative Example 1-9]

Using bis-{[4- (2-hydroxyethoxy) phenyl] fluorene-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 Except for parts (0.088 mol), DPG 89.73 parts by mass (0.419 mol), and calcium acetate monohydrate 7.31 × 10 ^-4 parts by mass (4.15 × 10 ^-6 mol), the same manner as in Example 1-1 was used. Synthesis was performed to obtain pellets of polycarbonate. Using the obtained polycarbonate pellets, various evaluations described above were performed. The evaluation results are shown in Table 1.

The value of the wavelength dispersion (R450 / R550) of the resin in this example is close to 1, and it has flat wavelength dispersion. In the resin of this example, it is presumed that if the amount of the structural unit derived from Compound 15 is increased, the inverse wavelength dispersion is exhibited, but the inferior wavelength dispersion is judged to be low in appearance.

[Comparative Example 1-10]

茀 -9,9-diethanol (Compound 16) 32.66 parts by mass (0.128 mol), ISB 54.34 parts by mass (0.372 mol), DPC 109.30 parts by mass (0.510 mol), calcium acetate monohydrate 1.32 × 10 ^-3 mass Except for parts (7.50 × 10 ^-6 mol), synthesis was performed in the same manner as in Example 1-1 to obtain pellets of polycarbonate. The above-mentioned various evaluations were performed using the obtained polycarbonate pellets. The evaluation results are shown in Table 1.

The resin of this example exhibits inverse wavelength dispersion, but the inverse wavelength dispersion exhibits poor performance, and the photoelastic coefficient also becomes high. In addition, in this example, the resin foamed slightly during polymerization or melt-forming, and the thermal stability was poor.

[Comparative Example 1-11]

68.07 parts by mass (0.155 mol) of BHEPF, 22.84 parts by mass (0.156 mol) of ISB, 0.97 parts by mass of PEG (9.75 × 10 ^-4 mol, 67.60 parts by mass (0.316 mol) of DPC, 5.36 × 10 ^{-4 of} magnesium acetate tetrahydrate Except for mass parts (2.50 × 10 ^-6 mol), a polycarbonate was obtained by synthesis in the same manner as in Example 1-1. Using the obtained polycarbonate particles, various evaluations described above were performed. The evaluation results are shown in Table 1.

The content of the structural unit derived from BHEPF of the resin in this example is 67.8% by mass, which is very large, and it can be understood that the reverse wavelength dispersion of the structural unit has poor visibility. In addition, the photoelastic coefficient becomes a higher value.

[Comparative Example 1-12]

41.17 parts by mass (0.109 mol) of BCF, 51.59 parts by mass (0.170 mol) of SPG, 63.19 parts by mass (0.295 mol) of DPC, 4.90 x 10 ^-3 parts by mass (2.78 x 10 ^-5 mol) of calcium acetate monohydrate, and A polycarbonate was obtained in the same manner as in Example 1-1 except that the final polymerization temperature was set to 260 ° C. Using the obtained polycarbonate pellets, various evaluations described above were performed. The evaluation results are shown in Table 1.

Although the resin of this example shows relatively excellent optical characteristics, the obtained film is very brittle and easily fractured and has poor toughness.

In the following Examples 1-2 to 6 and Comparative Examples 1-13 to 1-17, synthetic resin was synthesized using larger polymerization equipment, and a long film was produced by the melt extrusion method, and its characteristics to evaluate. Here, the stretching is carried out especially under the conditions near the fracture limit, and the stretched film is stretched. The birefringence (alignment) is evaluated.

[Example 1-2]

Polymerization was performed using a batch polymerization apparatus including two reactors with a vertical reactor having a stirring wing and a reflux cooler controlled at 100 ° C. Added bis [9- (2-phenoxycarbonylethyl) fluorene-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 × 10 ^-4 parts by mass (2.19 × 10 ^-6 mol) of calcium acetate monohydrate as a catalyst. After the inside of the reactor was purged with reduced-pressure nitrogen, it was heated with a heat medium, and stirring was started when the internal temperature became 100 ° C. After 40 minutes from the start of the temperature rise, the internal temperature was brought to 220 ° C, and the temperature was controlled to maintain the temperature. At the same time, the pressure was reduced. After reaching 220 ° C, it was set to 13.3 kPa in 90 minutes. The phenol vapor by-produced along with the polymerization reaction was introduced into a reflux cooler at 100 ° C, and a certain amount of monomer components contained in the phenol vapor was returned to the reactor. The uncondensed phenol vapor was introduced into the condensation at 45 ° C Device for recycling. After introducing nitrogen into the first reactor and temporarily returning to atmospheric pressure, the oligomerized reaction solution in the first reactor was transferred to the second reactor. Then, the temperature rise and pressure reduction in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Thereafter, polymerization is performed until a specific stirring power is obtained. At the time when the specific power was reached, nitrogen was introduced into the reactor and the pressure was increased. The produced polyester carbonate was extruded in water, and the strands were cut to obtain pellets.

A long unstretched film having a length of 3 m, a width of 200 mm, and a thickness of 72 μm was produced from the obtained polyester carbonate by using the above-mentioned melt extrusion method. Then, longitudinal uniaxial stretching was performed by the method described above, and a retardation film was produced under the conditions near the breaking limit. The results of various evaluations are shown in Table 2.

The retardation film of this example exhibits inverse wavelength dispersion, and further has excellent properties such as alignment, photoelastic coefficient, heat resistance, and toughness.

[Example 1-3]

Using bis [9- (2-phenoxycarbonylethyl) fluorene-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 parts by mass (2.18 × 10 ^-6 mol), and the thickness of the unstretched film is 66 μm. Example 1-2 produced a retardation film in the same manner. The results of various evaluations are shown in Table 2.

The value of the birefringence of the retardation film of this example is larger than that of Embodiment 1-2, so it can be understood that the alignment degree of the polymer of the retardation film of this example is high.

[Example 1-4]

Using bis [9- (2-phenoxycarbonylethyl) fluorene-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 ), DPC 81.26 parts by mass (0.379 mol), calcium acetate monohydrate 3.73 × 10 ^-4 parts by mass (2.12 × 10 ^-6 mol), and the thickness of the unstretched film is set to 73 μm. Example 1-2 produced a retardation film in the same manner. The results of various evaluations are shown in Table 2.

The retardation film of this example has relatively high alignment and a low photoelastic coefficient.

[Example 1-5]

Using bis [9- (2-phenoxycarbonylethyl) fluorene-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) ), DPC 63.77 parts by mass (0.298 mol), calcium acetate monohydrate 1.19 × 10 ^-2 parts by mass (6.78 × 10 ^-6 mol), and the thickness of the unstretched film is set to 62 μm. Example 1-2 produced a retardation film in the same manner. The results of various evaluations are shown in Table 2.

The birefringence and photoelastic coefficient of the retardation film of this example are better than those of Examples 1-2.

[Example 1-6]

Using bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (compound 3) 29.18 parts by mass (0.046 mol), 30.38 parts by mass (0.208 mol), 41.27 parts by mass (0.136 mol) ), DPC 64.55 parts by mass (0.298 mol), calcium acetate monohydrate 1.21 × 10 ^-2 parts by mass (6.86 × 10 ^-5 mol), and the thickness of the unstretched film is set to 58 μm. Example 1-2 produced a retardation film in the same manner. The results of various evaluations are shown in Table 2.

The retardation of the retardation film of this example is weaker than that of Example 1-2, so that the value of birefringence can be greater than that of Example 1-2, and the alignment of the polymer can be improved. The value of R450 / R550 of the retardation film of this example is farther from the ideal value of R450 / R550 than that of Example 1-2. However, when the film thickness of the film is valued according to the application, Example 1- 6's retardation film.

[Comparative Example 1-13]

63.72 parts by mass using BHEPF (0.145mol), ISB 26.74 parts by mass (0.183mol), PEG 0.97 parts by mass ^{(9.75 × 10 -4 mol),} DPC 71.24 parts by mass (0.333mol), magnesium acetate tetrahydrate 7.06 × 10 ^{- A} retardation film was produced in the same manner as in Example 1-2 except that ⁴ parts by mass (3.29 × 10 ^-6 mol) and the thickness of the unstretched film was 76 μm. The results of various evaluations are shown in Table 2.

Compared with the embodiment, the retardation film of this example can be understood to be inferior in alignment, inverse wavelength dispersion and photoelastic coefficient.

[Comparative Example 1-14]

68.07 parts by mass (0.155 mol) of BHEPF, 22.84 parts by mass (0.156 mol) of ISB, 0.97 parts by mass (9.75 × 10 ^-4 mol) of PEG, 67.60 parts by mass (0.316 mol) of DPC, 5.36 × 10 ^- magnesium acetate tetrahydrate ^A retardation film was produced in the same manner as in Example 1-2 except that ⁴ parts by mass (2.50 × 10 ^-6 mol) and the thickness of the unstretched film was 87 μm. The results of various evaluations are shown in Table 2.

The wavelength dispersion of the retardation film in this example is closer to the ideal value of R450 / R550 than the wavelength dispersion of Comparative Examples 1-13, but by making the inverse wavelength dispersion stronger and the alignment reduced, it becomes the manifestation of inverse wavelength dispersion. Those with poor sex.

[Comparative Example 1-15]

32.20 parts by mass (0.085 mol) of BCF, 60.43 parts by mass (0.199 mol) of SPG, 64.40 parts by mass (0.301 mol) of DPC, 5.00 × 10 ^-3 parts by mass (2.84 × 10 ^-5 mol) of calcium acetate monohydrate, and A retardation film was produced 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. The results of various evaluations are shown in Table 2.

The retardation film of this example has the disadvantages of poor alignment and inverse wavelength dispersion, and the film is brittle.

[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), calcium acetate monohydrate 2.13 × 10 ^-3 parts by mass (1.21 × 10 ^-5 mol), and A retardation film was produced in the same manner as in Example 1-2 except that the final polymerization temperature was set to 260 ° C. and the thickness of the unstretched film was set to 98 μm. The results of various evaluations are shown in Table 2.

The birefringence of the retardation film of this example is significantly lower than that of the embodiment. Moreover, the photoelastic coefficient also becomes large. Since the amount of the aromatic structure on the main chain is large, the amount of the aromatic component used to express the anti-dispersion property must also be large, so it can be considered that the optical characteristics are reduced.

[Comparative Example 1-17]

86.84 parts by mass (0.198 mol) of BHEPF, 14.95 parts by mass (0.077 mol) of DMT, 28.90 parts by mass (0.135 mol) of DPC, 1.35 × 10 ^-2 parts by mass (3.96 × 10 ^-5 mol) of tetra-n-butyl titanate A retardation film was produced 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. The results of various evaluations are shown in Table 2.

The birefringence of the retardation film of this example is also significantly lower than that of the embodiment, and the photoelastic coefficient also becomes large.

"Examples 2-1 to 2-2, Reference examples 2-1 to 2-2"

The quality evaluation of the tertiary diester of the present invention and the property evaluation of the resin composition and the transparent film were performed by the following methods. In addition, the characteristic evaluation method is not limited to the following methods, and the operator can select appropriately.

The abbreviations and the like of the compounds used in the following Synthesis Examples and Examples are as follows.

ISB: Isosorbide (manufactured by ROQUETTE FRERES, trade name: POLYSORB)

DPC: Diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation)

CHDM: 1,4-cyclohexanedimethanol (cis, trans mixture, manufactured by SK Chemicals)

SPG: Spirodiol (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

BHEPF: 9,9-bis [4- (2-hydroxyethoxy) phenyl] -fluorene (manufactured by Osaka Gas Chemicals)

THF: tetrahydrofuran (without stabilizer, manufactured by WAKO)

(1) Thermal decomposition temperature of oligomeric fluorene monomer (TG-DTA)

The decomposition starting temperature and melting point of the oligomeric fluorene monomer were measured using a differential thermal-thermogravimetric analyzer (TG-DTA 6300 manufactured by SII NanoTechnology). About 4 mg of the analysis sample was put into an aluminum pan manufactured by the same 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 flow of 200 mL / min. According to the obtained TG data (thermogravimetric data), the temperature at the intersection of the extrapolated baseline of the low-temperature side baseline of the reduction movement and the tangent of the maximum tilt point of the reduction is set as the decomposition starting temperature. In addition, based on the obtained TG data (thermogravimetric data), the peak top of the sample where no decrease in sample weight was observed and a steep endothermic peak was observed was set as the melting point of the sample.

(2) Na, K, Cs, Fe content in the resin composition

Approximately 0.5 g of the resin composition sample was accurately weighed to a micrometer manufactured by PerkinElmer In a wave decomposition container, 2 mL of 97% sulfuric acid (ultra-high purity sulfuric acid manufactured by Tama Chemicals) was added, and the container was sealed and subjected to microwave heating at 230 ° C for 10 minutes. After cooling to room temperature (30 ° C or lower), 1.5 mL of 68% nitric acid (ultra-high purity nitric acid manufactured by Tama Chemicals) was added, the sealed state was set, and microwave heating was performed at 150 ° C for 10 minutes, followed by cooling to room temperature ( 30 ° C or lower), and added 2.5 mL of 68% nitric acid, sealed again, and microwave-heated at 230 ° C for 10 minutes to completely decompose the contents. The microwave heater is a Multiwave 3000 manufactured by PerkinElmer. The temperature is adjusted by adjusting the output between 300W and 1000W. After cooling to room temperature (30 ° C or lower), the liquid obtained in the above was diluted with pure water, and quantified by ICP-MS manufactured by Thermo Fisher Scientific.

(3) Residual monohydroxy compounds in the resin composition

About 1 g of a sample of the resin composition was accurately weighed, dissolved in 5 mL of dichloromethane, and acetone was added so that the total amount became 25 mL. The solution was filtered through a 0.2 μm disc filter, and quantification of phenol by liquid chromatography was performed to calculate the content ratio.

(4) Toughness of the film (bending test)

A film having a thickness of 100 to 200 μm is formed by the above-mentioned hot pressing method, and a rectangular test piece with a length of 40 mm and a width of 10 mm is produced from the film. Open the gap between the left and right joint surfaces by 40mm, and fix both ends of the test piece into the joint surface. Then, the interval between the left and right joining surfaces is narrowed at a speed of 2 mm / sec or less, so that the film does not protrude beyond the joining surface of the vise, and the entire film bent into a zigzag shape is compressed inside the joining surface. The case where the test piece was broken into two pieces (or three or more pieces) at the bending portion before the full contact between the joint surfaces was set as "fractured", and the case where the test piece was not broken and was bent even if the test surface was completely contacted between the joint surfaces was set. "Unbroken". For the same type of film, the test was repeated 5 times, and those who became "fractured" 4 or more times were set to "×: brittle failure", and those who were "fractured" 3 or less times were set to "○: no brittle failure ".

(5) Measurement of refractive index and Abbe number

From the film obtained by the above hot-pressing method, cut out a length of 40mm and a width of 8mm A rectangular test piece is made into a measurement sample. Using a multi-wavelength Abbe refractometer (DR-M4 / 1550 manufactured by Atago Co., Ltd.), interference filters with wavelengths of 656 nm (C line), 589 nm (D line), and 486 nm (F line) are used. The refractive index, nC, nD, and nF were measured. The measurement was performed at 20 ° C using monobromonaphthalene as the interface liquid. The Abbe number νd is calculated using the following formula.

νd = (1-nD) / (nC-nF)

The larger the Abbe number, the smaller the wavelength dependence of the refractive index.

The reduction viscosity, glass transition temperature, melt viscosity, and photoelastic coefficient of the resin composition were measured in the same manner as in Example 1-1 described above.

<Example 2-1>

Bis {[9- (2-ethoxycarbonylethyl) fluorene-9-yl] -methyl} fluorene (Compound 3), and bis [9- (2-ethoxycarbonylethyl) fluorene-9- Of methane] methane (compound 2)

A 1 L separable flask was charged with 35.0 g (102 mmol) of bis (fluoren-9-yl) methane (compound 1) and 175 mL of THF, and the mixture was stirred at 15 ° C. under a nitrogen atmosphere. After adding 28.68 g of a 50% by weight aqueous sodium hydroxide solution and 4.61 g (20.2 mL) of benzyltriethylammonium chloride, the mixture was stirred for 15 minutes. After adding 22.4 mL (224 mmol) of ethyl acrylate over 60 minutes, it was aged at 16 ° C. for 2 hours. When HPLC analysis was performed at the reaction end time point, Compound 2 (13.5 min) was 75.3 area%, and Compound 3 (15.2 min) was 8.4 area%. After neutralization with 3N hydrochloric acid, liquid separation was performed to remove the aqueous layer. At this time, 70 mL of toluene was added, and the organic layer was washed 5 times with 105 mL of water. After adding 35 mL of toluene and 35 mL of THF to the organic layer, the solution was heated to an internal temperature of 60 ° C. or higher and concentrated under reduced pressure to 70 mL. Add toluene 35mL Then, it was left to cool to 45 ° C, and 210 mL of methanol was added to perform crystallization of bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] methane (compound 2). The crystallized product was filtered, and the filtrate was allowed to stand at room temperature for several days, and the produced bis {[9- (2-ethoxycarbonylethyl) fluorene-9-yl] -methyl was recovered by filtration. } White crystals of hydrazone (compound 3).

Bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] methane (compound 2): 37.47 g (68.7 mmol, yield: 67.6%), white powder

HPLC analysis results Compound 2 (13.5min): 91.7% area%, Compound 3 (15.2min): 5.2 area%

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.03 (d, J = 7.6Hz, 4H), 6.97 (dt, J1 = 7.6Hz, J2 = 1.5Hz, 4H), 6.82 (dt, J1 = 7.6Hz, J2 = 1.3Hz, 4H), 6.77 (d, J = 7.6Hz, 4H), 3.88 (q, J = 7.1Hz, 4H), 3.12 (s, 2H), 2.23 (m, 4H), 1.13 (m, 4H ), 1,02 (t, J = 7.1Hz, 6H).

Decomposition starting temperature (under nitrogen environment): 295 ℃

m.p .: 141 ℃

Bis [[9- (2-ethoxycarbonylethyl) fluorene-9-yl] -methyl} fluorene (Compound 3): 0.20 g (0.3 mmol, yield: 0.3%), white crystals

HPLC analysis results Compound 2 (13.5min): 3.5 area%, Compound 3 (15.2min): 92.6 area%

¹ H-NMR (400MHz, CDCl ₃ ) δ 6.91-6.95 (m, H), 6.86-6.89 (m, 4H), 6.68-6.70 (m, 4H), 6.62-6.65 (m, 2H), 6.57-6.59 (m, 4H), 6.40-6.42 (m, 2H), 6.30-6.34 (m, 2H), 6.22-6.24 (m, 2H), 3.80 (q, 7.1Hz, 4H), 2.93 (s, 4H), 2.06 (m, 4H), 1.00 (m, 10H)

Decomposition starting temperature (under nitrogen environment): 364 ℃

m.p .: 166 ℃

After completion of the reaction, HPLC after crystallization and filtration was performed under the following conditions.

Column: Inertsil ODS-3V 150mm × 4.8mm

Temperature: 40 ° C

Dissolution conditions: 0-5min: tetrahydrofuran / water = 50/50, 20min: tetrahydrofuran / water = 100/0

Flow rate: 1.0ml / min

Injection volume: 2μl

<Example 2-2>

Bis {[9- (2-phenoxycarbonylethyl) fluorene-9-yl] -methyl} fluorene (compound 5), and bis [9- (2-phenoxycarbonylethyl) fluorene-9- Of methane] methane (compound 4)

In a 1 L separable flask, bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] methane (Compound 2, 84.1 g, 154.5 mmol) and bis {[9- (2 -Ethoxycarbonylethyl) fluorene-9-yl] -methyl} fluorene (Compound 3, 3.3 g, 6.9 mmol) in a tetrahydrofuran / o-xylene mixed solution After adding diphenyl carbonate (147.5 g, 5685.5 mmol) The internal temperature was gradually raised to 104 ° C in the greenhouse, and thereafter, the pressure was reduced to 3 kPa, and the solvent was distilled off. After recompression, tetraisopropyl orthotitanate (2.45 g, 8.61 mmol) was added, the pressure was reduced to 3 kPa again, and the temperature was gradually raised to 184 ° C. to distill off the reaction distillate. After reaching 184 ° C, the reaction was carried out for 3 hours, and then the temperature was lowered to 90 ° C, followed by repressurization, and the progress of the reaction was confirmed by HPLC analysis. When ortho-xylene (144 ml) was added and the temperature was lowered to 41 ° C, precipitation of crystals was found. After cooling to 40 ° C, methanol (356 mL) was added, and after further cooling to 5 ° C, suction filtration was performed. The obtained crude crystals were dispersed in o-xylene (272 mL), water (0.32 g) was added, and then the temperature was raised to 80 ° C. to be dissolved. The organic layer was washed twice with water (240 mL), and then subjected to pressure filtration (0.25 MPa) using a PTFE membrane filter (0.5 μm). Thereafter, 110 g of the solvent was distilled using an evaporator. After removal by distillation, the temperature was lowered to 50 ° C, and as a result, precipitation of crystals was found. After further cooling to 40 ° C, methanol (336 mL) was added, and after cooling to room temperature (20 ° C), suction filtration was performed, and the solution was dried under reduced pressure at 80 ° C to a constant amount, thereby obtaining bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (compound 4) 59.9 g (yield: 55.6%, 46.8 mmol), and bis {[9- (2-phenoxycarbonylethyl) A mixture of fluorene-9-yl] -methyl} fluorene (compound 5) 0.2 g (yield: 2.2%, 0.15 mmol).

HPLC analysis results Compound 4 (15.3min): 98.17 area%, Compound 5 (16.5min): 0.15% area

After completion of the reaction, HPLC after crystallization and filtration was performed under the following conditions.

Column: Inertsil ODS-3V 150mm × 4.8mm

Temperature: 40 ° C

Dissolution conditions: 0-5min: tetrahydrofuran / water = 50/50, 20min: tetrahydrofuran / water = 100/0

Flow rate: 1.0ml / min

Injection volume: 2μl

¹ H-NMR measurement result Compound 4

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.23-7.28 (m, 4H), 7.07-7.16 (m, 6H), 7.03 (dt, J1 = 6.9Hz, J2 = 2.0, 4H), 6.78-6.90 (m , 12H), 3.20 (s, 2H), 2.37 (t, J = 8.3Hz, 4H), 1.40 (t, J = 8.3Hz, 4H).

m.p. (Compound 4): 176 ° C

LC / MS measurement results

Compound 4 (13.1min): (Exact Mass) 640

(Positive) 663 [M + Na] ⁺ , 679 (M + K] ⁺ , (Negative) 639 [MH] ^-

Compound 5 (14.2min): (Exact Mass) 818

(Positive) 841 [M + Na] ⁺ , 875 [M + K] ⁺ , (Negative) 817 [MH] ^-

The LC-MS measurement conditions were performed under the following conditions.

LC system: Agilent 1200

Column: Inertsil ODS-3 5μm 4.6 × 150mm No. 2EI85047

Temperature: 40 ° C

Dissolution conditions: 0-5min: tetrahydrofuran / water = 50/50, 20min: tetrahydrofuran / water = 100/0

Flow rate: 1.0ml / min

Injection volume: 0.2 μl

Mass analysis device: Agilent LC / MS 6130

Ion mode: AJS (Positive / Negative)

Capillary Voltage: 4500V (P / N)

Fragment Voltage: 100V

Mass Range: m / z = 100-1500

Driving gas: N ₂ , DG = 12L / min, NP = 60psi, DGT = 300 ℃

Other conditions: SG = 12L / min, ST = 300 ℃, NV = 1000

[Synthesis example of polymer]

<Synthesis Example 2-1>

Bis [9- (2-ethoxy) containing 0.05 parts by mass (0.0001 moles) of bis {[9- (2-ethoxycarbonylethyl) fluorene-9-yl] -methyl} fluorene (Compound 3) Carbonylcarbonylethyl) fluoren-9-yl] methane (compound 2) 26.44 parts by mass (0.0489 moles), CHDM 10.37 parts by mass (0.072 moles) and tetra-n-butyl titanate as a catalyst 14.65 × 10 ^-3 A mass part (4.30 × 10 ^-5 mol) was put into a reaction vessel, and reacted at 220 ° C. under a nitrogen atmosphere for 120 minutes at normal pressure. Then, the pressure was reduced to 13.3 kPa over 30 minutes, and the pressure was maintained at 13.3 kPa for 30 minutes, and the generated ethanol was drawn out of the reaction vessel. Thereafter, the reaction solution was temporarily cooled to room temperature (20 ° C), and 31.43 parts by mass (0.215 moles) and 51.66 parts by mass of DPC (0.241 moles) were put into the same reaction vessel. The heating tank was placed under a nitrogen atmosphere. The temperature was set to 150 ° C., and if necessary, the raw materials were dissolved (about 10 minutes). After the dissolution, the temperature was raised to 220 ° C. over 30 minutes in the first step of the reaction, and the reaction was carried out at normal pressure for 60 minutes. Then, the pressure was reduced from normal pressure to 13.3 kPa over 90 minutes, and kept at 13.3 kPa for 30 minutes, and the generated phenol was extracted out of the reaction vessel.

Then, in the step of the second stage of the reaction, the temperature of the heating tank was raised to 240 ° C for 15 minutes, and the pressure was reduced to 0.10 kPa or less for 15 minutes, and the generated phenol was drawn out of the reaction vessel. After reaching a specific torque, the reaction is ended, and the polymer produced is extruded in water to obtain pellets of polycarbonate resin.

Table 3 shows the measurement results of the glass transition temperature and the like of the obtained resin composition, refractive index anisotropy, retardation ratio (Re450 / Re550), and film toughness of the stretched film when the film is formed and stretched.

<Synthesis example 2-2>

Bis [9- (2-phenoxy) containing 0.1 parts by mass (0.0001 moles) of bis {[9- (2-phenoxycarbonylethyl) fluorene-9-yl] -methyl} fluorene (Compound 5) Carbonylcarbonylethyl) fluoren-9-yl] methane (compound 4) 29.5 parts by mass (0.0458 moles), SPG 30.20 parts by mass (0.099 moles), ISB 40.34 parts by mass (0.276 moles), DPC 70.49 parts by mass ( 0.329 mol) and 9.91 × 10 ^-4 parts by mass (5.63 × 10 ^-6 mol) of calcium acetate monohydrate as a catalyst, put them into the reaction vessel, and set the temperature of the heating tank to 150 ° C in a nitrogen environment, as required Stir and dissolve the raw material (about 10 minutes). After dissolving, in the step of the first stage of the reaction, the temperature was raised to 220 ° C. over 30 minutes, and the reaction was performed at normal pressure for 60 minutes. Then, the pressure was reduced from normal pressure to 13.3 kPa over 90 minutes, and the pressure was maintained at 13.3 kPa for 15 minutes. The generated phenol was extracted out of the reaction vessel.

Then, in the second step of the reaction, the temperature of the heating tank was raised to 245 ° C. for 15 minutes, and the pressure was reduced to less than 0.10 kPa over 15 minutes, and the generated phenol was drawn out of the reaction vessel. When a certain torque is reached, the reaction is ended and the generated The polymer was extruded in water to obtain pellets of polyester carbonate.

Table 3 shows the measurement results of the glass transition temperature and the like of the obtained resin composition, refractive index anisotropy, retardation ratio (Re450 / Re550), and film toughness of the stretched film when the film is formed and stretched.

<Reference Example 2-1>

Bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] methane (compound 2) 22.65 parts by mass (0.042 mol), CHDM 10.77 parts by mass (0.075 mol), and tetratitanate as a catalyst 15.54 × 10 ^-3 parts by mass (4.57 × 10 ^-5 mol) of n-butyl ester was charged into a reaction container, and reacted at 220 ° C. and normal pressure for 120 minutes under a nitrogen environment. Then, the pressure was reduced to 13.3 kPa over 30 minutes, and the pressure was maintained at 13.3 kPa for 30 minutes, and the generated ethanol was drawn out of the reaction vessel. Thereafter, the reaction solution was temporarily 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 were put into the same reaction vessel, and the temperature of the heating bath was set to 150 ° C under a nitrogen atmosphere. If necessary, stir and dissolve the raw materials (about 10 minutes). After the dissolution, the temperature was raised to 220 ° C. over 30 minutes in the first step of the reaction, and the reaction was carried out at normal pressure for 60 minutes. Then, the pressure was reduced from normal pressure to 13.3 kPa over 90 minutes, and kept at 13.3 kPa for 30 minutes, and the generated phenol was extracted out of the reaction vessel.

Then, in the second step of the reaction, the temperature of the heating tank was raised to 240 ° C. over 15 minutes, and the pressure was reduced to less than 0.10 kPa over 15 minutes, and the generated phenol was drawn out of the reaction vessel. After reaching a specific torque, the reaction is completed, and the polymer produced is extruded in water to obtain pellets of polyester carbonate resin.

Table 3 shows the measurement results of the glass transition temperature and the like of the obtained resin composition, refractive index anisotropy, retardation ratio (Re450 / Re550), and film toughness of the stretched film when the film is formed and stretched.

<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 7.28 × 10 ^-4 parts by mass (3.39 × 10 ^-6 mol) of magnesium acetate tetrahydrate as a catalyst was put into a reaction vessel, and the temperature of the heating tank was set to 150 ° C. under a nitrogen atmosphere, and stirred as needed, and The material was dissolved (about 10 minutes). After dissolving, in the step of the first stage of the reaction, the temperature was raised to 220 ° C. over 30 minutes, and the reaction was performed at normal pressure for 60 minutes. Then, the pressure was reduced from normal pressure to 13.3 kPa over 90 minutes, and kept at 13.3 kPa for 30 minutes, and the generated phenol was extracted out of the reaction vessel.

Then, in the second step of the reaction, the temperature of the heating tank was raised to 240 ° C. over 15 minutes, and the pressure was reduced to less than 0.10 kPa over 15 minutes, and the generated phenol was drawn out of the reaction vessel. After reaching a specific torque, the reaction is completed, and the polymer produced is extruded in water to obtain pellets of polyester carbonate resin.

Table 3 shows the measurement results of the glass transition temperature and the like of the obtained resin composition, refractive index anisotropy, retardation ratio (Re450 / Re550), and film toughness of the stretched film when the film is formed and stretched.

<Calculation of conformational energy and angle>

In order to study the relationship between the chemical structure and the optical properties of oligomeric fluorene, the energy calculation of the specific configuration (conformation) derived from the repeating unit of the oligomeric fluorene monomer was performed as follows and the ring and the main in the configuration Calculation of the angle formed by the chain.

For the software system, PC Spartan Pro 1.0.5 (Windows (registered trademark) 32-bit version) manufactured by American Wavefunction Corporation about the AM1 method is used. In addition, the input values related to the calculation accuracy such as the convergence determination value are all preset values using the software described above.

The calculation was performed on the structures derived from Compound 3 and Compound 2 shown below. Here, regarding compounds 3 and 2 as diester monomers, a resin polymerized by transesterification is assumed, and a structure in which both ester groups are methyl esters is calculated.

As shown below, the bond A between the carbon atom at position 茀 and the carbon atom bonded to the adjacent 茀 side and the 、 bond, the atom bonded to the side chain of 茀, and the main chain of the atom The dihedral angle formed by the interatomic bond B is 180 ° (that is, the side chain is in a trans configuration), and 60 ° and -60 ° (that is, the side chain is in a twisted configuration between the two types) is the initial structure The equilibrium structure and its energy (heat generation) are obtained by the AM1 method. Here, in each compound, a substituent having a methyl ester bonded to a carbon atom at the 茀 -position 9 is referred to as a side chain. Here, in order to estimate the three-dimensional structure of each repeating unit in the polymer, both of the two side chains existing in each compound were changed. That is, the so-called trans configuration in Table 4 refers to a structure in which two side chains of each monomer are in a trans configuration, and the so-called torsional configuration exists in two of each monomer. Both of the side chains are in a twisted configuration. In addition, there are two types of intertwisted configurations: 60 ° and -60 °, and two types of two side chains are calculated: 60 ° and -60 °.

At this time, the energy difference between the two configurations of the two side chains of each monomer which are in the trans configuration and the two intertwisted configurations is calculated. Table 4 describes these three configurations. The energy difference (kJ / mol) when the most stable shape is set to 0 (kJ / mol). When the energy difference is 4 kJ / mol or more, a configuration with a low energy (heat generation) (a configuration set to 0 (kJ / mol)) is set to a stable configuration. Regarding the validity of the results of the AM1 method in this calculation, it is confirmed that the same tendency as that of the B3LYP / 6-31G ^* method, which is a higher calculation in Japanese Patent Application No. 2013-214986, has been confirmed.

In addition, regarding the trans configuration and the two intertwisted configurations, the angle formed by the main chain and the cymbal ring is calculated and recorded.

In addition, the angle formed by the main chain and the cymbal ring is determined in the following manner. First, a straight line connecting carbon atoms of methyl groups at both ends is set as a main chain direction, and a plane passing through carbon atoms at positions 3, 6, and 9 of 茀 is set to a 茀 plane. At this time, the straight line on the 茀 -plane crossing the direction of the main chain exists infinitely, but the straight line on the 茀 -plane where the angle with the direction of the main chain becomes the smallest. Let this angle be the angle formed by the main chain and the loop. Here, Compound 3 has three fluorene groups in the molecule, so the central fluorene ring is used to calculate the angle formed by the main chain and the fluorene ring.

In Table 4, when the compounds 3 and 2 are compared, the energy (generating heat) of both trans configurations is equal to the energy (generating heat) of the two intertwisted configurations, or the trans form is slightly stable.

In the comparison between compound 3 and compound 2, the main chain of trans configuration In the angle, the compound 3 having 3 fluorenyl groups is 84.2 °, the compound 2 having 2 fluorenyl groups is 74.6 °, and the compound 3 shows a value close to 90 °.

The present inventors have found that the fluorene ring is orthogonal to the main chain in the resin composition, thereby manifesting its optical characteristics. Furthermore, in Japanese Patent Application No. 2013-214986, the following cases were confirmed: the difference between the angle formed by the main chain and the ring in the stable configuration obtained by calculation and the ATR analysis of polarized light, and the inverse wavelength dispersion characteristic Correlation, the closer the angle obtained by calculation is to 90 °, the more clearly the difference spectrum of polarized ATR analysis is observed, and the stronger the inverse wavelength dispersion characteristic is obtained. When the angle of the trans configuration is 50 ° or more, preferably 60 ° or more, more preferably 70 ° or more, and even more preferably 80 ° or more, the inverse wavelength dispersion is expected to be exhibited, and the repeated structures used are all exhibited Inverse wavelength dispersion.

According to the comparison between Reference Example 2-1 and Reference Example 2-2, when the use of a retardation film exhibiting inverse wavelength dispersion is assumed, the same retardation ratio (Re450 / Re550) of 0.90 is exhibited. Reference Example 2-1 (polyester carbonate) contains far less fluorene-containing monomers than Reference Example 2-2 (polycarbonate) using BHEPF. Therefore, it can be said that the compound 2 has a high effect of exhibiting anti-wavelength dispersion. For those who use BHEPF. It can be considered that the reason is that the ratio of fluorene of the diester of compound 2 is higher than that of BHEPF. Compared with BHEPF, the ratio of the soft alkyl group of compound 2 is low and rigid, so it is easy to become a fluorene ring perpendicular to the main State of the chain.

According to the simulation results, it can be considered that the stability of the trans configuration of compound 2 is equal to that of the torsional configuration, or that the trans configuration is slightly more stable than that of the torsional configuration. In contrast, the trans configuration of compound 3 is stable. , And its presence ratio is high. Furthermore, in each of the trans configurations of compound 3 and compound 2, the angles formed by the main chain and the fluorene ring are both 70 ° or more, and it is expected that a high reverse wavelength dispersion property is exhibited. Furthermore, in compound 3, the angle formed by the main chain and the fluorene ring exceeds 80 °, and it can be considered that the inverse wavelength dispersion of compound 2 or more can be exhibited. Therefore, it can be considered that the inverse wavelength equivalent to compound 2 can be exhibited in a smaller amount than compound 2. Dispersion.

In addition, the melting point of compound 3 is 20 ° C or more higher than that of compound 2, and the decomposition initiation temperature is also higher. Therefore, it is assumed that the glass transition temperature of the resin is higher than that of the compound 2 Resin is considered to have high thermal stability.

<茀 ration>

The chemical structural formula derived from the repeating unit derived from the fluorene ring-containing monomer synthesized in Synthesis Example 2-1 and the ratio to fluorene are shown in Table 5. The 茀 ratio is calculated from the following formula. The molecular weight of the fluorene skeleton in the following formula is calculated based on 13 carbon atoms (excluding hydrogen atoms).

茀 ratio (%) = molecular weight of 茀 skeleton / molecular weight of repeating unit × 100

As described above, it is considered that the required optical characteristics can be efficiently exhibited by increasing the ratio of plutonium in the repeating unit, but the plutonium ratios of compound 2, compound 3, compound 4, and compound 5 are all 70%. From the above, it can be considered that the use of the resin composition of the present invention is suitable for efficiently developing the optical characteristics required. On the other hand, the ratio of fluorene in the repeating unit derived from BHEPF is less than 50%, and the required optical characteristics are not effectively developed. It can be considered that in order to develop the required optical characteristics, it is necessary to improve the unit with fluorene. Body use ratio.

Based on the above, when the use of a retardation film exhibiting inverse wavelength dispersion is assumed, the resin composition containing the polymer having a trifluorene repeating unit of the present invention appears as follows: even if a trimethyl diester is used in a small amount, Various physical properties such as heat resistance or positive inherent birefringence and phase difference ratio can also be achieved.

<< Example 3-1 >>

The abbreviations and the like of the compounds used in the following examples are as follows.

ISB; Isosorbide (manufactured by ROQUETTE FRERES, trade name; POLYSORB)

DPC; Diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation)

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) fluorene-9-yl] -methyl} fluorene (Compound 2)

<Synthesis Example 3-1A> Synthesis of bis (fluoren-9-yl) methane (compound 1)

Rhenium (120 g, 722 mmol) and N, N-dimethylformamidine (480 ml) were added to a 1 L four-necked flask, followed by nitrogen substitution, and then cooled to 5 ° C or lower. Sodium ethoxide (24.6 g, 361 mmol) was added, and paraformaldehyde (8.7 g, 289 mmol) was added in small amounts multiple times so as not to exceed 10 ° C., and stirred. After 2 hours, 1N hydrochloric acid (440 ml) was added dropwise to stop the reaction. The obtained suspension solution was suction-filtered, and spray-washed with demineralized water (240 ml). Thereafter, the obtained crude product was dispersed in desalted water (240 ml) and stirred for 1 hour. This suspension was subjected to suction filtration, and then spray-washed with demineralized water (120 ml). The obtained crude product was dispersed in toluene (480 ml), and then dehydrated using a Dean-Stark apparatus under heating and refluxing conditions. After returning to room temperature (20 ° C), pump down Filtration and drying under reduced pressure at 80 ° C. until a constant amount was obtained, thereby obtaining 84.0 g of bis (fluoren-9-yl) methane (compound 1) as a white solid (yield: 84.5%, HPLC purity: 94.0%).

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.83 (d, J = 7.6Hz, 4H), 7.56 (dd, J1 = 7.6Hz, J2 = 0.8Hz, 4H), 7.41 (t, J = 7.3Hz, 4H ), 7.29 (dt, J1 = 7.3Hz, J2 = 1.3Hz, 4H), 4.42 (t, J = 7.6Hz, 2H), 2.24 (d, J = 7.6Hz, 2H).

<Synthesis 3-1B-1> Synthesis of 9-{[(2-ethoxycarbonylethyl) fluorene-9-yl] -methyl} fluorene (Compound 2)

To a 1 L separable flask was added the bis (fluoren-9-yl) methane obtained in Synthesis Example 3-1A (Compound 1, 34.0 g, 98.7 mmol), N-benzyl-N, N, N-trichloro Ethylammonium (4.47g, 19.6mmol), tetrahydrofuran (170ml), after nitrogen substitution, the internal temperature was controlled to 15 ° C ~ 18 ° C, and a 50wt / wt% sodium hydroxide aqueous solution (25.93g) was added. As a result, the color of the solution Turns pale yellow. Thereafter, ethyl acrylate (10.7 ml, 103 mmol) was added dropwise over 30 minutes, and then analyzed by HPLC.

(HPLC conditions)

Column: Inertsil ODS-3V 150mm × 4.8mm

Temperature: 40 ° C

Dissolution conditions: 0 ~ 5min: tetrahydrofuran / water = 50/50, 20min: tetrahydrofuran / water = 100/0

Flow rate: 1.0ml / min

Injection volume: 2 μL

(HPLC analysis result)

Compound 1 (13.9min): 15 area%, Compound 2 (13.1min): 61 area%, Compound 3 (13.5min): 15 area%

<Synthesis Example 3-1B-2> 9-{[(2-ethoxycarbonylethyl) fluorene-9-yl] -methyl} fluorene (Compound 2)

To a 50 mL three-necked flask was added Compound 1 (1.0 g, 2.9 mmol) and benzyl triethyl chloride. Ammonium (132 mg, 0.58 mmol), THF (5 mL), and stirred at room temperature under a nitrogen atmosphere. After adding ethyl acrylate (290 mg, 2.9 mmol) over 30 minutes, it was aged at room temperature for 3 hours. After aging at 16 ° C for 1 hour, neutralization was performed with 3N hydrochloric acid. Toluene (5 mL) was added here, and the toluene phase was washed once with a saturated aqueous sodium hydrogen carbonate solution (5 mL), and the toluene phase was washed three times with water (5 mL). After toluene was distilled off in an evaporator, the residue was purified by silica gel chromatography to obtain compound 2 (0.63 g, 1.4 mmol, yield: 49%, white crystals).

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.74-7.80 (m, 2H), 7.53-7.56 (m, 4H), 7.38-7.45 (m, 4H), 7.19 (t, J = 7.5Hz, 2H), 7.03 (dt, J1 = 7.5Hz, J2 = 1.0Hz, 2H), 6.60 (d, J = 7.5Hz, 2H), 3.93 (q, J = 7.0Hz, 2H), 3.12 (t, J = 4.6Hz, 1H), 2.73 (d, J = 4.6Hz, 2H), 2.48-2.52 (m, 2H), 1.58-1.62 (m, 2H), 1.10 (t, J = 7.0Hz, 3H).

In the case of adding 1 equivalent of ethyl acrylate using Compound 1 as a raw material from Synthesis Example 3-1B-1, the speed of the addition reaction of ethyl acrylate is the same as that in the second addition In this case, it is theoretically certain that the ratio of Compound 1 to Compound 2 to Compound 3 becomes 1: 2: 1. However, it was surprising that in this reaction, it was found that the area ratio of HPLC became 1: 4: 1, and Compound 2 of the single adduct was selectively produced. The reason is believed to be that the structure in which the three fluorene rings of compound 3 are stacked is the most stable structure. In contrast, the structure in which the two fluorene rings of compound 1 and compound 2 are inverted is the most stable structure. When adding a second ethyl acrylate, one fluorene ring must be inverted to perform the addition. The proton ring-derived protons of compound 1 and compound 2 were observed on the δ 6.60-7.80 ppm integral low magnetic field side in ¹ H-NMR. In contrast, the proton ring-derived protons of compound 3 at δ 6.77 The high magnetic field side of -7.03ppm was observed, and the strong shielding effect was found. Therefore, it is also supported to stack the ring structure.

In the case where there are usually two substituent introduction sites, it may become difficult to selectively introduce a reactive functional group into only one place, but in the case of a specific oligomeric fluorene compound In this case, it may be considered that the specific reactive functional group can be easily introduced into only one place due to the difference in stereoreactivity, and it can also be produced industrially.

In addition, when a reactive substituent is introduced into an oligomeric fluorene compound such as compound 1 by addition reaction or substitution reaction, it is considered that an oligomeric fluorene having one reactive functional group can be selectively produced similarly. Therefore, it can be widely used in addition to ethyl acrylate.

<Application of oligomeric fluorene having 1 reactive substituent as a resin raw material>

For example, it can be considered that the monoester body of compound 2 functions as a terminal capping agent by using it as a raw material of polyester or polyester carbonate, so it can be considered as a molecular weight regulator of polyester or polycarbonate. it works.

<Application of oligomeric fluorene compounds having two different reactive functional groups as resin raw materials>

For example, it can be considered that, as the monoester of compound 2 further introduces a hydroxyl group as a reactive substituent, an oligomeric fluorene compound having 2 different reactive functional groups can be synthesized, and only a polymer having a high fluorene content can be obtained Esters are therefore useful.

<< Examples 4-1 ~ 4-4, Comparative Examples 4-1 ~ 4-2 >>

The quality evaluation of the oligomeric fluorene monomer and the property evaluation of the resin composition and the transparent film of the present invention were performed by the following methods. In addition, the characteristic evaluation method is not limited to the following methods, and the operator can select appropriately.

The abbreviations and the like of the compounds used in the following Synthesis Examples and Examples are as follows.

ISB; isosorbide (manufactured by ROQUETTE FRERES, trade name; POLYSORB)

DPC; Diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation)

CHDM; 1,4-cyclohexanedimethanol (cis, trans mixture, manufactured by SK Chemicals)

BHEPF: 9,9-bis [4- (2-hydroxyethoxy) phenyl] -fluorene (manufactured by Osaka Gas Chemicals)

(1) Powder X-ray diffraction of oligomeric diesters

The powder X-ray diffraction pattern of the oligomeric diester was measured using a powder X-ray diffraction measurement device (Spectris PANalitical Division X-Pert 'Pro).

(2) Particle size distribution measurement of oligomeric fluorene diester

The particle size distribution of the oligomeric diester was measured using a laser diffraction and scattering type particle size distribution measuring device (MT3300EX manufactured by Microtrac-bel) in methanol in a solvent.

(3) Rotation repose angle of oligomeric diester

The rotation rest angle of the oligomeric diester was measured by a cylinder rotation method using a three-wheeled rest angle measuring device (manufactured by Tsutsui Rika Chemical Co., Ltd.).

(4) Evaluation of thermal stability of oligomeric fluorene diesters

500 mg of an oligomeric diester was added to a 30 mL flask, and stirred at 185 ° C. for 7 hours under a nitrogen atmosphere. Visually confirm the hue before and after heating. Further, a 1 wt% THF solution of the oligomeric fluorene diester before and after heating was prepared, and the absorbance at a wavelength of 400 nm was measured using an ultraviolet-visible absorption spectrophotometer (UV-1650PC manufactured by Shimadzu Corporation).

<Example 4-1>

<Example 4-1A> bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] methane (compound 2) Synthesis

To a 1 L separable flask, add bis (fluoren-9-yl) methane (50 g, 145.2 mmol), benzyltriethyltriethylammonium chloride (6.6 g, 29.0 mmol), and tetrahydrofuran (250 mL), and replace with nitrogen. Then, the temperature was controlled to 17 ° C. to 19 ° C. under a water bath, and a 50 wt / vol% sodium hydroxide aqueous solution (26.5 mL) was added. As a result, the color of the solution became light red. Thereafter, ethyl acrylate (15.1 mL, 145.2 mmol) was added dropwise over 30 minutes. Thereafter, benzyltriethylammonium chloride (6.6 g, 29.0 mmol) was added, and further, ethyl acrylate (30.2 mL, 290.2 mmol) was added, and the progress of the reaction was followed by HPLC, followed by stirring for 2 hours. After confirming that the single adduct was 2% or less by HPLC, the solution was cooled with an ice bath, and 3N hydrochloric acid (166.4 mL) was added dropwise under temperature equilibrium, followed by quenching. After the aqueous layer was discarded, 100 mL of toluene was added, and the organic layer was washed with a saturated sodium bicarbonate aqueous solution (150 mL), and then the organic layer was washed with demineralized water (150 mL). After that, tetrahydrofuran was distilled off under reduced pressure, and then methanol (200 mL) was added to perform crystallization. After suction filtration, it was dried under reduced pressure at 100 ° C until a constant amount was obtained, thereby obtaining 61.9 g of bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] methane (compound 1) as a white solid. (Yield: 78.0%, HPLC purity: 87.4 area%).

<HPLC conditions>

Column: Inertsil ODS-3V 150mm × 4.8mm

Temperature: 40 ° C

Dissolution conditions: 0-5min: tetrahydrofuran / water = 50/50, 20min: tetrahydrofuran / water = 100/0

Flow rate: 1.0mL / min

Injection volume: 2 μL

HPLC analysis results Compound 4 (5.9min): 0.0 area% (0.0% by mass), Compound 5 (10.4min): 3.0 area% (2.9% by mass), Compound 3 (13.5min): 87.4% by area (89.0% by mass)

() Indicates the quantitative value calculated from the calibration curve.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.03 (d, J = 7.6Hz, 4H) 6.97 (dt, J1 = 7.6Hz, J2 = 1.5Hz, 4H), 6.82 (dt, J1 = 7.6Hz, J2 = 1.3Hz, 4H), 6.77 (d, J1 = 7.6Hz, 4H), 3.88 (q, J = 7.1Hz, 4H), 3.12 (s, 2H), 2.23 (m, 4H), 1.13 (m, 4H) 1.02 (t, J = 7.1Hz, 6H).

m, p .: 141 ℃

<Example 4-1B> Synthesis of bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (Compound 2)

To a 1 L four-necked flask were added bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] methane (Compound 1, 49.7 g, 91.2 mmol), diphenyl carbonate (98.3 g, 459 mmol), Tetraisopropyl orthotitanate (1.3 mL, 4.59 mmol), the degree of reduced pressure was adjusted to 3 to 2 kPa, and the by-products were distilled off in a temperature range of 140 ° C to 150 ° C, and stirred for 10 hours. After cooling to 90 ° C and confirming the completion of the reaction by HPLC, toluene (100 mL) was added and the mixture was cooled to 50 ° C. At this time, methanol (250 mL) was added, and after cooling to room temperature, suction filtration was performed. The obtained white solid was dispersed in toluene (100 mL) and heated under reflux for 30 minutes. After cooling to 50 ° C, methanol (250 mL) was added. After cooling to room temperature (20 ° C), suction filtration was performed, and the solution was dried under reduced pressure at 100 ° C to a constant amount, thereby obtaining bis [9- (2-phenoxycarbonylethyl) 乙基 -9 as a white solid. -Base] methane (compound 2) 35.2 g (yield: 60%, HPLC purity: 98.4 area%).

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.23-7.28 (m, 4H), 7.07-7.16 (m, 6H), 7.03 (dt, J1 = 6.9Hz, J2 = 2.0, 4H), 6.78-6.90 (m , 12H), 3.20 (s, 2H), 2.37 (t, J = 8.3Hz, 4H), 1,40 (t, J = 8.3Hz, 4H).

m.p .: 176 ℃

Ti content: 330 mass ppm

<Example 4-2> Synthesis of bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (compound 2)

Diphenyl carbonate (74.9 parts by mass) was added to a 250 LGL reactor at 120 ° C. Perform dissolution. At this time, bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] methane (Compound 1, 38.1 parts by mass) and tetraisopropyl orthotitanate (1.0 parts by mass) were added, and the pressure was reduced. The degree was adjusted to 3.0 kPa, the by-products were distilled off, and stirred for 7 hours until the internal temperature reached 185 ° C. After returning to normal pressure with nitrogen, it was cooled to 90 ° C. After the completion of the reaction was confirmed by HPLC, toluene (66 parts by mass) was added, transferred to a 400LGL reactor, and cooled to 50 ° C. At this time, methanol (151 parts by mass) was added, and after cooling to 5 ° C, centrifugal filtration was performed. The obtained crude product was dispersed in toluene (66 parts by mass) and heated under reflux for 30 minutes. After cooling to 50 ° C, methanol (151 parts by mass) was added, and after cooling to 22 ° C, centrifugal filtration was performed. Further, the obtained crude product was dispersed in toluene (66 parts by mass) and heated under reflux for 30 minutes. After cooling to 50 ° C, methanol (151 parts by mass) was added, and after cooling to 22 ° C, centrifugal filtration was performed. 27.2 g of bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (compound 2) was obtained as a white solid by drying under reduced pressure at 80 ° C. (yield: 61 %, HPLC purity: 99.5 area%).

Ti content ratio: 40 mass ppm

<Example 4-3> Synthesis of bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (compound 2)

To a 1 L separable flask was added the bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (compound 2, 60 g) and toluene (120 mL) obtained in Example 4-2, and the temperature was raised. After dissolving at 80 ° C, demineralized water (180 mL) was added, and after stirring for 30 minutes, the aqueous layer was discarded by a liquid separation operation. Demineralized water (180 mL) was added again, and after stirring for 30 minutes, the aqueous layer was discarded by a liquid separation operation, and then the organic layer was filtered under pressure (0.2 MPa, ADVANTEC PTFE membrane filter, pore diameter 0.5 μm: H050A47A). The organic layer was added to a 1 L separable flask, stirred, and cooled to 40 ° C. At this time, methanol (300 mL) was added, and after cooling to 22 ° C, suction filtration was performed. 54.1 g of bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (compound 2) was obtained as a white solid by drying under reduced pressure at 80 ° C (yield: 90). %).

Ti content ratio: <0.1 mass ppm

<Example 4-4>

The bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (compound 2, 61.7 g) obtained in Example 4-2 was dissolved in chloroform, and a silica gel column chromatography ( Eluent: chloroform). With respect to the obtained chloroform solution, chloroform was distilled off under reduced pressure using an evaporator, and MeOH (300 mL) was added. After cooling to room temperature (20 ° C), suction filtration was performed, and the solution was dried under reduced pressure at 80 ° C to a constant amount, thereby obtaining bis [9- (2-phenoxycarbonylethyl) 乙基 -9 as a white solid. -Base] methane (compound 2) 59.8 g (yield: 97%, HPLG purity: 99.5 area%).

Ti content ratio: <0.1 mass ppm

<Comparative Example 4-1> Synthesis of bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (Compound 2)

To a 500 mL four-necked flask were added bis [9- (2-ethoxycarbonylethyl) fluorene-9-yl] methane (compound 1, 35.0 g, 64.3 mmol), diphenyl carbonate (68.8 g, 321 mmol), Tetraisopropyl orthotitanate (0.95 mL, 3.24 mmol), the degree of reduced pressure was adjusted to 2.8 to 3.2 kPa, the by-products were distilled off and stirred for 6 hours at a temperature range of 135 ° C to 150 ° C. After cooling to 90 ° C and confirming the completion of the reaction by HPLC, toluene (70 mL) was added and the mixture was cooled to 50 ° C. At this time, methanol (175 mL) was added, and after cooling to 5 ° C, suction filtration was performed. The obtained white solid was dispersed in toluene (70 mL) and heated under 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, and the solution was dried under reduced pressure at 80 ° C to a constant amount, thereby obtaining bis [9- (2-phenoxycarbonylethyl) 乙基 -9 as a white solid. -Yl] methane (compound 2) 32.2 g (yield: 78%, HPLC purity: 99.0 area%).

Ti content ratio: 770 mass ppm

<Comparative Example 4-2>

[Chemical 146]

<Comparative Example 4-2A> Synthesis of bis [9- (2-methoxycarbonylethyl) fluorene-9-yl] methane (Compound 3)

To a 200 mL four-necked flask were added bis (fluoren-9-yl) methane (10.01 g, 29.06 mmol), N-benzyl-N, N, N-triethylammonium chloride (1.32 g, 5.78 mmol), and tetrahydrofuran. (50 mL), after nitrogen substitution, the temperature was controlled to 15-20 ° C. in a water bath, and a 50% aqueous sodium hydroxide solution (8 mL) was added. As a result, the color of the solution became light red. Thereafter, the internal temperature was controlled to 17 to 18 ° C. using an ice bath, and methyl acrylate (7.8 mL, 86 mmol) was added dropwise over 3 hours. The progress of the reaction was followed by HPLC, and after stirring for 3 hours, it was cooled in an ice bath, and while 3N hydrochloric acid (22 mL) was added dropwise, the internal temperature was controlled so as not to exceed 18 ° C., and quenched. To the organic layer obtained by liquid separation was added toluene (20 mL), and after washing with demineralized water, the solvent was distilled off under reduced pressure and concentrated. The concentrated solution was returned to room temperature (20 ° C), and methanol (40 mL) was added to perform crystallization. 7.05 g of bis [9- (2-methoxycarbonylethyl) fluorene-9-yl] methane (compound 3) was obtained as a white solid after suction filtration and drying under reduced pressure at 80 ° C to a constant amount. (Yield: 47.0%, HPLC purity: 80.0 area%).

<HPLC conditions>

Column: Inertsil ODS-3V 150mm × 4.8mm

Temperature: 40 ° C

Dissolution conditions: 0-5min: tetrahydrofuran / water = 50/50, 20min: tetrahydrofuran / water = 100/0

Flow rate: 1.0ml / min

Injection volume: 2 μL

HPLC analysis results Compound 4 (5.9min): 12.8 area% (12.8% by mass), compound 6 (not detected): Not detected, compound 3 (11.8min): 80.0% by area (84.6% by mass)

() Indicates the quantitative value calculated from the calibration curve.

¹ H-NMR (400MHz, CDCl ₃ ) δ 7.02 (m, 4H), 6.97 (m, 4H), 6.84-6.76 (m, 8H), 3.39 (s, 6H), 3.13 (s, 2H), 2.25 ( m, 4H), 1.15 (m, 4H).

<Comparative Example 4-2B> Synthesis of bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (Compound 2)

To a 50 mL three-necked flask was added bis [9- (2-methoxycarbonylethyl) fluorene-9-yl] methane (compound 3, 6.0 g, 11.6 mmol), diphenyl carbonate (12.1 g, 56.6 mmol), and Tetraisopropyl titanate (0.16 mL, 0.55 mmol) was heated to 145 ° C and stirred for 1 hour. It was confirmed by HPLC that the reaction did not proceed. Therefore, tetraisopropyl orthotitanate (0.32 mL, 1.1 mmol) was further added. After 1 hour, HPLC analysis was performed again. As a result, the disappearance of the peak of Compound 4 and the progress of the reaction were confirmed. Stir for 1 hour at ℃. After confirming the completion of the reaction by HPLC, toluene (15 ml) was added, and the mixture was heated under reflux for 1 hour. After cooling to 50 ° C, methanol (18 mL) was added. After cooling to room temperature (20 ° C), suction filtration was performed. The obtained white solid was dispersed in toluene (12 mL) and heated under reflux for 1 hour. After cooling to 50 ° C, methanol (18 mL) was added. After cooling to room temperature (20 ° C), suction filtration was performed, and the solution was dried under reduced pressure at 100 ° C to a constant amount, thereby obtaining bis [9- (2-phenoxycarbonylethyl) 乙基 -9 as a white solid. -Yl] methane (compound 2) 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) fluorene-9-yl] methane (compound 2,1201 parts by mass) in a glass-lined 12m ³ reactor was heated at 86 ° C. The temperature was gradually lowered, and methanol (551 parts by mass) was added at a time point when the temperature reached 60 ° C, and seed crystals were further added at a time point when the temperature reached 55 ° C to precipitate crystals. Then, it cooled to 40 degreeC over 5 hours, methanol (3548 mass parts) was added over 1 hour, and it cooled to 21 degreeC over 5 hours. The crystals were obtained by centrifugal filtration in 10 batches, and dried in a conical dryer at 80 ° C in two batches until a constant amount was obtained, thereby obtaining bis [9- (2-phenoxycarbonylethyl) fluorene- as a white solid. 1-125 parts by mass of 9-yl] methane (compound 2) (recovery rate: 94%, HPLC purity: 99.8 area%).

Average particle size: 178μm, cumulative particle size above 50μm%: 99%

Rotation angle: 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) fluorene-9-yl] methane (compound 2,1224 parts by mass) was placed in a glass-lined 12m ³ reactor from 81 ° C. Slowly lower the temperature and add seeds when the temperature reaches 68 ° C. Then, it cooled to 49 degreeC, methanol (4579 mass parts) was added over 1 hour, and it cooled to 21 degreeC over 5 hours. The crystals were obtained by centrifugal filtration in 6 batches, and dried in a cone dryer at 80 ° C in 2 batches until a constant amount was obtained, thereby obtaining bis [9- (2-phenoxycarbonylethyl) fluorene- as a white solid. 10-43 parts by mass of 9-yl] methane (compound 2) (recovery rate: 85%, HPLC purity: 99.8 area%).

Average particle size: 44μm, 50% or more cumulative particle size%: 30%

Rotation angle: 62 °

<Reference Example 4-3>

After replacing the glass-lined 1m ³ reactor with nitrogen, bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (compound 2, 250 parts by mass) and o-xylene (450 parts by mass) were added. Parts), heated 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 within 1 hour, and started centrifugation filtration.

The first centrifugation allowed smooth filtration, but the crystals in the reactor gradually became fine. As a result, the slurry properties are dramatically deteriorated, and filtration can be performed until the third centrifugation, but subsequent extraction becomes difficult and the centrifugal filtration is interrupted. The obtained by the third centrifugation was dried at 80 ° C until a constant amount was obtained, thereby obtaining bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (Compound 2) as a white solid. ) 63.2 parts by mass (recovery rate: 25%).

1st centrifugation

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: 220μm, cumulative particle diameter above 50μm%: 88%

3rd centrifugation

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 size: 25μm, cumulative particle size above 50μm%: 5%

Comparing Example 4-1 with Example 4-2, it can be seen that by increasing the number of crystallization times of toluene / methanol, the target oligomeric diaryl diaryl ester (compound 2) has a reduced Ti content from 330 ppm to 40 ppm. . In addition, if Example 4-1 is compared with Comparative Example 4-1, it can be seen that in Comparative Example 4-1, the toluene / methanol crystallization temperature was lowered from room temperature to 5 ° C, so that the yield was 60%. It was improved to 78%, but the residual amount of Ti was significantly increased from 330 ppm to 770 ppm and deteriorated. In Comparative Example 4-2, when a raw material containing oligomeric dicarboxylic acid was used in a proportion of more than 10% by mass, if the transesterification reaction catalyst was used in a specific amount, the reaction did not proceed and it was necessary to Added transesterification catalyst. The reason is believed to be that the oligomeric dicarboxylic acid and the Ti compound of the transesterification reaction catalyst form a complex and are deactivated. Therefore, it can be seen that the Ti content of the obtained oligomeric fluorene diaryl ester (compound 2) is greatly increased. 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, silica gel column chromatography was applied to Example 4-2. The obtained compound is refined, whereby the Ti content can be reduced below the detection limit. Especially with water washing steps and The refining method of pressure filtration is relatively excellent because it has a relatively low cost and can also be implemented industrially.

The Ti content in the oligomeric fluorene diesters of each Example and Comparative Example and the results of thermal stability evaluation are summarized and shown in Table 6.

Next, based on Table 6, the change in hue of the crystals in the molten state by heating is discussed. Regarding the color tone before heating, it was a slightly yellowish yellowish color in Example 4-1, but Example 4-2, Example 4-3, and Example 4-4 were white. In contrast, Comparative Examples 4-1 and 4-2 were colored yellow before self-heating. Further, heating was performed at 185 ° C for 7 hours. As a result, no coloring was found in Example 4-3 and Example 4-4, and colorless and transparent crystals were obtained. It was found that in Example 4-2, Example 4-1, Comparative Example 4-1, and Comparative Example 4-2, as the Ti content increased, the coloring tended to become noticeably thicker, especially Comparative Example 4-1 and Comparative Example 4 The crystals of -2 are brown after heating.

The detailed reason for the coloring is not clear, but chelation of the metal component is considered to be one of the reasons.

Then, based on FIG. 1, the change in hue before and after heating is discussed based on the change in absorbance at 400 nm of a 1% by weight THF solution. According to FIG. 1, in Example 4-2 (40 ppm), Example 4-3 (<0.1 ppm), and Example 4-4 (<0.1 ppm), no change in the absorbance of the THF solution was observed before and after heating. In Example 4-1 (330ppm) and Comparative Example 4-1 (770 In ppm), the Ti content was about 2 times, but the difference in absorbance was found to be a difference close to 4 times. Based on the above, it was confirmed that there was a large gap between the 330 ppm of Example 4-1 and the 770 ppm of Comparative Example 4-1 regarding the effect of Ti content on hue. In Comparative Example 4-2 (3300 ppm), the color tone was deteriorated, the precipitation of insoluble components was intense, and the absorbance measurement at 400 nm was difficult.

According to the above situation, there is a case where, by using the oligomeric fluorene diester of the present invention, there is less change in color tone even in a molten state, and therefore, it is possible to suppress the coloration of the resin composition that can be generated during the melting process. .

Comparing Reference Example 4-1 and Reference Example 4-2 for crystallization in a 12 m ³ glass-lined reactor as shown in FIG. 2, the average grain size of the crystals obtained in Reference Example 4-2 The smaller diameter is 44 μm, and the rotation rest angle, which is an index of powder flowability, also shows a higher value of 62 °. On the other hand, in Reference Example 4-1, by adding and dividing methanol, the average particle diameter of the crystals was increased to 178 μm, and the rotation rest angle was also improved to 55 °. From the above, the following appears. By using a crystal having a large average particle diameter according to the present invention, there is no problem in the addability even if it is used as a resin raw material.

In Reference Example 4-3, when crystallization was performed using only o-xylene as a good solvent, it was clear that good crystals having an average particle size of 220 μm and larger after drying in the first centrifugation were obtained. The properties changed to a thick soup-like suspension with higher viscosity. The average particle size after drying for the third centrifugation was micronized to 25 μm. After the third centrifugation, the fluidity was further deteriorated. Therefore, extraction from the reaction solution became difficult, the centrifugal filtration was interrupted, and the solution was dissolved again. Further, XRD analysis was performed on the powder obtained by drying the powder obtained from the first centrifugation, and as a result, the peaks of 2θ = 5.6 °, 8.5 °, 11.0 °, 12.5 °, 12.9 °, 14.9 °, 16.3 °, 19.1 ° were observed. The powder obtained by drying the third centrifugation did not observe the above-mentioned peaks. According to the above situation, it is clear that the powder in the first centrifugation contains quasi-stable crystals, and gradually turns into a stable phase to be micronized.

When o-xylene is used as the good solvent and methanol is used as the poor solvent in Reference Example 4-1 At 2θ = 5.6 °, 8.5 °, 11.0 °, 12.5 °, 12.9 °, 14.9 °, 16.3 °, 19.1 °, the peaks were not observed and did not cause micronization. Therefore, it can be considered that the adjacent two can be used by good solvents. For aromatic hydrocarbons represented by toluene, alcohol-based solvents represented by methanol are used as poor solvents to obtain particles with a larger average particle size.

[Synthesis example of polymer]

<Reference Example 4-4>

Bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane (compound 2) 26.63 parts by mass (0.042 moles), CHDM 10.78 parts by mass (0.075 moles), and ISB 33.58 parts by mass ( 0.230 moles), 56.33 parts by mass of DPC (0.263 moles), and 5.36 × ^10-4 parts by mass (3.04 × 10 ^-6 moles) of calcium acetate monohydrate as a catalyst are put into a reaction vessel. The temperature of the heating tank was set to 150 ° C, and if necessary, the raw materials were dissolved while being stirred (about 10 minutes). After dissolving, in the step of the first stage of the reaction, the temperature was raised to 220 ° C. over 30 minutes, and the reaction was performed at normal pressure for 60 minutes. Then, the pressure was reduced from normal pressure to 13.3 kPa over 90 minutes, and kept at 13.3 kPa for 30 minutes, and the generated phenol was extracted out of the reaction vessel.

Then, in the second step of the reaction, the temperature of the heating tank was raised to 240 ° C. over 15 minutes, and the pressure was reduced to less than 0.10 kPa over 15 minutes, and the generated phenol was drawn out of the reaction vessel. After reaching a specific torque, the reaction is completed, and the polymer produced is extruded in water to obtain polycarbonate pellets.

Table 7 shows the measurement results of the refractive index anisotropy, retardation ratio (Re450 / Re550), and the like of the stretched film when the obtained resin composition is formed into a film and stretched.

<Reference Example 4-5>

9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BHEPF) 62.40 parts by mass (0.142 moles), ISB 28.78 parts by mass (0.197 moles), DPC 73.40 parts by mass (0.343 moles) Ear), and 7.28 × 10 ^-4 parts by mass (3.39 × 10 ^-6 mol) of magnesium acetate tetrahydrate as a catalyst are put into the reaction vessel, and the temperature of the heating tank is set to 150 ° C. in a nitrogen atmosphere, and carried out as needed Stir and dissolve the material (about 10 minutes). After dissolving, in the step of the first stage of the reaction, the temperature was raised to 220 ° C. over 30 minutes, and the reaction was performed at normal pressure for 60 minutes. Then, the pressure was reduced from normal pressure to 13.3 kPa over 90 minutes, and kept at 13.3 kPa for 30 minutes, and the generated phenol was extracted out of the reaction vessel.

Then, in the second step of the reaction, the temperature of the heating tank was raised to 240 ° C. over 15 minutes, and the pressure was reduced to less than 0.10 kPa over 15 minutes, and the generated phenol was drawn out of the reaction vessel. After reaching a specific torque, the reaction is completed, and the polymer produced is extruded in water to obtain polycarbonate pellets.

Table 7 shows the measurement results of the refractive index anisotropy, retardation ratio (Re450 / Re550), and the like of the stretched film when the obtained resin composition is formed into a film and stretched.

It can be known from Table 7 that if the polyester carbonate using compound 2 of reference example 4-4 is compared with the polycarbonate using BHEPF of reference example 4-5, those of reference example 4-4 use less monomer. It has the same inverse wavelength dispersion as the phase difference ratio (Re450 / Re550) is the same. Furthermore, the photoelastic coefficient is also a value less than half. Based on the above, it can be said that the oligomeric fluorene diester of the present invention is a very excellent monomer.

Although the present invention has been described in detail and with reference to specific embodiments, it is clear to the practitioner that various changes or modifications can be added without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application filed on February 27, 2014 (Japanese Patent Application No. 2014-037216), and a Japanese patent application filed on March 19, 2014 (Japanese Patent Japanese Patent Application No. 2014-056873), Japanese Patent Application (Japanese Patent Application No. 2014-078068) filed on April 4, 2014, and Japanese Patent Application (Japanese Patent Application No. 2014-084649, filed on April 16, 2014) ), Whose content is incorporated herein by reference.

Claims (11)

A resin characterized in that it is a polycondensation resin having a repeating structural unit including an aromatic structure, and the content of the aromatic structure in the repeating structural unit satisfies the following formula (I). At least one of the structural units represented by the formulas (1) and (2), 5 ≦ A ≦ -22.5 × B + 38.3 (I) where 0.75 ≦ B ≦ 0.93 A: a repeating structure constituting a resin The content of the aromatic structure in the unit [mass%] B: the ratio (R450 / R550) of the phase difference (R450) at 450nm and the phase difference (R550) at 550nm of the stretched film made of resin (In the formulae (1) and (2), 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 and may be Alkyl groups having 1 to 10 carbon atoms having substituents, aryl groups having 4 to 10 carbon atoms having substituents, fluorenyl groups having 1 to 10 carbon atoms having substituents, and 1 to 10 carbon atoms having substituents Alkoxy group of 10, alkoxy group of 1 to 10 carbons which may have a substituent, aryloxy group of 1 to 10 carbons which may have a substituent, amine group which may have a substituent, carbon which may have a substituent A vinyl group having 1 to 10, an ethynyl group having 1 to 10 carbons 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; wherein R ⁴ At least two adjacent groups in ~ R ⁹ may be bonded to each other to form a ring). A resin characterized in that it is a polycondensation resin having a repeating structural unit including an aromatic structure, and the content of the aromatic structure in the repeating structural unit satisfies the following formula (III), and the glass transition of the resin is The temperature is 110 ° C or more and 160 ° C or less. The aromatic structure is benzene-like aromatic ring or heteroaromatic ring, 5 ≦ A ≦ -22.5 × B + 34.8 (III), among which 0.75 ≦ B ≦ 0.93 A: constituting the resin Content of the aromatic structure in the repeating structural unit [mass%] B: The ratio (R450 / R550) of the phase difference (R450) at 450 nm and the phase difference (R550) at 550 nm of the stretched film made of the resin. If the resin of claim 1 or 2 has a refractive index under the sodium d-line (589 nm) of 1.49 to 1.56. For example, the resin of claim 1 or 2 has a storage elastic modulus of 1 GPa or more and 2.7 GPa or less. For example, the resin of item 1 or 2 has a melt viscosity at a measurement temperature of 240 ° C and a shear rate of 91.2 sec ^-1 of 700 Pa · s to 5000 Pa · s. The resin of claim 1 or 2, wherein the resin is at least one resin selected from the group consisting of polycarbonate, polyester, and polyester carbonate. For example, the resin of claim 1 or 2, wherein the aromatic structure contained in the repeating structural unit is only fluorene. If the resin of claim 1 or 2 contains a structural unit represented by the following formula (3), A transparent film containing the resin according to any one of claims 1 to 8. A retardation film is obtained by extending a transparent film as claimed in claim 9 in at least one direction. For example, the retardation film of claim 10 includes a single layer and has a film thickness of 10 μm or more and 60 μm or less.