CN106062035B

CN106062035B - Polycondensation system resin and the optical film formed by it

Info

Publication number: CN106062035B
Application number: CN201580010538.3A
Authority: CN
Inventors: 并木慎悟; 平见优; 平见优一; 上原久俊; 林宽幸; 高见芳惠; 野上弘之
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Rayon Co Ltd
Priority date: 2014-02-27
Filing date: 2015-02-26
Publication date: 2018-05-29
Anticipated expiration: 2035-02-26
Also published as: KR20160126998A; CN106062035A; TW201540702A; TWI673262B; KR20210020179A; WO2015129833A1; KR102278717B1; CN108586723A; KR102341901B1

Abstract

It is an object of the invention to provide a kind of balancedly excellent resin of the various characteristics such as optics physical property, heat resistance, mechanical properties, thermal stability and the optical films and phase difference film that are obtained using the resin.The present invention relates to a kind of resins, it is the resin of the polycondensation system with the constitutional repeating unit comprising aromatic structure, the resin is characterized in that the content of the aromatic structure in the constitutional repeating unit meets following formula (I)s, and the resin has structural unit.5≤A≤22.5 × B+38.3 (I) wherein, 0.75≤B≤0.93A：Form content [quality %] B of the aromatic structure in the constitutional repeating unit of resin：The ratio between phase difference (R450) of the stretched film made of resin in 450nm and phase difference (R550) in 550nm (R450/R550).

Description

Polycondensation system resin and the optical film formed by it

Technical field

The present invention relates to a kind of excellent resin of the various characteristics such as optics physical property, heat resistance, mechanical properties, thermal stability, And the optical film obtained using the resin.

Moreover, it relates to three new fluorenes diester, oligomeric fluorenes diester compositions, Yi Jihan comprising the three fluorenes diester There is the resin combination of the polymer with the repetitive unit from three new fluorenes diester, obtained using the resin combination Stretched film, circular polarizing disk and image display device.

Moreover, it relates to new oligomeric fluorenes, the oligomeric fluorenes composition comprising the oligomeric fluorenes and using this is oligomeric The resin combination that fluorenes obtains.

Moreover, it relates to oligomeric fluorenes diester and used the oligomeric fluorenes diester resin combination manufacturing method.

Background technology

In recent years, the optics used in the optical system of optical lens, optical film, optical record medium etc is with transparent Resin needs increasing.Wherein, the thin flat particularly using liquid crystal display or organic el display as representative is shown The popularization of device (FPD) is notable, for improving contrast and coloring (color つ I), expanding field angle, prevent external light reflection etc. The purpose of the raising of display quality is developing and utilizing various optical films.

In organic el display, 1/4 wavelength plate of the reflection for preventing exterior light has been used.In order to inhibit to colour, Clean black display can be carried out, for being used for the phase difference film of 1/4 wavelength plate, it is desirable that can be in each wavelength of visibility region Under obtain preferable phase difference characteristics, wide band wavelength dispersion characteristics.

As with this comparable phase difference film, such as disclose the description below：According to the mode pair that respective slow axis is orthogonal 2 kinds of different phase difference films of birefringent wavelength dispersion carry out lamination, thus obtain the phase difference film (patent document of wide band 1).It there is further disclosed herein following methods：By respective slow axis for certain specifically configure in the way of to 1/2 wavelength plate and 1/4 Wavelength plate carries out lamination, so as to can obtain phase difference film (patent document 2).Furthermore disclosed by with specific degree of acetylation The wide band phase difference film (patent document 3) that cellulose acetate is formed；By having the poly- carbon of the bis-phenol structure of fluorenes ring comprising side chain The phase difference film that acid ester copolymer is formed, the phase difference film show the smaller inverse wave length dispersiveness of the more short then phase difference of wavelength (patent document 4).

In recent years, it was recently reported that many above-mentioned side chains have the resin of fluorenes ring, it is proposed that play the optical characteristics for coming from fluorenes ring And the feature of heat resistance etc, as useful material (patent document 5) in optical applications.

In these resins, commonly using double [4- (2- hydroxyl-oxethyls) benzene of monomer, i.e. 9, the 9- for being easier to obtain Base] fluorenes, double (the 4- hydroxy-3-methyls phenyl) fluorenes (patent document 6,7) of 9,9-.

In addition, also in resin of the exploitation with new construction.Two aminations that there is fluorenes ring in side chain are disclosed in patent document 8 Object is closed, has further stated that the stretched film of the polyimide resin using the diamine compound.Patent Document 9 discloses make With the polycarbonate resin for the fluorene compound that aromatic rings is free of on main chain.Patent Document 10 discloses in same intramolecular Dihydroxy compounds or diester compound with 2 fluorenes rings have further stated that and have used the dihydroxy compounds or class Close the stretched film of the polyester resin of object.

The description below is disclosed in patent document 11,12：By by the repetition with fluorenes ring in polycarbonate resin The content control of unit is particular range, and the stretched film formed by the polycarbonate resin shows the more short then phase difference of wavelength more Small inverse wave length dispersiveness, thus, there is excellent performance as phase difference film.Show that the more short then phase difference of wavelength is smaller The phase difference film of so-called inverse wave length dispersiveness can obtain preferable phase difference characteristics under each wavelength of visibility region, as circle Polarizer image display device prevent it is useful in external light reflection and field angle amendment etc..

It is double commonly using 9,9- described in patent document 11 or 12 as the dihydroxy compounds in side chain with fluorenes ring [4- (2- hydroxyl-oxethyls) phenyl) fluorenes, double (the 4- hydroxy-3-methyls phenyl) fluorenes of 9,9-.It is disclosed in patent document 13 same One intramolecular has the diester compound of 2 fluorenes rings, has further stated that the polyester resin using the diester compound.In patent In document 10, the dihydroxy compounds or diester compound that there is 2 fluorenes rings in same intramolecular are disclosed, is further stated that Use the stretched film of the dihydroxy compounds or the polyester resin of diester compound.

Particularly, it is known that：The polyester of two fluorene compounds with 2 fluorenes rings has been used with higher glass transition Temperature and negative birefringence, thus useful in reflecting polarizer purposes (patent document 10).In addition it is known：As resinogen Material, different to functional end-group 2 kinds of two fluorene compounds share.

On the other hand, in the purposes of the protecting group of the amino of peptide synthesis in solid state, it is known that end only has 1 reactive official Two fluorene compounds (patent document 14, non-patent literature 1) that can be rolled into a ball.

It is double commonly using 9,9- described in patent document 11 or 12 as the dihydroxy compounds in side chain with fluorenes ring [4- (2- hydroxyl-oxethyls) phenyl) fluorenes, double (the 4- hydroxy-3-methyls phenyl) fluorenes of 9,9-.

Known to another aspect：Although not being that inverse wave length disperses purposes, specific diester compound is being used as polyester In the case of carbonate source, from light penetration aspect, the content for making the chlorine included in the compound is specified amount (patent document 15) below.

Prior art literature

Patent document

Patent document 1：The flat 5-27118 publications of Japanese Laid-Open

Patent document 2：The flat 10-68816 publications of Japanese Laid-Open

Patent document 3：Japanese Laid-Open 2000-137116 publications

Patent document 4：No. 3325560 publication of Japan's patent

Patent document 5：The flat 10-101786 publications of Japanese Laid-Open

Patent document 6：No. 5119250 publication of Japan's patent

Patent document 7：No. 5204200 publication of Japan's patent

Patent document 8：Japanese Laid-Open 2008-112124 publications

Patent document 9：Japanese Laid-Open 2008-222965 publications

Patent document 10：No. 2012/0170118 specification of U.S. Patent Application Publication No.

Patent document 11：International Publication No. 2006/041190

Patent document 12：International Publication No. 2011/149073

Patent document 13：No. 3324084 publications of U.S. Patent No.

Patent document 14：International Publication No. 1991/08190

Patent document 15：The flat 2-20518 publications of Japanese Laid-Open

Non-patent literature

Non-patent literature 1：Synthesis (synthesis), 1992,819.

The content of the invention

The subject that the invention solves

The development in FPD fields is surprising, for phase difference film, it is desirable that optical characteristics, quality, reliability etc. are further improved, And the it is required that filming of film.And then also requirement reduces material cost, improves the production in each processes such as film, stretching, lamination Rate.Along with this, it is desirable that phase difference film has both various characteristics.For example, as the material for phase difference film, it is necessary to following materials Material, which has required wavelength dispersibility, while has both low photoelastic coefficient, high-fire resistance, melt processable, machinery The various characteristics such as intensity, and intrinsic birefringence is big, and flexibility and draftability are excellent, and high molecularly oriented is can obtain by stretching Degree.

But phase difference film is carried out as patent document 1 or patent document 2 in the method for lamination, polarizer can become It is thick.Further it is necessary to by slow axis to carry out lamination to each phase difference film in the way of particular configuration, have polarizer productivity or The problem of yield rate is deteriorated.Patent document 3, the phase difference film of patent document 4 have inverse wave length dispersiveness, and sheet of membrane can obtain width The phase difference characteristics of band domain, but the heat resistance of the cellulose acetate of patent document 3 is insufficient, and there is the ruler caused by moisture absorption It is very little deformation and lead to the problem of image spot (portrait spot).

It is known：The phase difference film formed by the polycarbonate resin with fluorenes ring of patent document 4,6,7, which is used as, to be shown The phase difference film of inverse wave length dispersiveness or image display device for preventing that the circular polarizing disk of external light reflection is useful.But The research of people is understood according to the present invention, has used the resin of double (the 4- hydroxy-3-methyls phenyl) fluorenes of 9,9- since film is crisp, it is difficult into Row obtains the stretching of high-orientation, has used 9,9- double [4- (2- hydroxyl-oxethyls) phenyl] although the resin draftability of fluorenes compares It is excellent, but photoelastic coefficient is slightly higher, and the poor reliability under high temperature.

As the means improved to various characteristics, it is contemplated that change copolymer composition or adjustment ratio, 9,9- double (4- Hydroxy-3-methyl phenyl) fluorenes one side heat resistance is very high, the characteristic to become fragile but then with resin, it is difficult to keep Improve the flexibility of resin while the heat resistance of appropriateness.In addition, in the feelings of double [4- (2- hydroxyl-oxethyls) phenyl] fluorenes of 9,9- Under condition, in order to show desired inverse wave length dispersiveness, it is necessary to containing 50 mass %~70 mass % or so these monomers Ingredient, the degree of freedom of the MOLECULE DESIGN based on copolymerization are low, it is difficult to take into account the characteristics such as heat resistance or mechanical strength and optical characteristics.

In addition, containing the polycarbonate resin of the glycol of fluorenes ring on the use described in patent document 9, inverse wave length is disperseed Property, the characteristics such as photoelastic coefficient, heat resistance deficiency.On the polyester described in patent document 10, describe negative index respectively to The refractive index of the opposite sex, i.e. draw direction is less than the refractive index for stretching right angle orientation.But as phase difference film, it is necessary to have just Refractive anisotrop, condition is not satisfied for above-mentioned drawn polyester film.In addition, also not on phase difference in patent document 10 Wavelength dependency record.

As described above, existing phase difference film is difficult to balancedly obtain inverse wave length dispersiveness, optical characteristics, heat resistance, machine The various characteristics such as tool intensity.In order to thoroughly improve the characteristic of phase difference film, it is desirable that by the new chemical combination of the balancing good of various characteristics Object is used for raw material.

The first object of the present invention is solution the above subject, provides optics physical property, heat resistance, mechanical properties, thermostabilization The excellent resin of various characteristics and the optical films obtained using the resin such as property.

Additionally, it is known that：The stretched film formed by the polycarbonate resin with fluorenes ring of patent document 11,12 is as display Go out inverse wave length dispersiveness phase difference film or image display device for preventing that the circular polarizing disk of external light reflection is useful.But It is, according to the present invention the research of people that patent document 11 has used 9,9- double (4- hydroxy-3-methyls phenyl) although the resin of fluorenes With high-fire resistance, but in order to show desired inverse wave length dispersiveness, it is necessary to improve the repetitive unit with fluorenes ring Ratio, thus crisp film is easily formed, there are problems for flexibility.On the other hand, patent document 12 has used the double [4- of 9,9- (2- hydroxyl-oxethyls) phenyl] although the resin flexibility of fluorenes is excellent, in order to show desired inverse wave length dispersiveness, Need the ratio of repetitive unit of the raising with fluorenes ring, it is difficult to take into account the various physical property such as heat resistance and optics physical property.Therefore, in order to The various physical property such as the optics physical property and heat resistance, flexibility of further improved resin, it is desirable that by optics physical property and mechanical strength etc. The noval chemical compound of the balancing good of various physical property is used for raw material.

Disclose the polyester obtained using two fluorene compounds in patent document 13 and 10, but due to two fluorene structured, it is heat-resisting Property is still unsatisfactory.In addition, it is also indefinite that film use, optical characteristics etc. are not used as in patent document 13, specially It is not studied in sharp document 10 as phase difference film, the wavelength dependency of phase difference is also indefinite.

The second object of the present invention is to provide a kind of new fluorene compound, with sufficient heat resistance, and it is few When amount manufactures resin combination using the fluorene compound and carries out film shaping, excellent optical characteristics can be shown, so as to Improve the degree of freedom of resin design.Further it is provided that the resin combination obtained using new fluorene compound.

In addition, as described in patent document 10, as the method that specific physical property is assigned to resin, can enumerate by The method that two kinds of different Oligofluorenylene compounds of the reactive functional groups of end are shared.But Oligofluorenylene compounds are difficult to It obtains, in order to manufacture the resin with desired physical property, it is necessary to separately synthesize two kinds of Oligofluorenylene compounds as raw material, needs Time and cost are wanted, the practicability as industrial product is it may be said that deficiency.

Present inventor has performed further investigation, it turns out that, it is high, to the desired physical property of resin imparting as practicability Method is useful using the Oligofluorenylene compounds in two ends with different reactive functional groups.As this oligomeric fluorenes The manufacturing method of compound can enumerate following methods：First, as raw material, manufacture is oligomeric with 1 reactive functional groups Fluorene compound, next, importing the reactive functional groups different from above-mentioned reactive functional groups to above-mentioned Oligofluorenylene compounds.

As in the manufacturing method of the Oligofluorenylene compounds with 1 reactive functional groups, such as known non-patent literature 1 The method of record, but be difficult to selectively obtain the Oligofluorenylene compounds with 1 reactive functional groups in this method, therefore deposit It is being difficult to efficiently manufacture the problem for the Oligofluorenylene compounds that there is differential responses functional group in two ends.

Therefore, the third object of the present invention is to provide the Oligofluorenylene compounds with specific reactive functional groups, Optionally there are desired reactive functional groups, the monomer or list of the resin combination of optical applications can be suitable as Body raw material.

In addition, the present inventor has made intensive studies the resin combination that inverse wave length is disperseed, it turns out that, by making By the use of specific oligomeric fluorenes diester compound as starting monomer, even if the content ratio in resin is low, it is possibility to have the performance of effect ground Go out desired optical characteristics, the degree of freedom of resin design can be improved.

In general, in terms of resin combination is manufactured, in order to make the physical property of polymerization speed and obtained resin combination For defined situation, it is necessary to closely control the amount ratio of raw material.Oligomeric fluorenes diester compound is normally solid, as resin group In order to control its amount ratio when closing the raw material use of object, it is preferably made to melt and use.Present inventor has performed further investigation, as a result The following situations of new discovery：According to the difference of amount of metal contained in the compound, by compound meeting during smelting process Generate coloring, it is difficult to which the monomer of the resin combination as optical applications uses.

On the other hand, had using the manufacturing method of the polyestercarbonate resins of diester compound it is various, as one As property method, it is known that with molten condition glycols, diaryl carbonate and two esters are polymerize by ester-interchange method molten Melt condensation methods.In this method, in the case where using diaryl carbonate and dialkyl ester as two esters, ester exchange reaction It is significantly different from the reaction speed of polycarbonate polymerization, thus there are dialkyl esters to be difficult to be introduced into asking in polyestercarbonate resins Topic, as two esters, it is preferable to use diaryl esters.In addition, there is the oligomeric fluorene diaryl of aryl in two ends as manufacture The method for closing object, can enumerate the method that two ends of oligomeric fluorenes diester compound are substituted by aryl, but new discovery is following Situation：According to the difference of the amount of carboxylic acid contained in the oligomeric fluorenes diester compound, obtained oligomeric fluorene diaryl chemical combination Amount of metal in object can raise, by that can generate coloring during smelting process.

Therefore, the fourth object of the present invention is to provide a kind of oligomeric fluorenes diester compound, for that can be suitable as light It learns the monomer of the resin combination of purposes and the oligomeric fluorenes diester of the degree of freedom of resin design can be improved, can inhibit to pass through Producible coloring during smelting process.

And then it is an object of the invention to provide a kind of oligomeric fluorenes diester compound, may be used as can for manufacture Inhibit the raw material of the oligomeric fluorene diaryl ester compounds of coloring.

Solution for solving the problem

In view of above-mentioned first purpose, present inventor has performed in-depth study repeatedly, it turns out that following resins can table Reveal excellent optical characteristics and mechanical properties, have thus completed the present invention, which is characterized in that, forms the repetition of resin The content of aromatic structure in structural unit is in particular range and can show desired wavelength dispersibility.That is, it is of the invention Main points it is as follows.

[1-1]

A kind of resin is the resin of the polycondensation system with the constitutional repeating unit comprising aromatic structure, the resin It is characterized in that,

The content of aromatic structure in the constitutional repeating unit meets following formula (I)s,

The resin has selected from least one of the structural unit represented by following formula (1) and formula (2) structural unit.

5≤A≤-22.5×B+38.3 (I)

Wherein, 0.75≤B≤0.93.

A：Form the content [quality %] of the aromatic structure in the constitutional repeating unit of resin

B：The ratio between phase difference (R450) of the stretched film made of resin in 450nm and phase difference (R550) in 550nm (R450/R550)

[changing 1]

(in formula (1) and (2), R¹~R³It is each independently Direct Bonding or the carbon original with or without substituent group Subnumber is 1~4 alkylidene.

R⁴~R⁹It is each independently hydrogen atom, the alkyl that the carbon number with or without substituent group is 1~10, tool Have or aryl that the carbon number without substituent group is 4~10, with or without the carbon number of substituent group be 1~10 Acyloxy, the carbon number with or without substituent group that acyl group, the carbon number with or without substituent group are 1~10 Alkoxy for 1~10, with or without substituent group carbon number be 1~10 aryloxy group, with or without substitution The amino of base, vinyl of the carbon number for 1~10 with or without substituent group, the original of the carbon with or without substituent group Subnumber is 1~10 acetenyl, the sulphur atom with substituent group, the silicon atom with substituent group, halogen atom, nitro or cyano. Wherein, R⁴~R⁹In, adjacent at least two group can be mutually bonded to form ring.)

[1-2]

A kind of resin is the resin of the polycondensation system with the constitutional repeating unit comprising aromatic structure, the resin It is characterized in that, the content of the aromatic structure in the constitutional repeating unit meets following formula (III)s, and the vitrifying of the resin turns Temperature is less than 110 DEG C or more 160 DEG C.

5≤A≤-22.5×B+34.8 (III)

Wherein, 0.75≤B≤0.93.

[1-3]

Resin as described in [1-1] or [1-2], wherein, the refractive index in sodium d lines (589nm) of the resin for 1.49~ 1.56。

[1-4]

Such as the resin any one of [1-1]~[1-3], wherein, the storage modulus of the resin is more than 1GPa It is 2.7GPa following.

[1-5]

Such as the resin any one of [1-1]~[1-4], wherein, the resin is in 240 DEG C of measuring temperature, shear velocity 91.2sec^-1Under the conditions of melt viscosity be more than 700Pas below 5000Pas.

[1-6]

Such as the resin any one of [1-1]~[1-5], wherein, above-mentioned resin be selected from by makrolon, polyester, At least one of the group of polyestercarbonate composition resin.

[1-7]

Such as the resin any one of [1-1]~[1-6], wherein, the aromatic series that above-mentioned constitutional repeating unit is included Structure is only fluorenes.

[1-8]

Such as the resin any one of [1-1]~[1-7], contain the structural unit represented by following formula (3).

[changing 2]

[1-9]

A kind of hyaline membrane contains the resin any one of [1-1]~[1-8].

[1-10]

A kind of phase difference film is obtained by stretching the hyaline membrane described in [1-9] at least one direction.

[1-11]

Phase difference film as described in [1-10], is made of simple layer, and film thickness is less than 10 μm or more 60 μm.

In view of above-mentioned second purpose, present inventor has performed in-depth study repeatedly, it turns out that, specific three fluorenes diester Compound has sufficient heat resistance, and uses on a small quantity and manufacture resin combination and carry out showing excellent light during film shaping Characteristic is learned, is had thus completed the present invention.

That is, main points of the invention are as follows.

[2-1]

A kind of three fluorenes diester, which is characterized in that it includes 3 fluorenes unit a with or without substituent group,

The carbon atom of 9 of fluorenes unit a is bonded or directly with one another by the alkylene with or without substituent group Base is bonded with or without the arlydene of substituent group or with or without the sub- aralkyl of substituent group with chain.

[2-2]

The three fluorenes diester as described in [2-1], which is characterized in that it is represented by the following general formula (1).

[changing 3]

(in formula,

R¹And R²Be each independently Direct Bonding or with or without substituent group carbon number be 1~4 Asia Alkyl.

R^3aAnd R^3bBe each independently with or without substituent group carbon number be 1~10 alkylidene, have or The arlydene or be 6~10 with or without the carbon number of substituent group that carbon number without substituent group is 4~10 Sub- aralkyl.

R⁴~R⁹It is each independently hydrogen atom, the alkyl that the carbon number with or without substituent group is 1~10, tool Have or aryl that the carbon number without substituent group is 4~10, with or without the carbon number of substituent group be 1~10 Acyloxy, the carbon number with or without substituent group that acyl group, the carbon number with or without substituent group are 1~10 Alkoxy for 1~10, with or without substituent group carbon number be 1~10 aryloxy group, with or without substitution The amino of base, vinyl of the carbon number for 1~10 with or without substituent group, the original of the carbon with or without substituent group Subnumber is 1~10 acetenyl, the sulphur atom with substituent group, the silicon atom with substituent group, halogen atom, nitro or cyanogen Base.Wherein, R⁴~R⁹In, adjacent at least two group can be mutually bonded to form ring.)

R¹⁰It is the organic substituent that carbon number is 1~10.)

[2-3]

The three fluorenes diester as described in [2-2], which is characterized in that the R in above-mentioned general formula (1)¹⁰It is with or without substitution The carbon number of base is 4~10 aryl.

[2-4]

A kind of oligomeric fluorenes diester compositions, to include the three fluorenes diester and two any one of [2-1]~[2-3] The oligomeric fluorenes diester compositions of fluorenes diester, which is characterized in that

Above-mentioned two fluorenes diester includes 2 fluorenes unit b with or without substituent group,

The carbon atom of 9 of fluorenes unit b is bonded or directly with one another by the alkylene with or without substituent group Base, the arlydene with or without substituent group or the sub- aralkyl with or without substituent group are bonded with chain.

[2-5]

Oligomeric fluorenes diester compositions as described in [2-4], which is characterized in that above-mentioned two fluorenes diester is by the following general formula (2) institute It represents.

[changing 4]

(in formula,

R¹~R³Be each independently Direct Bonding or with or without substituent group carbon number be 1~4 Asia Alkyl.

R¹⁰It is the organic substituent that carbon number is 1~10.)

[2-6]

Oligomeric fluorene diaryl ester composition as described in [2-4] or [2-5], which is characterized in that compared with the total of composition Quality, the content ratio of above-mentioned three fluorenes diester is more than 1 mass %.

[2-7]

A kind of resin combination, to be formed as the polymer of repetitive unit by three fluorenes with divalent or being gathered containing this The resin combination of object is closed, which is characterized in that,

Three fluorenes of above-mentioned divalent include 3 fluorenes unit a with or without substituent group, and the carbon of 9 of fluorenes unit a is former Son directly with one another bonding or by with or without substituent group alkylidene, with or without substituent group arlydene, Or it is bonded with or without the sub- aralkyl of substituent group with chain.

[2-8]

Resin combination as described in [2-7], which is characterized in that three fluorenes of above-mentioned divalent are represented by the following general formula (11).

[changing 5]

(in formula,

[2-9]

Resin combination as described in [2-7] or [2-8], which is characterized in that further two fluorenes with divalent are used as weight for it Multiple unit,

Two fluorenes of above-mentioned divalent include 2 fluorenes unit b with or without substituent group, and the carbon of 9 of fluorenes unit b is former Son directly with one another bonding or by with or without substituent group alkylidene, with or without substituent group arlydene, Or it is bonded with or without the sub- aralkyl of substituent group with chain.

[2-10]

Such as the resin combination any one of [2-7]~[2-9], which is characterized in that in the phase that wavelength 450nm is measured Potential difference (Re450) meets following formula (20) with the ratio between the phase difference (Re550) measured in wavelength 550nm.

Re450/Re550≤1.0 (20)

[2-11]

A kind of formed body, which is characterized in that it is to be molded the resin combination any one of [2-7]~[2-10] Obtained from.

[2-12]

A kind of optical component, which is characterized in that it is as the resin combination shape any one of [2-7]~[2-10] Into.

[2-13]

A kind of film, which is characterized in that it is formed as the resin combination any one of [2-7]~[2-10].

[2-14]

A kind of stretched film, which is characterized in that it is obtained by stretching the film described in [2-13] at least one direction.

[2-15]

A kind of 1/4 λ plates, which is characterized in that it is formed as the stretched film described in [2-14].

[2-16]

A kind of circular polarizing disk, which is characterized in that it has 1/4 λ plates described in [2-15].

[2-17]

A kind of image display device, which is characterized in that it possesses the circular polarizing disk described in [2-16].

In view of above-mentioned 3rd purpose, present inventor has performed in-depth study repeatedly, it turns out that, by using with specific The olefin(e) compounds of reactive functional groups substitute the Oligofluorenylene compounds that two ends are hydrogen, can with high selectivity and efficiently To desired Oligofluorenylene compounds, and then, monomer or list of the Oligofluorenylene compounds as the resin combination of optical applications Body raw material is suitable, has thus completed the present invention.

That is, main points of the invention are as follows.

[3-1]

A kind of oligomeric fluorenes, the oligomeric fluorenes include the carbon of 9 of the fluorenes unit a of 2 or more with or without substituent group Atom each other by with or without substituent group alkylidene, with or without substituent group arlydene or have or Oligomeric fluorene structural units (hereinafter referred to " the oligomeric fluorene structured list that sub- aralkyl without substituent group is formed with chain bonding First a "), which is characterized in that,

The carbon atom of 9 of the fluorenes unit a of any one end in the oligomeric fluorene structural units a has following formula (A) Represented reactive functional groups, the carbon atom of 9 of the fluorenes unit a of another end have hydrogen atom.

[changing 6]

(in formula, R^a~R^cIt is each independently hydrogen atom, the alkane that the carbon number with or without substituent group is 1~10 The aryl or the carbon number with or without substituent group that base, the carbon number with or without substituent group are 4~10 For 6~10 aralkyl, X is ester group, amide groups, carboxyl, cyano or nitro.* it is the carbon atom knot with 9 of fluorenes unit a The associative key of conjunction.)

[3-2]

Oligomeric fluorenes as described in [3-1], which is characterized in that it is represented by the following general formula (1).

[changing 7]

(in formula, R³It is 1~4 to be each independently Direct Bonding or the carbon number with or without substituent group Alkylidene.

R⁴~R⁹It is each independently hydrogen atom, the alkyl that the carbon number with or without substituent group is 1~10, tool Have or aryl that the carbon number without substituent group is 4~10, with or without the carbon number of substituent group be 1~10 Acyloxy, the carbon number with or without substituent group that acyl group, the carbon number with or without substituent group are 1~10 Alkoxy for 1~10, with or without substituent group carbon number be 1~10 aryloxy group, with or without substitution The amino of base, vinyl of the carbon number for 1~10 with or without substituent group, the original of the carbon with or without substituent group Subnumber is 1~10 acetenyl, the sulphur atom with substituent group, the silicon atom with substituent group, halogen atom, nitro or cyanogen Base.Wherein, R⁴~R⁹In, adjacent at least two group can be mutually bonded to form ring.

R^a~R^cIt is each independently hydrogen atom, the alkyl that the carbon number with or without substituent group is 1~10, tool Have or aryl that the carbon number without substituent group is 4~10 or the carbon number with or without substituent group be 6~ 10 aralkyl.

X is ester group, amide groups, carboxyl, cyano or nitro.

N represents 1~5 integer value.)

[3-3]

A kind of oligomeric fluorenes, the oligomeric fluorenes include the carbon of 9 of the fluorenes unit a of 2 or more with or without substituent group Atom each other by with or without substituent group alkylidene, with or without substituent group arlydene or have or Sub- aralkyl without substituent group is bonded the oligomeric fluorene structural units a of getting up with chain, which is characterized in that,

The carbon atom of 9 of the fluorenes unit a of any one end in the oligomeric fluorene structural units a has following formula (A) Represented reactive functional groups, the carbon atom of 9 of the fluorenes unit a of another end is with different from the reactive functional groups Reactive functional groups.

[changing 8]

(in formula, R^a~R^cIt is each independently hydrogen atom, the alkane that the carbon number with or without substituent group is 1~10 The aryl or the carbon number with or without substituent group that base, the carbon number with or without substituent group are 4~10 For 6~10 aralkyl, X is ester group, amide groups, carboxyl, cyano or nitro.* it is the carbon atom knot with 9 of fluorenes unit The associative key of conjunction.)

[3-4]

Oligomeric fluorenes as described in [3-3], which is characterized in that it is represented by the following general formula (2).

[changing 9]

R¹⁰For Direct Bonding, with or without substituent group carbon number be 1~10 alkylidene, with or without The Asia virtue that arlydene that the carbon number of substituent group is 4~10 or carbon number with or without substituent group are 6~10 Alkyl,

Or selected from being 1~10 alkylidene, with or without taking by the carbon number with or without substituent group Arlydene that the carbon number of Dai Ji is 4~10 and with or without substituent group carbon number be 6~10 sub- aralkyl The group of 2 or more in the group of composition by oxygen atom, with or without the sulphur atom of substituent group, with or without taking The group that the nitrogen-atoms or carbonyl of Dai Ji is formed by connecting.

R^a~R^cIt is each independently hydrogen atom, the alkyl that the carbon number with or without substituent group is 1~10, tool Have or aryl that the carbon number without substituent group is 4~10 or the carbon number with or without substituent group be 6~ 10 aralkyl,

X be ester group, amide groups, carboxyl, cyano or nitro,

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

N represents 1~5 integer value.)

[3-5]

A kind of oligomeric fluorenes composition, the oligomeric fluorenes composition are characterized in that it includes any one of [3-1]~[3-4] The oligomeric fluorenes (hereinafter referred to " oligomeric fluorenes A ") and with the chemical constitution different from the oligomeric fluorenes A oligomeric fluorenes (under Referred to herein as " oligomeric fluorenes B "),

The carbon atoms of 9 of the above-mentioned oligomeric fluorenes B comprising the fluorenes unit b of 2 or more with or without substituent group is each other By with or without substituent group alkylidene, with or without the arlydene of substituent group or with or without taking The oligomeric fluorene structural units (hereinafter referred to " oligomeric fluorene structural units b ") that the sub- aralkyl of Dai Ji is got up with chain bonding,

There is following formula (B) institute on the carbon atom of 9 of the fluorenes unit b of two ends in the oligomeric fluorene structural units b The identical reactive functional groups represented.

[changing 10]

(in formula, R^d~R^fIt is each independently hydrogen atom, the alkane that the carbon number with or without substituent group is 1~10 The aryl or the carbon number with or without substituent group that base, the carbon number with or without substituent group are 4~10 For 6~10 aralkyl, X¹For ester group, amide groups, carboxyl, cyano or nitro.* it is the carbon atom with 9 of fluorenes unit b With reference to associative key.)

[3-6]

A kind of resin combination, which is characterized in that it is as the polymerization of the oligomeric fluorenes any one of [3-1]~[3-4] The polymer of object or the oligomeric fluorenes composition described in [3-5] is formed or comprising the polymer.

[3-7]

A kind of film is formed as the resin combination described in [3-6].

[3-8]

A kind of stretched film is obtained by stretching the film described in [3-7] at least one direction.

[3-9]

A kind of image display device has the stretched film described in [3-8].

[3-10]

A kind of manufacturing method of oligomeric fluorenes, which is characterized in that make in the presence of a base oligomeric fluorenes represented by following formula (3) with The olefine reaction with electron-withdrawing group represented by following formula (4), obtains the oligomeric fluorenes represented by following formula (1).

[changing 11]

X is ester group, amide groups, carboxyl, cyano or nitro.

N represents 1~5 integer value.)

[3-11]

A kind of manufacturing method of oligomeric fluorenes, which is characterized in that above-mentioned formula (1) institute table for obtaining the method by [3-10] The oligomeric fluorenes shown is reacted with the compound with electrophilicity, obtains the oligomeric fluorenes represented by following formula (2).

[changing 12]

(in formula,

R³Be each independently Direct Bonding or with or without substituent group carbon number be 1~4 alkylene Base.

Or selected from being 1~10 alkylidene, with or without taking by the carbon number with or without substituent group Arlydene that the carbon number of Dai Ji is 4~10 and with or without substituent group carbon number be 6~10 sub- aralkyl The group of 2 or more in the group of composition by oxygen atom, with or without the sulphur atom of substituent group, with or without taking The group that the nitrogen-atoms or carbonyl of Dai Ji is formed by connecting,

X be ester group, amide groups, carboxyl, cyano or nitro,

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

N represents 1~5 integer value.)

In view of above-mentioned 4th purpose, present inventor has performed in-depth study repeatedly, it turns out that, by making oligomeric fluorenes two The content ratio of metal ingredient contained by ester compounds is specific scope, and the stability under molten condition improves, and can press down System coloring.

In addition, as manufacturing the raw material for the oligomeric fluorene diaryl ester compounds that can inhibit coloring, using making carboxylic acid Content ratio be particular range oligomeric fluorenes diester compound, so as to reduce institute in obtained diaryl ester compound The content ratio of the metal ingredient contained.

That is, main points of the invention are as follows.

[4-1]

A kind of oligomeric fluorenes diester is the oligomeric fluorenes two for including the fluorenes unit of 2 or more with or without substituent group Ester, which is characterized in that

The carbon atom of 9 of the fluorenes unit be bonded directly with one another or by with or without substituent group alkylidene, It arlydene with or without substituent group or is bonded with or without the sub- aralkyl of substituent group with chain, also,

The content ratio of metal is below 500 mass ppm.

[4-2]

Oligomeric fluorenes diester as described in [4-1], wherein, above-mentioned metal is selected from by the 1st race of long period type periodic table, the 2nd At least one of the group that race, the 12nd race, the 14th race and transition metal form metal.

[4-3]

Oligomeric fluorenes diester as described in [4-1] or [4-2], which is characterized in that it is represented by the following general formula (1).

[changing 13]

(in formula, R¹~R³Be each independently Direct Bonding or with or without substituent group carbon number for 1~ 4 alkylidene.

R¹⁰It is the organic substituent that carbon number is 1~10.

N represents 1~5 integer value.)

[4-4]

Oligomeric fluorenes diester as described in [4-3], which is characterized in that the R in above-mentioned general formula (1)¹⁰It is that carbon number is 4~10 Aryl.

[4-5]

The carbon atom of 9 of above-mentioned fluorenes unit is bonded or directly with one another by the alkylene with or without substituent group Base, the arlydene with or without substituent group or the sub- aralkyl with or without substituent group are bonded with chain, and And

The content ratio of carboxylic acid is below 10 mass %.

[4-6]

Oligomeric fluorenes diester as described in [4-5], which is characterized in that it is represented by the following general formula (1).

[changing 14]

R¹⁰It is the organic substituent that carbon number is 1~10.

N represents 1~5 integer value.)

[4-7]

A kind of manufacturing method of oligomeric fluorene diaryl ester, which is characterized in that the oligomeric fluorenes diester described in by [4-6] is as former Material substitutes above-mentioned R with aryl¹⁰Base obtains diaryl ester.

[4-8]

A kind of manufacturing method of resin combination, which is characterized in that oligomeric any one of by [4-1]~[4-6] Fluorenes diester is used as raw material.

The effect of invention

The balancing good of the various characteristics such as optical characteristics, heat resistance, mechanical property, the reliability of resin of the present invention.Cause This, resin of the invention can be suitable in the optical films such as phase difference film.

In addition, the new fluorene compound of the present invention has sufficient heat resistance, and resin is manufactured using the fluorene compound Composition simultaneously carries out showing excellent optical characteristics during film shaping, so as to improve the degree of freedom of resin design.

In addition, the Oligofluorenylene compounds of the present invention selectively have desired reactive functional groups, can be suitble to use Make the monomer or raw material monomer of the resin combination of optical applications.

In addition, the present invention oligomeric fluorenes diester compound can be suitable as optical applications resin combination monomer, Or the raw material of monomer, it is producible when and the degree of freedom of resin design can be improved, and then can inhibited by smelting process Coloring.

Description of the drawings

Fig. 1 is that tenor in the oligomeric fluorenes diester to embodiment 4-1~4-4 and comparative example 4-1 and heating are front and rear The graph that absorbance difference is compared.

Fig. 2 is the graph of the particle diameter distribution for the oligomeric fluorenes diester for representing reference example 4-1 and reference example 4-2.

Specific embodiment

In the following, embodiments of the present invention are described in detail, but the explanation for the technical characteristic recorded below is only this An example (typical example) of the embodiment of invention, without departing from its main points, then the present invention is not limited to following contents.

It should be noted that " constitutional repeating unit " refers to the structure that identical repeated structure occurs in resin in the present invention Unit is by each forming the structural unit of the resin into joining line.More specifically, such as in polycarbonate resin In the case of, constitutional repeating unit is also known as including carbonyl.

In addition, " structural unit " refers to the part-structure for forming resin, it is the specific portion contained by constitutional repeating unit Separation structure.For example, refer to by the part-structure clamped by linking group adjacent in resin；Or it is present in the end of polymer Part-structure clamped by partial polymerisation reactivity group and the linking group adjacent with the polymerism reactive group, more specifically Ground is said, such as in the case of polycarbonate resin, carbonyl is linking group, will be by the part-structure clamped by adjacent carbonyl Referred to as structural unit.

In the present invention, " weight " is identical with " quality " meaning.

In the present invention, " with or without substituent group " is identical with " can be substituted " meaning.

In the present invention, " general formula " is only denoted as " formula " sometimes.

《Invention 1》

In the following, the resin and film of the present invention 1 are described in detail.

It should be noted that (general formula) formula (1)~(9) recorded below, (11)~(15) are used to illustrate in the present invention 1 Each structure.

The 1st aspect of the present invention is related to a kind of resin, is the contracting with the constitutional repeating unit comprising aromatic structure The resin of poly- system, the resin are characterized in that the content of the aromatic structure in the constitutional repeating unit meets following formula (I)s, The resin has selected from least one of the structural unit represented by following formula (1) and formula (2) structural unit.

5≤A≤-22.5×B+38.3 (I)

Wherein, 0.75≤B≤0.93.

[changing 15]

(in formula (1) and (2), R¹~R³It is each independently Direct Bonding, the carbon number with or without substituent group For 1~4 alkylidene.

The 2nd aspect of the present invention is related to a kind of resin, is the contracting with the constitutional repeating unit comprising aromatic structure The resin of poly- system, the resin are characterized in that the content of the aromatic structure in the constitutional repeating unit meets following formula (III), and the glass transition temperature of the resin is less than 120 DEG C or more 160 DEG C.

5≤A≤-22.5×B+34.8 (III)

Wherein, 0.75≤B≤0.93.

The resin of the present invention is the resin of polycondensation system.The resin of polycondensation system is represented through Glossary of basic Defined in terms in polymer science (polymer science basic terms compilation) (IUPAC recommends 1996) The resin that polycondensation (polycondensation) is obtained is carried out using the intermolecular condensation reaction that grows through of polymer chain The obtained resin of polymerization.The resin of the polycondensation system of the present invention is preferably at least 1 in carbonic acid ester bond and ester bond The resin of a key, more particularly, it is preferable that being any one of makrolon, polyester and polyestercarbonate resin.On these Resin can enumerate following advantages：Heat resistance, mechanical properties, melt processable are excellent, in addition, by by the monomer of 2 or more into Row copolymerization, easily by the various physical characteristics controls such as optics physical property, heat resistance, mechanical properties in desired scope.

The resin of the present invention includes aromatic structure, as aromatic structure, as long as the cyclic structure with armaticity Any structure can then be included.More specifically, the aromatic rings of benzenoid form, the aromatic rings of non-benzenoid form, heteroaromatic can be enumerated Deng wherein it is preferred that the aromatic rings or heteroaromatic of benzenoid form.In the present invention, on the fragrance in the constitutional repeating unit for forming resin The computational methods of the content of race's structure name out specific example and illustrate.

[molecular weight in the calculating of various aromatic structures]

Carbon atom, the hydrogen included in the molecular weight of aromatic structure in the present invention in the cyclic structure with armaticity is former Son, hetero atom.Carbon atom, the hetero atom being bonded with the cyclic structure with armaticity are not included in aromatic structure.In addition, Whens vinyl, acetenyl, carbonyl etc. are bonded in the cyclic structure with armaticity, the conjugated system of aromatic rings extends to these Functional group, but be not included in the substituent group that the cyclic structure with armaticity is bonded in aromatic structure.

[changing 16]

The molecular weight of aromatic structure：C₆H₄=76.10

The molecular weight of aromatic structure：C₁₀H₆=126.15

The molecular weight of aromatic structure：C₆H₄× 2=152.19

The molecular weight of aromatic structure：C₆H₃=75.09

The molecular weight of aromatic structure：C₄H₂O=66.06

The molecular weight of aromatic structure：C₅H₄N=78.09

[changing 17]

The molecular weight of aromatic structure：C₆H₄× 2=152.19

The molecular weight of aromatic structure：C₆H₃× 2=150.18Aromatic series knot The molecular weight of structure：C₁₀H₆=126.15

[calculated example 1]

[changing 18]

The molecular weight of constitutional repeating unit：C₁₀H₈O₄=192.17

The molecular weight of aromatic structure in constitutional repeating unit：C₆H₄=76.10

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

[calculated example 2]

[changing 19]

Constitutional repeating unit A

Constitutional repeating unit B

For the copolymer resins and constitutional repeating unit A and constitutional repeating unit of constitutional repeating unit A and constitutional repeating unit B The molar ratio of B is m：N=3：7 situation.

The molecular weight of constitutional repeating unit A：C₃₀H₂₄O₅=464.51

The molecular weight of aromatic structure in constitutional repeating unit A：C₆H₄× 4=304.38

The molecular weight of constitutional repeating unit B：C₁₆H₁₄O₃=254.28

Molecular weight=C of aromatic structure in constitutional repeating unit B₆H₄× 2=152.19

The content of aromatic structure：

(304.38 × 0.3+152.19 × 0.7)/(464.51 × 0.3+254.28 × 0.7) × 100=62.3 [matter Measure %]

The present invention resin be characterized in that, be calculated as above composition resin constitutional repeating unit in aromatic series knot The content of structure meets following (I) formulas.Further preferably meet following (II) formulas, particularly preferably meet 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)

Wherein, 0.75≤B≤0.93.

When the value of the R450/R550 of above-mentioned formula (I) is less than 1, phase difference has inverse wave length dispersiveness, as 1/4 wavelength In the case of plate use, it can be obtained close to preferable phase difference characteristics in extensive wavelength region.As showing the head sea One of method of long dispersiveness, can enumerate make the refractive index compared with the backbone constituents of polymer chain wavelength dispersion (wavelength according to Relying property) big ingredient is orientated in the vertical direction of main chain.In general, the wavelength dispersion of the more long then refractive index of aromatic conjugated system It is bigger, thus the resin with inverse wave length dispersiveness preferably comprises aromatic structure.On the other hand, virtue is contained in backbone constituents In the case of fragrant race, the aromatic component on main chain shows strong positive wavelength dispersibility, therefore can cancel inverse wave length and disperse Property.If in addition, usually largely containing aromatic series, photoelastic coefficient or refractive index can increase, and be not preferred as optics physical property Direction.Above-mentioned formula (I) means the efficient aromatic structure of the performance that importing inverse wave length is disperseed, by other aromatic components It is suppressed to required Min..By that for such MOLECULE DESIGN, can obtain photoelastic while with inverse wave length dispersiveness The resin of the balancing good of the optical characteristics such as property coefficient or orientation.Hereinafter specific preferred molecular structure is illustrated.

It, should using the value of the wavelength dispersion measured in the evaluation for having used stretched film as the value of B (R450/R550) Stretched film is obtained by the unstretching film made using pressure sintering by resin.

The resin of the present invention is preferably had selected from the structural unit represented by the following general formula (1) and the following general formula (2) institute The structural unit of one or more of the group of structural unit composition of expression.Hereinafter, the structural unit is known as oligomeric fluorenes knot sometimes Structure unit.

[changing 20]

In above-mentioned general formula (1) and above-mentioned general formula (2), R¹~R³It is each independently Direct Bonding, with or without substitution The carbon number of base is 1~4 alkylidene.

R⁴~R⁹It is each independently hydrogen atom, the alkyl that the carbon number with or without substituent group is 1~10, tool Have or aryl that the carbon number without substituent group is 4~10, with or without the carbon number of substituent group be 1~10 Acyloxy, the carbon number with or without substituent group that acyl group, the carbon number with or without substituent group are 1~10 Alkoxy for 1~10, with or without substituent group carbon number be 1~10 aryloxy group, with or without substitution The amino of base, vinyl of the carbon number for 1~10 with or without substituent group, the original of the carbon with or without substituent group Subnumber is 1~10 acetenyl, the sulphur atom with substituent group, the silicon atom with substituent group, halogen atom, nitro or cyanogen Base.

In R¹And R²In, as " alkylidene that the carbon number with or without substituent group is 1~4 ", such as can adopt With following alkylidene.The alkylidene of the straight-chains such as methylene, ethylidene, n-propylene, positive butylidene；Methylmethylene, two Methylmethylene, ethyl methylene, propylmethylene, (1- Methylethyls) methylene, 1- methyl ethylidene, 2- methyl Asia second Base, 1- ethylethylene residues, 2- ethylethylene residues, 1- methyl propylenes, 2- methyl propylenes, 1,1- dimethylethylenes, 2,2- Dimethylpropylidene, 3- methyl propylenes etc. have the alkylidene of branch.Herein, R¹And R²In branch position by according to fluorenes Number that the carbon of ring side is assigned by the mode of 1 represents.

R¹And R²Selection can be on the especially important influence of the performance of inverse wave length dispersiveness generation.Above-mentioned resin is in fluorenes ring phase Most strong inverse wave length dispersiveness is shown in the state of vertical orientated for main chain direction (draw direction).In order to make taking for fluorenes ring To state close to above-mentioned state, strong inverse wave length dispersiveness is shown, it is preferred to use the carbon number on the main chain of alkylidene For 2~3 R¹And R².In the case where carbon number is 1, inverse wave length dispersiveness can not be unexpectedly shown sometimes.As it Main cause, consideration are the steric hindrances of the carbonate group or ester group due to the linking group as oligomeric fluorene structural units, from And it is not vertical direction etc. that the orientation of fluorenes ring, which is fixed in compared with main chain direction,.On the other hand, when carbon number is excessive, The fixed decrease of the orientation of fluorenes ring, so as to inverse wave length dispersiveness it is possible that weakening.In addition, the heat resistance of resin also reduces.

As shown in above-mentioned general formula (1) and general formula (2), on R¹And R², one end of alkylidene is bonded with fluorenes ring, the other end with Any one bonding in oxygen atom or carbonyl carbon contained by linking group.From thermal stability, heat resistance and inverse wave length dispersiveness Aspect set out, the preferably other end of alkylidene and carbonyl bond with carbon.As described later, as with oligomeric fluorene structured monomer, It is specific to be contemplated that the structure of glycol or diester (hereinafter, diester also includes dicarboxylic acids), but preferably carry out diester for raw material Polymerization.

In addition, from make it is easy to manufacture from the aspect of, preferably R¹And R²Using identical alkylidene.

In R³In, as " alkylidene that the carbon number with or without substituent group is 1~4 ", such as may be employed Following alkylidene.The alkylidene of the straight-chains such as methylene, ethylidene, n-propylene, positive butylidene；Methylmethylene, diformazan Methylene, ethyl methylene, propylmethylene, (1- Methylethyls) methylene, 1- methyl ethylidene, 2- methyl ethylidene, 1- ethylethylene residues, 2- ethylethylene residues, 1- methyl propylenes, 2- methyl propylenes, 1,1- dimethylethylenes, 2,2- diformazans Base propylidene, 3- methyl propylenes etc. have the alkylidene of branch.

R³It is preferred that the carbon number on the main chain of alkylidene is 1~2, particularly preferred carbon number is 1.Using on main chain The excessive R of carbon number³When, with R¹And R²Similarly the immobilization of fluorenes ring weakens, it is possible to cause the drop of inverse wave length dispersiveness Low, photoelastic coefficient increase, reduction of heat resistance etc..On the other hand, when the carbon number on main chain is few, optical characteristics or resistance to It is hot good, but thermal stability is deteriorated in the case of being connected at 9 of two fluorenes rings with Direct Bonding.

In R¹~R³In, as the substituent group that alkylidene can have, substituent group illustrated below may be employed, it can also Using the substituent group beyond these.Halogen atom in fluorine atom, chlorine atom, bromine atoms and iodine atom；Methoxyl group, ethyoxyl Wait the alkoxy that carbon numbers are 1~10；The carbon numbers such as acetyl group, benzoyl are 1~10 acyl group；Acetamido, benzene The carbon numbers such as formamido are 1~10 amide groups；Nitro；Cyano；1~3 hydrogen atom can be by above-mentioned halogen atom, above-mentioned The carbon numbers such as substituted, phenyl, the naphthalenes such as alkoxy, above-mentioned acyl group, above-mentioned amide groups, above-mentioned nitro, above-mentioned cyano for 6~ 10 aryl.

The quantity of above-mentioned substituent group is not particularly limited, preferably 1~3.In the case where substituent group is 2 or more, The species of substituent group can be the same or different.When the quantity of substituent group is excessive, it is possible that can inhibit to react in polymerization, Or generate thermal decomposition.In addition, from the aspect that can industrially manufacture at low cost, preferably R¹~R³To be unsubstituted.

In R⁴~R⁹In, as " alkyl that the carbon number with or without substituent group is 1~10 ", such as can adopt With following alkyl.The alkyl of the straight-chains such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, positive decyl；Isopropyl Base, 2- methyl-propyls, 2,2- dimethyl propyls, 2- ethylhexyls etc. have the alkyl of branch；Cyclopropyl, cyclopenta, cyclohexyl, The isothrausmatic alkyl of cyclooctyl.

The carbon number of abovementioned alkyl is preferably less than 4, more preferably less than 2.If in the range of this, then fluorenes ring is difficult each other To generate steric hindrance, have and obtain the tendency of the desired optical characteristics from fluorenes ring.

As the substituent group that abovementioned alkyl can have, substituent group illustrated below may be employed, these can also be used Substituent group in addition.Halogen atom in fluorine atom, chlorine atom, bromine atoms and iodine atom；The carbon atoms such as methoxyl group, ethyoxyl Number is 1~10 alkoxy；The carbon numbers such as acetyl group, benzoyl are 1~10 acyl group；Acetamido, benzamido Wait the amide groups that carbon numbers are 1~10；Nitro；Cyano；1~3 hydrogen atom can by above-mentioned halogen atom, above-mentioned alkoxy, The carbon numbers such as substituted, phenyl, the naphthalenes such as above-mentioned acyl group, above-mentioned amide groups, above-mentioned nitro, above-mentioned cyano are 6~10 virtue Base

The quantity of above-mentioned substituent group is not particularly limited, preferably 1~3.In the case where substituent group is 2 or more, The species of substituent group can be the same or different.When the quantity of such substituent group is excessive, it is possible that can inhibit in polymerization Reaction generates thermal decomposition.In addition, from the aspect that can industrially manufacture at low cost, preferably R⁴~R⁹It is taken for nothing Generation.As the concrete example of abovementioned alkyl, trifluoromethyl, benzyl, 4- methoxy-benzyls, methoxy etc. can be enumerated.

In addition, in R⁴~R⁹In, as " aryl that the carbon number with or without substituent group is 4~10 ", such as can To use following aryl.The aryl such as phenyl, 1- naphthalenes, 2- naphthalenes；The heteroaryls such as 2- pyridyl groups, 2- thienyls, 2- furyls.

The carbon number of above-mentioned aryl is preferably less than 8, more preferably less than 7.If in the range of this, then fluorenes ring is difficult each other To generate steric hindrance, have and obtain the tendency of the desired optical characteristics from fluorenes ring.

In R⁴~R⁹In, as the substituent group that above-mentioned aryl can have, substituent group illustrated below may be employed, also may be used With using the substituent group beyond these.Halogen atom in fluorine atom, chlorine atom, bromine atoms and iodine atom；Methyl, ethyl, The carbon numbers such as isopropyl are 1~10 alkyl；The carbon numbers such as methoxyl group, ethyoxyl are 1~10 alkoxy；Acetyl group, The carbon numbers such as benzoyl are 1~10 acyl group；The carbon numbers such as acetamido, benzamido are 1~10 amide groups； Nitro；Cyano.The quantity of above-mentioned substituent group is not particularly limited, preferably 1~3.In the situation that substituent group is 2 or more Under, the species of substituent group can be the same or different.In addition, from the aspect that can industrially manufacture at low cost, It is preferred that R⁴~R⁹To be unsubstituted.

As the concrete example of above-mentioned aryl, 2- aminomethyl phenyls, 4- aminomethyl phenyls, 3,5- 3,5-dimethylphenyls, 4- can be enumerated Benzoylphenyl, 4- methoxyphenyls, 4- nitrobenzophenones, 4- cyano-phenyls, 3- trifluoromethyls, 3,4- dimethoxy benzenes Base, 3,4- methylene dihydroxyphenyl, 2,3,4,5,6- pentafluorophenyl groups, 4- methylfuran bases etc..

In addition, in R⁴~R⁹In, as " acyl group that the carbon number with or without substituent group is 1~10 ", such as can To use following acyl group.Formoxyl, acetyl group, propiono, 2- methylpropionyls, 2,2- Dimethylpropanoyls, 2- ethyl hexyls The aliphatic acyl radicals such as acyl group；The aromatic acyls such as benzoyl, 1- naphthyl carbonyls, 2- naphthyl carbonyls, 2- furyl carbonyls.

The carbon number of above-mentioned acyl group is preferably less than 4, more preferably less than 2.If in the range of this, then fluorenes ring is difficult each other To generate steric hindrance, have and obtain the tendency of the desired optical characteristics from fluorenes ring.

As the substituent group that above-mentioned acyl group can have, substituent group illustrated below may be employed, these can also be used Substituent group in addition.Halogen atom in fluorine atom, chlorine atom, bromine atoms and iodine atom；The carbon such as methyl, ethyl, isopropyl Atomicity is 1~10 alkyl；The carbon numbers such as methoxyl group, ethyoxyl are 1~10 alkoxy；Acetamido, benzamide The carbon numbers such as base are 1~10 amide groups；Nitro；Cyano；1~3 hydrogen atom can be by above-mentioned halogen atom, above-mentioned alcoxyl The carbon numbers such as base, acetyl group, benzoyl are the substitutions such as 1~10 acyl group, above-mentioned amide groups, above-mentioned nitro, above-mentioned cyano , the aryl that the carbon numbers such as phenyl, naphthalene are 6~10.

The quantity of above-mentioned substituent group is not particularly limited, preferably 1~3.In the case where substituent group is 2 or more, The species of substituent group can be the same or different.In addition, from the aspect that can industrially manufacture at low cost, preferably R⁴~R⁹To be unsubstituted.

As the concrete example of above-mentioned acyl group, chloracetyl, trifluoroacetyl group, Methoxyacetyl, phenoxy group can be enumerated Acetyl group, 4- methoxybenzoyls base, 4- nitro benzoyls, 4- cyanobenzoyls, 4- trifluoromethylbenzoyl etc..

In addition, in R⁴~R⁹In, as " acyloxy that the carbon number with or without substituent group is 1~10 ", such as Following acyloxy may be employed.The fat such as formoxyl, acetyl group, propiono, bytyry, acryloyl group, methylacryloyl Race's acyloxy；The aromatic series acyloxy such as benzoyl.

As the substituent group that above-mentioned acyloxy can have, substituent group illustrated below may be employed, this can also be used Substituent group beyond a little.Halogen atom in fluorine atom, chlorine atom, bromine atoms and iodine atom；Methyl, ethyl, isopropyl etc. Carbon number is 1~10 alkyl；The carbon numbers such as methoxyl group, ethyoxyl are 1~10 alkoxy；Acetamido, benzoyl The carbon numbers such as amido are 1~10 acylamino-；Nitro；Cyano；1~3 hydrogen atom can be by above-mentioned halogen atom, above-mentioned alcoxyl The carbon numbers such as base, acetyl group, benzoyl are the substitutions such as 1~10 acyl group, above-mentioned acylamino-, above-mentioned nitro, above-mentioned cyano , the aryl that the carbon numbers such as phenyl, naphthalene are 6~10.

The quantity of above-mentioned substituent group is not particularly limited, preferably 1~3.In the case that substituent group is 2 or more, take The species of Dai Ji can be the same or different.In addition, from the aspect that can industrially manufacture at low cost, R⁴~R⁹ It is preferably unsubstituted.As the concrete example of above-mentioned acyl group, chloracetyl, trifluoroacetyl group, Methoxyacetyl, benzene can be enumerated Oxygroup acetyl group, 4- methoxybenzoyls base, 4- nitro benzoyls, 4- cyanobenzoyls, 4- trifluoromethylbenzoyl Deng.

In addition, in R⁴~R⁹In, as " the alkoxy or fragrant oxygen that the carbon number with or without substituent group is 1~10 Base ", such as following alkoxy and aryloxy group may be employed.Methoxyl group, ethyoxyl, isopropoxy, tert-butoxy, trifluoro methoxy The alkoxies such as base；The aryloxy group such as phenoxy group.

The preferred alkoxy in above-mentioned alkoxy and above-mentioned aryloxy group, the carbon number of alkoxy is preferably less than 4, more excellent Elect less than 2 as.If in the range of this, then fluorenes ring is difficult to generate steric hindrance each other, has and obtains from the desired of fluorenes ring The tendency of optical characteristics.

In addition, in R⁴~R⁹In, as the concrete structure of " with or without the amino of substituent group ", such as may be employed Following amino can also use the amino beyond these.Amino；N- methylaminos, N, N- dimethylaminos, N- ethyl ammonia Base, N, N- diethylaminos, N, N- methylethylamines, N- propylcarbamics, N, N- dipropylaminos, N- isopropylaminos, N, The aliphatic amines such as N- diisopropylaminoethyls；The aromatic series amino such as N- phenyl aminos, N, N- diphenyl aminos；Formamido, second The amide groups such as amide groups, caprinoyl amido, benzamido, chloracetyl amido；Benzyoxycarbonylamino, tertbutyloxycarbonylamino Wait alkoxycarbonyl amidos.

As above-mentioned amino, it is preferred to use without the high proton of acid degree, molecular weight is small, has and can improve fluorenes ratio Tendency, N, N- dimethylaminos, N- ethylaminos or N, N- diethylamino, more preferably using N, N- dimethylaminos.

In addition, in R⁴~R⁹In, as " the vinyl or acetylene that the carbon number with or without substituent group is 1~10 Base ", such as following vinyl and acetenyl may be employed, the vinyl etc. beyond these can also be used.Vinyl, 2- first Base vinyl, 2,2- dimethyl ethenyls, 2- phenyl vinyls, 2- acetyl group vinyl, acetenyl, methylacetylenyl, tertiary fourth Ethyl-acetylene base, phenylene-ethynylene, acetyl group acetenyl, trimethylsilylacetylenyl.

The carbon number of above-mentioned vinyl and above-mentioned acetenyl is preferably less than 4.If in the range of this, then fluorenes ring is difficult each other To generate steric hindrance, have and obtain the tendency of the desired optical characteristics from fluorenes ring.In addition, the conjugated system of fluorenes ring becomes It is long, so as to be easy to get strong inverse wave length dispersiveness.

In addition, in R⁴~R⁹It is middle such as to may be employed following containing sulfenyl as the sulphur atom of substituent group " have ", also may be used To contain sulfenyl using beyond these.Sulfo group；The alkane such as methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, isopropelsulfonyl Base sulfonyl；The aryl sulfonyls such as benzenesulfonyl, p-methylphenyl sulfonyl；Methylsulfinyl, ethylsulfinyl, propyl are sub- The alkyl sulphinyls such as sulfonyl, isopropylsulphinyl；The aryl sulfenyls such as phenylsufinyl, p-methylphenyl sulfinyl Base；The alkylthio groups such as methyl mercapto, ethylmercapto group；The arylthios such as thiophenyl, p-methylphenyl sulfenyl；Methoxysulfonyl, ethyoxyl sulphonyl The alkyloxysulfonyls such as base；The aryloxy sulfonyls such as phenoxysulfonyl groups；Amino-sulfonyl；N- methylaminosulfonyls, N- second Base amino-sulfonyl, N- tert-butylaminos sulfonyl, the alkane such as N, N- dimethylamino-sulfonyls, N, N- diethylamino sulfonyls Base sulfonyl；The n-aryl sulfonyls such as N- phenylaminosulfonyl groups, N, N- diphenyl amino sulfonyls.It should be noted that Sulfo group can also be with the forming salts such as lithium, sodium, potassium, magnesium, ammonium.

Above-mentioned containing in sulfenyl, it is preferred to use without the high proton of acid degree, molecular weight is small, can improve fluorenes ratio, Methylsulfinyl, ethylsulfinyl or phenylsufinyl, more preferably using methylsulfinyl.

In addition, in R⁴~R⁹In, as " silicon atom with substituent group ", such as following silicyl may be employed.Three The trialkylsilkls such as methyl silicane base, triethylsilyl；Trimethoxysilyl, triethoxysilyl Etc. trialkoxysilyls.Among these, the preferred trialkylsilkl of stably operable.

In addition, in R⁴~R⁹In, as " halogen atom ", fluorine atom, chlorine atom, bromine atoms, iodine atom may be employed.These Among, it is preferred to use be easier to import and because with it is electron-withdrawing due to there is reactive tendency, the fluorine for improving fluorenes 9 Atom, chlorine atom or bromine atoms more preferably use chlorine atom or bromine atoms.

In addition, in R⁴~R⁹In, adjacent 2 groups can be mutually bonded to form ring.As its concrete example, can enumerate Substitution with the skeleton illustrated in following [A] groups is fluorene structured.

[A]

[changing 21]

As described above, by making R⁴~R⁹For above-mentioned specific atoms or substituent group, so as between main chain and fluorenes ring, fluorenes ring Steric hindrance each other is few, has the tendency that can obtain the desired optical characteristics from fluorenes ring.

Fluorenes ring contained by above-mentioned oligomeric fluorene structural units is preferably any one of following compositions：R⁴~R⁹All hydrogen The composition of atom；Alternatively, R⁴And/or R⁹To select any in free halogen, acyl group, nitro, cyano and the group of sulfo group composition Kind and R⁵~R⁸For the composition of hydrogen atom.During with the former composition, it can be derived and included by industrial cost also low fluorenes The compound of above-mentioned oligomeric fluorene structural units.In addition, during composition with the latter, the reactivity raising of fluorenes 9, therefore comprising In the building-up process of the compound of above-mentioned oligomeric fluorene structural units, there is the tendency for being suitable for various induced reactions.Above-mentioned fluorenes ring Any one of more preferably following compositions：R⁴~R⁹The composition of all hydrogen atoms；Alternatively, R⁴And/or R⁹It is former by fluorine to be selected from Any one of group that son, chlorine atom, bromine atoms and nitro form and R⁵~R⁸For the composition of hydrogen atom；Particularly preferably R⁴ ~R⁹The composition of all hydrogen atoms.By using above-mentioned composition, fluorenes ratio can be improved, and fluorenes ring is difficult to generate sky each other Between steric hindrance, also have obtain the tendency of the desired optical characteristics from fluorenes ring.

In the oligomeric fluorene structural units of the divalent represented by above-mentioned general formula (1) and general formula (2), as preferred structure, tool Body can enumerate the structure with the skeleton illustrated in following [B] groups.

[B] group

[changing 22]

The oligomeric fluorene structural units of the present invention are with being commonly used from double [4- (2- hydroxyl-oxethyls) benzene of 9,9- in the past Base] fluorenes structural unit (following structural formula (9)), the structural unit from double (the 4- hydroxy-3-methyls phenyl) fluorenes of 9,9- it is (following Structural formula (10)) it compares, there are following characteristics.

In the past, the main chain that the aromatic components such as the benzyl ring of the main chain of polymer are not introduced into polymer is introduced into, because This can reduce photoelastic coefficient.

The above-mentioned aromatic component for being introduced into main chain shows the bigger positive wavelength dispersibility of the more short then birefringence of wavelength, Thus, the inverse wave length dispersiveness of the fluorenes ring from side chain was cancelled in the past, and the inverse wave length dispersiveness as resin entirety reduces.With This is opposite, and aromatic component is not introduced into main chain, so as to more strongly show inverse wave length dispersiveness.

By importing two fluorenes rings in a molecule, so as to assign high-fire resistance.

Main chain is made of soft alkylidene chain, thus can assign flexibility, melt processable to resin.

[changing 23]

The resin of the present invention contains links group and above-mentioned oligomeric fluorenes knot comprising at least one of carbonic acid ester bond and ester bond The resin of structure unit.As the makrolon of resin with above-mentioned connection group, the heat resistance of polyester and polyestercarbonate, machine Tool characteristic, melt processable are excellent.In addition, by with other monomer copolymerizations, so as to by above-mentioned oligomeric fluorene structural units ratio It relatively easily imports in resin, and is desired model with easily the ratio of the oligomeric fluorene structural units in resin is controlled The advantages of enclosing.

As the method imported above-mentioned oligomeric fluorene structural units in resin, for example, will have above-mentioned oligomeric fluorenes The glycol or diester of structural unit and other glycol or the method for diester copolymerization.Specifically, by with glycol and following logical The combination of carbonic diester represented by formula (11) is polymerize, so as to obtain makrolon.In addition, by with glycol and The combination of diester is polymerize, and can obtain polyester.In addition, it is carried out by the combination with glycol, diester and carbonic diester Polymerization, can obtain polyestercarbonate.

[changing 24]

In above-mentioned general formula (11), A¹And A²The aliphatic that carbon number respectively with or without substituent group is 1~18 Alkyl or the aromatic hydrocarbyl with or without substituent group, A¹And A²It can be the same or different.

As the monomer with above-mentioned oligomeric fluorene structural units, for example, specific represented by the following general formula (12) Glycol or the following general formula (13) represented by specific diester.

[changing 25]

In above-mentioned general formula (12) and general formula (13), R¹~R³It is each independently Direct Bonding, with or without substituent group Carbon number be 1~4 alkylidene.

A³And A⁴The aliphatic hydrocarbon that carbon number for hydrogen atom or respectively with or without substituent group is 1~18 Base or the aromatic hydrocarbyl with or without substituent group, A³And A⁴It can be the same or different.

It is represented it is preferable to use above-mentioned general formula (13) as the above-mentioned monomer of the oligomeric fluorene structural units with above-mentioned divalent Specific diester.Compared with the specific glycol represented by above-mentioned general formula (12), thermal stability compares above-mentioned specific diester Well, the fluorenes ring and in polymer is orientated in preferred direction, has the tendency for showing stronger inverse wave length dispersiveness.

On the other hand, it is obtained by glycol and polymerizeing for carbonic diester if being compared to makrolon and polyester Makrolon has the good tendency of balance of heat resistance and mechanical property.Therefore, the resin as the present invention particularly preferably will Above-mentioned specific diester with oligomeric fluorene structural units is introduced into the polyestercarbonate formed in the structure of makrolon.

The A of above-mentioned general formula (13)³And A⁴For hydrogen atom or in the case of being the aliphatic alkyls such as methyl or ethyl, logical Polymerisation is difficult to happen sometimes under the polymerizing condition of the makrolon often used.Therefore, the A of above-mentioned general formula (13)³And A⁴It is preferred that For aromatic hydrocarbyl.

In addition, in the case where the carbonic diester represented by above-mentioned general formula (11) is also used to carry out polymerisation, if above-mentioned The A of general formula (11)¹、A²With the A of above-mentioned general formula (13)³、A⁴Be identical structure, then the ingredient departed from the polymerization is identical, Easily recycle and recycle.In addition, from the serviceability aspect in polymerisation reactivity and recycling, A¹~A⁴Particularly preferably For phenyl.It should be noted that A¹~A⁴In the case of phenyl, the ingredient departed from polymerisation is phenol.

In the resin of the present invention, aftermentioned positive refracting power anisotropy and sufficient inverse wave length dispersiveness, need in order to obtain It is specific scope by the proportion adjustment of the above-mentioned oligomeric fluorene structural units in above-mentioned resin.As in the above-mentioned resin of adjusting The method of the ratio of above-mentioned oligomeric fluorene structural units, for example,：By the monomer with above-mentioned oligomeric fluorene structural units with The method that other monomers are copolymerized；The side that resin with above-mentioned oligomeric fluorene structural units and other resins are blended Method.Due to can critically control the content of oligomeric fluorene structural units and can obtain high transparency, can be obtained in the entire surface of film To uniform characteristic, thus the method for being preferably copolymerized the monomer with above-mentioned oligomeric fluorene structural units and other monomers.

Compared with all resins, the content of the above-mentioned oligomeric fluorene structural units in above-mentioned resin is preferably more than 1 mass % Below 40 mass %, more preferably below 35 mass % of more than 10 mass %, further preferably 32 matter of more than 15 mass % Measure below %, particularly preferably below 30 mass % of more than 20 mass %.When the content of oligomeric fluorene structural units is excessive, photoelasticity Coefficient or reliability can be deteriorated or be possible to that high birefringence can not be obtained by stretching.Further, since oligomeric fluorene structured list Member ratio rise shared in resin, thus the scope of MOLECULE DESIGN narrows, and is difficult to improve when requiring the modification of resin.Separately On the one hand, it is assumed that desired inverse wave length dispersiveness, the feelings have been obtained even by very small amount of oligomeric fluorene structural units Under condition, according to the slightly fluctuation of oligomeric fluorenes content, optical characteristics can sensitively change, thus be difficult to limit various characteristics It is manufactured in a certain range.

The resin of the present invention is preferably obtained by that will have the monomer of above-mentioned oligomeric fluorene structural units with other monomer copolymerizations It arrives.As the other monomers being copolymerized, for example, dihydroxy compounds, diester compound.

From optical characteristics, mechanical property, heat resistance etc., resin of the invention preferably comprises the following general formula (3) Structural unit as copolymer composition.

[changing 26]

As the dihydroxy compounds that can import the structural unit represented by above-mentioned general formula (3), can enumerate in sky Between the relation of isomers, isobide (ISB), isomannite, different idose.They can be used alone, and can also incite somebody to action Two or more is applied in combination.Among these, from obtaining and polymerisation reactivity aspect, most preferably with ISB.

Structural unit represented by above-mentioned general formula (3) preferably comprised in above-mentioned resin more than 5 mass % 70 mass % with Under, further preferably below 65 mass % of more than 10 mass %, particularly preferably containing 60 mass % of more than 20 mass % with Under.If the content of the structural unit represented by above-mentioned general formula (3) is very few, heat resistance may be insufficient.On the other hand, it is if above-mentioned The content of structural unit represented by general formula (3) is excessive, then heat resistance excessively raises, and mechanical property, melt processable are deteriorated.Separately Outside, since the structural unit represented by above-mentioned general formula (3) is bibulous structure, thus in the case where content is excessive, tree The water absorption rate rise of fat, is likely to occur size distortion in the environment of high humility.

In addition, the resin of the present invention can combine or without using above-mentioned general formula with the structural unit of above-mentioned general formula (3) (3) structure and further include other structures unit.(structural unit hereinafter, is known as " other structures list sometimes Member ".)

As above-mentioned other structures unit, particularly preferably there is the following general formula (4)~(8) institute for not containing aromatic component The structural unit of expression.

[changing 27]

In above-mentioned general formula (4), R^1-10The alkylidene that expression is 2~20 with or without the carbon number of substituent group.

As the dihydroxy compounds for the structural unit that can import above-mentioned general formula (4), such as following two may be employed Hydroxy compounds.Ethylene glycol, 1,3- propylene glycol, 1,2- propylene glycol, 1,4- butanediols, 1,3 butylene glycol, 1,2- butanediols, 1,5- The dihydroxy of the straight-chain aliphatics hydrocarbon such as heptandiol, 1,6-HD, 1,9- nonanediols, 1,10- decanediols, 1,12- dodecanediols Based compound；The dihydroxy compounds of the branched chain aliphatic hydrocarbons such as neopentyl glycol, hexylene glycol.

[changing 28]

In above-mentioned general formula (5), R^1-11The ring alkylidene that expression is 4~20 with or without the carbon number of substituent group.

As the dihydroxy compounds for the structural unit that can import above-mentioned general formula (5), such as following two may be employed Hydroxy compounds.1,2- cyclohexanediols, 1,4- cyclohexanediols, 1,3- adamantane glycol, hydrogenated bisphenol A, 2,2,4,4- tetramethyls- Illustrated in 1,3- cyclobutanediols etc. as the secondary alcohol of ester ring type hydrocarbon and the dihydroxy compounds of the tertiary alcohol.

[changing 29]

In above-mentioned general formula (6), R^1-12The ring alkylidene that expression is 4~20 with or without the carbon number of substituent group.

As the dihydroxy compounds for the structural unit that can import above-mentioned general formula (6), such as following two may be employed Hydroxy compounds.1,2- cyclohexanedimethanols, 1,3- cyclohexanedimethanols, 1,4 cyclohexane dimethanol, Tricyclodecane Dimethanol, Pentacyclopentadecane dimethanol, 2,6- decahydronaphthalenes dimethanol, 1,5- decahydronaphthalenes dimethanol, 2,3- decahydronaphthalenes dimethanol, 2, The dihydroxy as derived from terpene compound such as 3- norcamphanes dimethanol, 2,5- norcamphanes dimethanol, 1,3- adamantane dimethanol, limonenes The dihydroxy compounds of primary alconol illustrated in based compound etc., as ester ring type hydrocarbon.

[changing 30]

In above-mentioned general formula (7), R^1-13The alkylidene that expression is 2~10 with or without the carbon number of substituent group, p are 1~40 integer.

As the dihydroxy compounds for the structural unit that can import above-mentioned general formula (7), such as following two may be employed Hydroxy compounds.The oxyalkylene groups glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol.

[changing 31]

In above-mentioned general formula (8), R^1-14It represents to be 2~20 with or without the carbon number of substituent group with acetal The group of ring.

As the dihydroxy compounds for the structural unit that can import above-mentioned general formula (8), such as following structures may be employed Dioxane glycol represented by the spiroglycol, following structural formula (15) represented by formula (14) etc..

[changing 32]

In addition, in addition to above-mentioned dihydroxy compounds, can also use it is illustrated below containing aromatic component two Hydroxy compounds.Double (4- hydroxy phenyls) propane of 2,2-, 2,2-bis(3-methyl-4-hydroxyphenyl) propane, double (the 4- hydroxyls of 2,2- Base -3,5- 3,5-dimethylphenyls) propane, double (4- hydroxyl -3,5- diethyl phenyls) propane of 2,2-, double (the 4- hydroxyls-(3- benzene of 2,2- Base) phenyl) propane, double (4- hydroxyls-(3,5- diphenyl) phenyl) propane of 2,2-, 2,2- be double (4- hydroxyl -3,5- dibromo phenyls) Double (4- hydroxy phenyls) ethane of propane, double (4- hydroxy phenyls) methane, 1,1-, double (4- hydroxy phenyls) butane of 2,2-, 2,2- are double (4- hydroxy phenyls) pentane, 1,1- double (4- hydroxy phenyls) -1- diphenylphosphino ethanes, double (4- hydroxy phenyls) diphenyl methanes, 1,1- Double (4- hydroxy phenyls) -2- ethyl hexanes, 1,1- double (4- hydroxy phenyls) decane, double (4- hydroxyl -3- nitrobenzophenones) methane, 3, Double (4- hydroxy phenyls) pentanes of 3-, double (2- (4- the hydroxy phenyls) -2- propyl) benzene of 1,3-, double (2- (4- the hydroxy phenyls) -2- of 1,3- Propyl) benzene, double (4- hydroxy phenyls) hexafluoropropane of 2,2-, 1,1-bis(4-hydroxyphenyl)-cyclohexane, double (4- hydroxy phenyls) sulfones, 2,4 '-dihydroxydiphenylsulisomer, double (4- hydroxy phenyls) thioethers, double (4- hydroxy-3-methyls phenyl) thioethers, double (4- hydroxy phenyls) The aromatic bisphenols class compound such as disulfide, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxy -3,3 '-Dichlorodiphenyl ether； Double (4- (2- hydroxyl-oxethyls) phenyl) propane of 2,2-, double (4- (2- hydroxy propyloxy groups) phenyl) propane of 2,2-, double (the 2- hydroxyls of 1,3- Base oxethyl) benzene, 4,4 '-bis- (2- hydroxyl-oxethyls) biphenyl, double (4- (2- hydroxyl-oxethyls) phenyl) sulfones etc. have and be bonded to The dihydroxy compounds of ether on aromatic group；Double (4- (2- hydroxyl-oxethyls) phenyl) fluorenes of 9,9-, double (the 4- hydroxyls of 9,9- Phenyl) fluorenes, double (the 4- hydroxy-3-methyls phenyl) fluorenes of 9,9-, double (4- (2- hydroxy propyloxy groups) phenyl) fluorenes of 9,9-, the double (4- of 9,9- (2- hydroxyl-oxethyls) -3- aminomethyl phenyls) fluorenes, double (4- (2- the hydroxy propyloxy groups) -3- aminomethyl phenyls) fluorenes of 9,9-, the double (4- of 9,9- (2- hydroxyl-oxethyls) -3- isopropyl phenyls) fluorenes, double (4- (2- the hydroxyl-oxethyls) -3- isobutyl phenenyls) fluorenes of 9,9-, 9,9- be double (4- (2- hydroxyl-oxethyls) -3- tert-butyl-phenyls) fluorenes, 9,9- double (4- (2- hydroxyl-oxethyls) -3- cyclohexyl phenyls) fluorenes, 9, Double (4- (2- the hydroxyl-oxethyls) -3- phenyls) fluorenes of 9-, 9,9- are double (4- (2- hydroxyl-oxethyls) -3,5- 3,5-dimethylphenyls) Double (4- (2- the hydroxyl-oxethyls) -3- tertiary butyl -6- aminomethyl phenyls) fluorenes of fluorenes, 9,9-, the double (4- (3- hydroxyl -2,2- dimethyl of 9,9- Propoxyl group) phenyl) fluorenes etc. has the dihydroxy compounds of fluorenes ring.

In addition, as the diester chemical combination that can be used in the copolymerization with the monomer with above-mentioned oligomeric fluorene structural units Object, such as dicarboxylic acids as shown below etc. may be employed.Terephthalic acid (TPA), phthalic acid, M-phthalic acid, 4,4 '-hexichol Base dicarboxylic acids, 4,4 '-diphenyl ether dicarboxylic acids, 4,4 '-benzophenone dicarboxylic acids, 4,4 '-diphenoxyethanedicarboxylic acid, 4, The aromatic dicarboxylic acids such as 4 '-diphenyl sulphone (DPS) dicarboxylic acids, 2,6 naphthalene dicarboxylic acid；1,2- cyclohexane dicarboxylic acids, 1,3- cyclohexane dicarboxylic acids, The ester ring types dicarboxylic acids such as 1,4- cyclohexane dicarboxylic acids；Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, nonyl two The aliphatic dicarboxylic acids such as acid, decanedioic acid.It should be noted that these dicarboxylic acid components can using dicarboxylic acids in itself in the form of as The raw material of above-mentioned polyestercarbonate, can also be by dicarboxylic esters or dicarboxylic dihydrazides such as methyl ester body, phenylester bodies according to autofrettage The dicarboxylic acid derivatives such as halogen are as raw material.

From optical characteristics aspect, as the above-mentioned other structures unit enumerated, it is preferable to use without aromatic series into The structural unit divided.If being cancelled in the main chain of polymer comprising aromatic component, the inverse wave length dispersiveness of fluorenes ring as described above, The content of oligomeric fluorene structural units must thus be increased, and photoelastic coefficient is also possible to be deteriorated.By using without fragrance The above-mentioned other structures unit of race's ingredient can prevent from being derived from the structural unit and aromatic component being made to introduce main chain.

On the other hand, in order to keep the balance with heat resistance, mechanical property etc. while optical characteristics is ensured, sometimes to It is also effective that the main chain or side chain of polymer, which introduce aromatic component,.In this case, for example by containing aromatic component Aromatic component can be imported polymer by above-mentioned other structures unit.

From the aspect of the balance for keeping various characteristics, the structural unit for including aromatic group in above-mentioned resin The content of (wherein, will be except the structural unit represented by above-mentioned general formula (1) and the structural unit represented by above-mentioned general formula (2)) is excellent It elects as below 5 mass %.

As the monomer with the above-mentioned other structures unit enumerated, particularly preferably using 1,4-CHDM, three Cyclodecane dimethanol, the spiroglycol, 1,4- cyclohexane dicarboxylic acids (and its derivative).Include the structural unit from these monomers The optical characteristics of resin or the balancing good of heat resistance, mechanical property etc..

In addition, in for the present invention in the case of most preferred polyestercarbonate, due to the polymerisation of diester compound Property than relatively low, thus from improve reaction efficiency from the aspect of, preferably without using except with the class of oligomeric fluorene structural units Close the diester compound beyond object.

According to the requirement performance of obtained resin, for importing the dihydroxy compounds of other structures unit or class Object is closed to may be used singly or in combination of two or more.The content of other structural units in resin is preferably 1 mass % More than below 60 mass %, further preferably below 55 mass % of more than 5 mass %, particularly preferably more than 10 mass % 50 Below quality %.The effect of heat resistance or imparting flexibility or toughness of the other structures unit due to especially undertaking adjustment resin, If thus content is very few, the mechanical property or melt processable of resin are deteriorated, if content is excessive, heat resistance or optical characteristics It is possible that it is deteriorated.

It is suitble to makrolon, polyester, polyestercarbonate that the resin with the present invention uses that can utilize conventionally used gather Conjunction method is manufactured.That is, above-mentioned resin can for example be manufactured using following methods：Use phosgene or carboxylic acid halide Solution polymerization process or interfacial polymerization；Or the melt phase polycondensation reacted without using solvent.In these manufacturing methods, melt Melt polymerization without using the high compound of solvent or toxicity, thus carrying capacity of environment can be reduced, and productivity is also excellent, thus It is preferred that it is manufactured by melt phase polycondensation.

In addition, pass through plasticization effect, resin caused by the residual solvents in resin using in the case of solvent in polymerization Glass transition temperature reduce, therefore, be difficult in aftermentioned stretching process by molecularly oriented control be certain.In addition, In the case that remaining has the organic solvent of the halogens such as dichloromethane system in resin, if being introduced into electronics using the formed body of the resin In equipment etc., it can also become the reason for corroding.Since the resin obtained by melt phase polycondensation is without solvent, thus for processing Process or the stabilisation of product property are also favourable.

When manufacturing above-mentioned resin by melt phase polycondensation, by the monomer with oligomeric fluorene structural units, other glycol Or the comonomer and polymerization catalyst of diester are mixed, and ester exchange reaction is carried out under melting, will be disengaged from ingredient except going to Outside system, while gradually step up reactivity.In the terminal stage of polymerization, make under conditions of high temperature, high vacuum reaction carry out to Target molecular weight.After the completion of reaction, from the resin of reactor discharge molten condition, obtain for the tree of the molded products such as phase difference film Fat raw material.

In the present invention, makrolon or polyestercarbonate can by by least contain oligomeric fluorene structural units monomer, More than one dihydroxy compounds and carbonic diester is used for raw material, makes their polycondensations and obtains.

As the carbonic diester for polycondensation reaction, the substance represented by above-mentioned general formula (11) can be usually enumerated.These Carbonic diester can be used alone, and can also be used in mixed way two or more.

[changing 33]

A¹And A²Preferably substituted or unsubstituted aromatic hydrocarbyl, more preferably unsubstituted aromatic hydrocarbyl.It needs It is bright, as the substituent group of aliphatic alkyl, ester group, ether, carboxylic acid, amide groups, halogen atom can be enumerated, as aromatic series The substituent group of alkyl can enumerate the alkyl such as methyl, ethyl.

As the carbonic diester represented by above-mentioned general formula (11), such as diphenyl carbonate (DPC), carbonic acid diformazan can be exemplified The substitution such as phenyl ester diphenyl carbonate, dimethyl carbonate, diethyl carbonate and dimethyl dicarbonate butyl ester etc., preferably diphenyl carbonate, Substitute diphenyl carbonate, particularly preferably diphenyl carbonate.It should be noted that carbonic diester is sometimes miscellaneous comprising chlorion etc. Matter inhibits polymerisation or the tone of obtained makrolon is made to be deteriorated sometimes, therefore it is preferable to use pass through as needed The substance that distillation etc. is refined.

For polycondensation reaction, by closely adjusting whole dihydroxy compounds used in reaction and diester compound Molar ratio can control the molecular weight of reaction speed or obtained resin.In the case of polycarbonate, preferably by carbonic acid Diester is adjusted to 0.90~1.10 compared with the molar ratio of whole dihydroxy compounds, is more preferably adjusted to 0.96~1.05, Particularly preferably it is adjusted to 0.98~1.03.In the case of polyesters, preferably by whole diester compounds compared with whole dihydroxy The molar ratio of compound is adjusted to 0.70~1.10, is more preferably adjusted to 0.80~1.05, particularly preferably it is adjusted to 0.85~ 1.00.In the case of polyestercarbonate, preferably by the total amount of carbonic diester and whole diester compounds compared with whole dihydroxies The molar ratio of based compound is adjusted to 0.90~1.10, is more preferably adjusted to 0.96~1.05, is particularly preferably adjusted to 0.98 ~1.03.

If above-mentioned molar ratio significantly deviates up and down, the resin of desired molecular weight can not be manufactured.It is if in addition, above-mentioned Molar ratio it is too small, then the C-terminal of manufactured resin increases, and the thermal stability of resin is deteriorated sometimes.If in addition, Above-mentioned molar ratio is excessive, then under identical conditions ester exchange reaction speed reduce or manufactured resin in carbonic acid The remaining quantity of diester or diester compound increases, and the remaining low molecular composition is in film or the when of stretching volatilizees, it is possible to cause The defects of film.

Melt phase polycondensation is usually implemented with multistep processes more than two steps.Polycondensation reaction can use 1 polymer reactor, Change condition successively and implemented with more than two steps process；The reactor of 2 or more can also be used, changes respective condition And implemented with processes more than two steps, it from production efficiency aspect, uses 2 or more, be preferably the reaction of 3 or more Device is implemented.Polycondensation reaction can be any one of the combination of batch-type, continous way or batch-type and continous way mode, From production efficiency and quality stability aspect, preferably continous way.

In polycondensation reaction, the balance for suitably controlling temperature in reaction system and pressure is critically important.If make temperature and Any one in pressure changes too quickly, then unreacted monomer is distillated outside reaction system.As a result, dihydroxy compounds It changes with the molar ratio of diester compound, the resin of desired molecular weight may be cannot get.

In addition, the polymerization speed of polycondensation reaction is controlled by C-terminal with ester group end or with the balance of carbonate group end System.Therefore, particularly in the case where being polymerize with continous way, if by unreacted monomer distillate make end group Balance changes, then it is certain to be difficult to polymerization speed control, and the variation of the molecular weight of obtained resin is it is possible that become larger. The molecular weight of resin is related with melt viscosity, therefore when carrying out melted masking to obtained resin, melt viscosity becomes It is dynamic, it is difficult to which that the qualities such as the film thickness of film are remained to the reduction of the quality that can centainly cause film, productivity.

In addition, if unreacted monomer distillates, the balance of end group is not only, the copolymerization composition of resin also offsets from desired Composition, it is possible to also the optical quality of phase difference film is had an impact.In the phase difference film of the present invention, aftermentioned phase difference Wavelength dispersibility is controlled by the oligomeric fluorenes in resin and the ratio of copolymer composition, if therefore ratio is destroyed in polymerization, nothing Method obtains the optical characteristics as design or in the case where obtaining long film, and optical characteristics can become due to the position of film Change, it is possible to the certain polarizer of quality can not be manufactured.

Specifically, as the reaction condition in the reaction of the 1st step, following condition may be employed.That is, polymer reactor Interior temperature maximum temperature usually 130 DEG C or more, preferably 150 DEG C or more, more preferably exist at 170 DEG C or more and usually Less than 250 DEG C, the scope preferably below 240 DEG C, more preferably below 230 DEG C set.In addition, the pressure of polymer reactor Power usually in below 70kPa (following, pressure representative absolute pressure), preferably in below 50kPa, more preferably in below 30kPa, simultaneously And usually in more than 1kPa, preferably in more than 3kPa, more preferably set in the scope of more than 5kPa.In addition, the reaction time Below below more than more than usually when 0.1 is small, preferably when 0.5 is small and usually when 10 is small, preferably when 5 is small, it is more excellent Be selected in 3 it is small when below scope set.On the reaction of the 1st step, while the list by generated diester compound source Hydroxy compounds distillation is removed to outside reaction system while implementing reaction.Such as diphenyl carbonate is being used as carbonic diester In the case of, it is phenol that the monohydroxy compound in addition to reaction system is gone to is distilled in the reaction of the 1st step.

In the reaction of the 1st step, more reducing reaction pressure then can more promote polymerisation, another aspect unreacted monomer Distillate and more increase.Inhibit distillating and promoting the reaction based on decompression for unreacted monomer in order to balance, using possessing returned cold The reactor of condenser is effective.In particular it is preferred that the initial reaction stage more than unreacted monomer uses reflux condenser.

The reaction later on the 2nd step, the pressure of the pressure of reaction system from the 1st step is slowly declined, then by institute While the monohydroxy compound of generation is rejected to outside reaction system, finally make the pressure of reaction system for below 5kPa, preferably For below 3kPa, more preferably below 1kPa.In addition, the maximum temperature of interior temperature usually 210 DEG C or more, preferably 220 DEG C with The upper and scope usually below 270 DEG C, preferably below 260 DEG C is set.In addition, the reaction time is usually small 0.1 When more than, preferably when 0.5 is small more than, more preferably when 1 is small more than and usually when 10 is small below, preferably when 5 is small with Under, more preferably when 3 is small below scope set.In order to inhibit coloring or heat deterioration, tone, good thermal stability are obtained Resin, the preferably maximum temperature of the interior temperature in the total overall reaction stage is less than 270 DEG C, is preferably less than 260 DEG C, is further excellent Elect less than 250 DEG C as.

Workable catalyst for ester exchange reaction (hereinafter sometimes called catalyst, polymerization catalyst) can during polymerization On reaction speed or carry out the tone of resin that polycondensation obtains or thermal stability brings very big influence.It is urged as used Agent does not limit as long as the transparency, tone, heat resistance, thermal stability and the mechanical strength that can meet manufactured resin It is fixed, can enumerate 1 race in long period type periodic table or 2 races (being hereinafter simply denoted as " 1 race ", " 2 race ") metallic compound, Alkaline boron compound, alkaline phosphating close the alkali compounds such as object, alkaline ammonium compound, amine compound.It is preferable to use selected from by The metallic compound of at least one of the group of metal and lithium composition of the 2nd race of long period type periodic table.

As 1 above-mentioned race's metallic compound, such as following compound may be employed, can also use beyond these 1 race's metallic compound.For example,：Sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium acid carbonate, carbonic acid Hydrogen potassium, lithium bicarbonate, caesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, acetic acid Caesium, odium stearate, potassium stearate, lithium stearate, stearic acid caesium, sodium borohydride, potassium borohydride, lithium borohydride, hydroboration caesium, four Phenylboric acid sodium, potassium tetraphenylboron, tetraphenylboronic acid lithium, tetraphenylboronic acid caesium, sodium benzoate, Potassium Benzoate, lithium benzoate, Benzoic acid caesium, disodium hydrogen phosphate, dipotassium hydrogen phosphate, two lithium of phosphoric acid hydrogen, two caesium of phosphoric acid hydrogen, disodium phenylphosphate, phosphenylic acid two Potassium, two lithium of phosphenylic acid, two caesium of phosphenylic acid；Sodium, potassium, lithium, the alkoxide of caesium, phenates；2 sodium salts of bisphenol-A, 2 sylvite, 2 lithium salts, 2 cesium salts etc..Wherein, from the tone aspect of polymerization activity and obtained makrolon, it is preferable to use lithium compounds.

As 2 above-mentioned race's metallic compounds, such as following compound may be employed, can also use beyond these 2 race's metallic compounds.For example,：Calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, carbonic acid Hydrogen barium, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, acetic acid Strontium, calcium stearate, barium stearate, magnesium stearate, strontium stearate etc..Wherein, it is preferable to use magnesium compound, calcium compound, barium Close object, from the tone aspect of polymerization activity and obtained makrolon, further preferably using magnesium compound and/or Calcium compound, most preferably with calcium compound.

It it should be noted that can also be complementary together with above-mentioned 1 race's metallic compound and/or 2 race's metallic compounds Ground shares alkaline boron compound, alkaline phosphating closes the alkali compounds such as object, alkaline ammonium compound, amine compound, particularly preferably Use the metallic compound selected from least one of the group being made of the metal and lithium of the 2nd race of long period type periodic table.

Object is closed as above-mentioned alkaline phosphating, such as following compound may be employed, can also be used beyond these Alkaline phosphating closes object.For example, triethyl phosphine, three n-propyl phosphines, tri isopropyl phosphine, tri-n-butyl phosphine, triphenylphosphine, Tributylphosphine or quaternary alkylphosphonium salt etc..

As above-mentioned alkaline ammonium compound, such as following compound may be employed, can also use beyond these Alkaline ammonium compound.For example, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, the tetrabutyl Ammonium hydroxide, N, N, N- front threes ethylethanolamine (choline), trimethylethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, front three Base phenyl ammonium hydroxide, triethyl methyl ammonium hydroxide, triethylbenzyl ammonium hydroxide, triethyl group phenyl ammonium hydroxide, three fourths Base benzyl ammonium hydroxide, tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyltriphenyl phosphonium ammonium hydroxide, methyl triphen Base ammonium hydroxide, butyl triphenyl ammonium hydroxide etc..

As above-mentioned amine compound, such as following compound may be employed, the amine beyond these can also be used Based compound.For example, 4-aminopyridine, 2-aminopyridine, N, N- dimethyl -4-aminopyridine, 4- diethylaminos Pyridine, 2 hydroxy pyrimidine, 2- methoxypyridines, 4-methoxypyridine, 2- dimethylaminos imidazoles, 2- methoxyl groups imidazoles, imidazoles, 2- mercaptoimidazoles, 2-methylimidazole, aminoquinoline, guanidine etc..

In general, compared with the whole dihydroxy compounds used in polymerization per 1mol, the dosage of above-mentioned polymerization catalyst is 0.1 μm of ol~300 μm ol, it is preferably 0.5 μm of ol~100 μm ol.As above-mentioned polymerization catalyst, using selected from by long period In the case of the metallic compound of at least one of the group of metal and lithium composition of the 2nd race of type periodic table, particularly using In the case of magnesium compound and/or calcium compound, as amount of metal, compared with above-mentioned whole dihydroxy compounds per 1mol, make With the above-mentioned polymerization catalyst of usually 0.1 μm of more than ol, preferably 0.3 μm of more than ol, particularly preferably 0.5 μm of more than ol. In addition, the dosage of above-mentioned polymerization catalyst is preferable for 30 μm of below ol, be preferably 20 μm of below ol, particularly preferably 10 μm of ol with Under.

In addition, by diester compound for monomer and in the case of manufacturing polyester or polyestercarbonate, can also with Above-mentioned alkali compounds share or without sharing in the case of using titanium compound, tin compound, germanium compound, antimony chemical combination The ester exchange catalysts such as object, zirconium compounds, lead compound, osmium compound, zinc compound, manganese compound.Compared with institute in reaction Whole dihydroxy compounds 1mol, the dosages of these ester exchange catalysts is with metal gauge usually 1 μm of ol~1mmol's In the range of use, be preferably 5 μm of ol~800 μm ol in the range of, particularly preferably 10 μm of ol~500 μm ol.

When catalytic amount is very few, polymerization speed is slow, thus the resin of desired molecular weight in order to obtain, it has to phase It should ground raising polymerization temperature.Therefore, the possibility that the tone of obtained resin is deteriorated increases, and unreacted raw material is poly- It closes and volatilizees in way, the molar ratio of dihydroxy compounds and diester compound is destroyed, it is possible to desired molecule be not achieved Amount.On the other hand, when the dosage of polymerization catalyst is excessive, it is possible to which concurrent undesirable side reaction causes obtained resin Tone be deteriorated or the coloring of resin during processing and forming.

If sodium, potassium, the caesium in 1 race's metal largely contain in resin, harmful effect may be brought to tone.And And these metals and from not only used catalyst, it is also possible to by being mixed into raw material or reaction unit.No matter source is such as What, the total amount of the compound of these metals in resin is excellent per 1mol compared with above-mentioned whole dihydroxy compounds with metal gauge Elect 2 μm of below ol, further preferably 1 μm of below ol, more preferably 0.5 μm of below ol as.

It should be noted that as the monomer with oligomeric fluorene structural units, using represented by above-mentioned general formula (13) In the case of diester compound manufacture polyestercarbonate, it is preferable to use A³And A⁴It is special for the above-mentioned diester compound of aromatic hydrocarbyl It is preferable to use A³And A⁴For the above-mentioned diester compound of phenyl.By using these diester compounds, polymerisation reactivity is good, The amount of catalyst, can improve the tone or thermal stability of obtained resin, and can reduce used in can reducing Foreign matter in resin.

The resin of the present invention can usually be cooled and solidified after polymerization as described above, and utilize rotary cutter etc. It is granulated.The method of granulation does not limit, and can enumerate following methods：With molten from the polymer reactor of terminal stage State is extracted out, and the method for curing and being granulated is allowed to cool in the form of strands；With molten from the polymer reactor of terminal stage Melt state to be supplied to resin in the extruder of single screw rod or twin-screw, after melting extrusion, be allowed to cool and cure and be granulated Method；Or extracted out from the polymer reactor of terminal stage with molten condition, curing is allowed to cool in the form of strands, temporarily And resin is supplied in the extruder of single screw rod or twin-screw again after being granulated, curing is allowed to cool after melting extrusion simultaneously The method being granulated；Etc..

The molecular weight of so obtained resin can be represented using reduced viscosity.When the reduced viscosity of resin is too low, shaping The mechanical strength of product is it is possible that reduce.Therefore, reduced viscosity is usually more than 0.20dL/g, is preferably more than 0.30dL/g.Separately On the one hand, when the reduced viscosity of resin is excessive, mobility when being molded reduces, and inclines with what productivity or mouldability reduced To.Therefore, reduced viscosity is usually below 1.20dL/g, is preferably below 1.00dL/g, more preferably below 0.80dL/g.It needs It is noted that reduced viscosity measures as follows：Using dichloromethane as solvent, makrolon concentration precision is adjusted to 0.6g/dL is measured at 20.0 DEG C ± 0.1 DEG C of temperature using Ubbelohde viscometer.

Above-mentioned reduced viscosity is related with the melt viscosity of resin, thus, the stirring of polymer reactor can usually be moved Output pressure of the gear pump of power or transporting molten resin etc. is used as the index of running management.That is, in above-mentioned running device Indicated value reaches the stage of desired value, makes the pressure recovery of reactor to normal pressure or discharges resin from reactor, so as to stop Polymerisation.

The melt viscosity of resin on the present invention, in 240 DEG C of temperature, shear velocity 91.2sec^-1Determination condition under it is excellent Elect more than 700Pas below 5000Pas as.More preferably more than 800Pas below 4500Pas, it is more preferably More than 900Pas below 4000Pas, particularly preferably more than 1000Pas below 3500Pas.It should be noted that Melt viscosity is measured using capillary rheometer (manufacture of Toyo Seiki Co., Ltd.).

The glass transition temperature of the resin of the present invention is preferably less than more than 110 DEG C 160 DEG C, be more preferably 120 DEG C with Upper less than 155 DEG C.When glass transition temperature is too low, then the tendency with heat resistance variation can cause size to become after film shaping Change, the reliability of the quality of phase difference film under conditions of use is it is possible that can be deteriorated.On the other hand, glass transition temperature is excessively high When, film generates the unevenness of film thickness sometimes when being molded either film becomes fragile or draftability is deteriorated, and damages film sometimes The transparency.

The storage modulus of above-mentioned resin be preferably more than 1GPa below 2.7GPa, more preferably more than 1.1GPa 2.5GPa with Under, further preferably more than 1.2GPa below 2.3GPa, particularly preferably more than 1.3GPa below 2.2GPa.Storage modulus is During above range, the treatability and excellent strength of film.The assay method of storage modulus illustrates in the item of following embodiments.

In order to obtain have present invention provide that particular range storage modulus polycarbonate resin adipose membrane, can be under The mode of stating is realized：Using the polycarbonate resin with specific structure specified in the present invention, also, it is molten for suitably adjusting it Melt-viscosity, the ratio for suitably selecting its structural unit, adjusting its structural unit, added in polycarbonate resin plasticizer etc. into The film forming condition or stretching condition that row is appropriately combined or selection is appropriate.

Using in the case of diester compound in polycondensation reaction, by-product monohydroxy compound can be remained in resin, It volatilizees in the film of film or when stretching, forms peculiar smell, operating environment is made to be deteriorated or it is possible that pollute transfer roller etc., make film Appearance damage.In the case where using particularly useful carbonic diester i.e. diphenyl carbonate (DPC), the boiling point of by-product phenol Compare it is high, using decompression under reaction also can not fully remove, easily remain in resin.

Therefore, the monohydroxy compound in carbonic diester source contained in resin of the invention is preferably 1500 mass Below ppm.Further preferably below 1000 mass ppm, particularly preferably below 700 mass ppm.It is it should be noted that right For monohydroxy compound, to solve the above-mentioned problems, content is more few better, is difficult to make remaining in the case of melt phase polycondensation Monohydroxy compound in macromolecule is zero, needs excessive labour to be removed.In general, by making monohydroxy chemical combination The content of object is reduced to 1 mass ppm, can fully inhibit the above problem.

In order to reduce the monohydroxy compound using carbonic diester source in the resin for remaining in the present invention as the low of representative Molecular chaperones, be de-gassed processing to resin using extruder as described above or make the pressure of polymerization terminal stage for 3kPa with Under, be preferably below 2kPa, further preferably below 1kPa be effective.

Reduce polymerization terminal stage pressure in the case of, if excessively reduce reaction pressure, molecular weight drastically on It rises, is difficult to control reaction sometimes, therefore preferably make the end group concentration of resin excessive for C-terminal excess or ester group end, End group balance is destroyed to be manufactured.Wherein from thermal stability aspect, it is 50mol/ preferably to make C-terminal amount Ton is following, particularly preferably less than 40mol/ tons.C-terminal amount can utilize¹H-NMR etc. is quantified.C-terminal amount can It is adjusted with molar ratio by whole dihydroxy compounds and whole diester compounds.

As needed, molecular weight when being molded in order to prevent etc. reduces or tone is deteriorated, can be in the resin of the present invention Mixture heat stabilizer.As the heat stabilizer, commonly known hindered phenolic heat stabilizer and/or the thermostabilization of phosphorus system can be enumerated Agent.

As hindered phenolic compound, such as following compound may be employed.Can enumerate 2,6 di t butyl phenol, 2,4- DI-tert-butylphenol compounds, 2- tertiary butyl -4- metoxyphenols, 2- tertiary butyl -4,6- xylenols, 2,6- di-t-butyls - 4- methylphenols, 2,6- di-t-butyl -4- ethyl -phenols, 2,5 di tert butyl hydroquinone, n-octadecane base -3- (3 ', 5 ' - Di-t-butyl -4 '-hydroxy phenyl) propionic ester, 2- tertiary butyls -6- (3 '-tertiary butyl -5 '-methyl -2 '-hydroxybenzyl) -4- methyl Phenyl acrylate, 2,2 '-methylene-bis- (4- methyl-6-tert-butylphenols), 2,2 '-methylene-bis- (6- cyclohexyl -4- first Base phenol), 2,2 '-ethylidene-bis- (2,4- DI-tert-butylphenol compounds), four [methylene -3- (3 ', 5 '-di-t-butyls -4 '-hydroxyl Phenyl) propionic ester] methane, 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene etc..Wherein, preferably For four [methylene -3- (3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) propionic ester] methane, n-octadecane base -3- (3 ', 5 '-two Tertiary butyl -4 '-hydroxy phenyl) propionic ester, 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene.

As phosphorus series compound, for example, may be employed phosphorous acid as shown below, phosphoric acid, phosphonous acid, phosphonic acids and they Ester etc. can also use the phosphorus series compound beyond these compounds.For example, triphenyl phosphite, phosphorous acid three (nonyl phenyl) ester, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, tridecyl phosphite, three monooctyl ester of phosphorous acid, phosphorous acid three (octadecyl) ester, phosphorous acid didecyl list phenylester, phosphorous acid dioctyl list phenylester, phosphorous acid diisopropyl monophenyl, Phosphorous acid monobutyl diphenyl ester, phosphorous acid list decyl diphenyl ester, phosphorous acid list octyl group diphenyl ester, double (2,6- di-t-butyl -4- first Base phenyl) pentaerythritol diphosphites, 2,2- di-2-ethylhexylphosphine oxides (4,6- di-tert-butyl-phenyls) octyl group phosphite ester, double (nonyls Phenyl) pentaerythritol diphosphites, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, distearyl Ji Wusi Alcohol diphosphites, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl phosphate list neighbour's biphenyl Ester, dibutylphosphoric acid ester, dioctylphosphoric acid ester, diisopropyl phosphate, (the 2,4- di-tert-butyls of 4,4 '-biphenylene diphosphinic acid four Base) ester, phosphniline dimethyl phthalate, phosphniline diethyl phthalate, phenyl-phosphonic acid dipropyl etc..These heat stabilizers can be used alone, Two or more can be shared.

The heat stabilizer can be added in melt polymerization in reaction solution, can also be added to using extruder in resin And it is kneaded.When film is filmed by extrusion by melting, can add in an extruder above-mentioned heat stabilizer etc. into Row film, can also add above-mentioned heat stabilizer etc. using extruder in advance in resin, the shapes such as particle are made and are used.

On the combined amount of these heat stabilizers, in the case where resin used in the present invention is set to 100 mass parts, More than preferably 0.0001 mass parts, more than more preferably 0.0005 mass parts, more than further preferably 0.001 mass parts, In addition it is preferably 1 below mass part, more preferably 0.5 below mass part, further preferably 0.2 below mass part.

It, as needed, can be with commonly known anti-oxidant of mixture for oxidation resistant purpose in the resin of the present invention Agent.As the antioxidant, such as compound shown below may be employed, the compound beyond these can also be used.Example It is stearic that pentaerythrite four (3-thiopropionate), pentaerythrite four (3- lauryl thiopropionates), glycerine -3- can such as be enumerated Base thiopropionate, triethylene glycol-bis- [3- (3- tertiary butyl -5- methyl -4- hydroxy phenyls) propionic esters], 1,6-HD-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], [3- (3,5- di-tert-butyl-hydroxy phenyls) third of pentaerythrite-four Acid esters], octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester, three (3,5- bis- of 1,3,5- trimethyls -2,4,6- Tertiary butyl-4-hydroxy benzyl) benzene, N, N- hexamethylene bis (3,5- di-t-butyl -4- hydroxy-hydrocineamides), 3,5- bis- Tertiary butyl-4-hydroxy-benzylphosphonic acid ester-diethyl ester, three (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid esters, 4,4 '- Double { 1,1- dimethyl -2- [the β-(3- tertiary butyl -4- hydroxyls of biphenylene diphosphinic acid four (2,4- di-tert-butyl-phenyls) ester, 3,9- Base -5- aminomethyl phenyls) propiono oxygroup] ethyl } -2,4,8,10- four oxa- loop coil (5,5) hendecane etc..Above-mentioned is anti-oxidant Agent can be used alone, and can also share two or more.In the case where setting resin of the invention as 100 mass parts, these The combined amount of antioxidant is preferably more than 0.0001 mass parts, and more than preferably 0.5 mass parts.

Further, in the resin of the present invention, can also without detriment in the range of the object of the invention containing usually making It is ultra-violet absorber, antitack agent, antistatic agent, lubrication prescription, lubricant, plasticizer, bulking agent, nucleating agent, fire retardant, inorganic Filler, modified impact agent, foaming agent, dyes/pigments etc..

In addition, for the purpose that the characteristics such as the mechanical property to resin or solvent resistance are modified, resin of the invention It can also be with aromatic copolycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic (third Olefin(e) acid), amorphous polyolefin, ABS, AS, polylactic acid, a kind or 2 in the synthetic resin or rubber etc. such as poly butylene succinate Kind or more be kneaded and polymer alloy be made.

Mentioned component can be utilized rotary drum mixer, V simultaneously or in any order by above-mentioned additive or modifying agent The mixers such as type mixer, nauta mixer (NAUTA MIXER), Banbury, open mill, extruder are blended in this hair In bright resin, manufactured, wherein, from the aspect for improving dispersiveness, preferably by extruder, particularly preferably using double Screw extruder is kneaded.

The birefringence of the resin obtained as described above is small, and heat resistance and mouldability are also excellent, and then colours less, has both high saturating Bright property, thus can be used for optical film, CD, optical prism, take object lens etc., be especially suitable for phase difference film.

As the method for using the resin of the present invention that unstretching film is filmed, may be employed：Dissolve above-mentioned resin Remove in a solvent and after being poured into a mould the tape casting of solvent, make above-mentioned resin melting without using solvent and be filmed it is molten Melt film method.As melted masking method, specifically have using the extrusion by melting of T moulds, rolling-molding method, pressure sintering, coetrusion, Fusion method, multilayer extrusion, film blowing etc. altogether.The film-forming method of unstretching film is not particularly limited, since the tape casting can Caused by leading to the problem of residual solvents, thus preferred molten film method, wherein the easiness from progress stretch processing afterwards From the aspect of, it is preferable to use the extrusion by meltings of T moulds.

Using melted masking method carry out unstretching film it is molding in the case of, forming temperature is preferably less than 270 DEG C, more excellent Elect less than 265 DEG C, particularly preferably less than 260 DEG C as.When forming temperature is excessively high, in obtained film by foreign matter or bubble The defects of caused by generation, may increase or film may colour.But when forming temperature is too low, the melt viscosity of resin It is excessively high, it is difficult to carry out the shaping of base film, it may be difficult to unstretching film in uniform thickness is manufactured, thus the lower limit of forming temperature is usual For 200 DEG C or more, preferably 210 DEG C or more, more preferably 220 DEG C or more.Herein, the forming temperature of unstretching film refers to melt Temperature during shaping in film method, the value being usually measured to the mould outlet temperature of resin melt extrusion.

If in addition, there are foreign matter in film, in the case where being used as polarizer, as light transmission (Guang order け) the shortcomings of quilt It recognizes.In order to remove the foreign matter in resin, preferably following methods：Polymer filter is installed after above-mentioned extruder, right After resin is filtered, is squeezed out from mold and carry out film shaping.At this time, it may be necessary to use piping connecting extruder or polymer filtration Device, mold, so as to transporting molten resin, but in order to strongly inhibit the heat deterioration in piping, according to residence time shortest side It is critically important that formula, which configures each equipment,.In addition, the transmission of film after extrusion and coiling process carry out in toilet, it is desirable that as far as possible Pay attention to non-cohesive on film thering is foreign matter.

The thickness of unstretching film according to the stretching conditions such as the design of the film thickness of the phase difference film after stretching or stretching ratio come It determines, if but it is blocked up, uneven thickness (deviation) is easily generated, if excessively thin, fracture during stretching, thus thickness may be caused Usually 30 μm or more, be preferably more than 40 μm, further preferably 50 μm or more, and usually less than 200 μm, preferably Less than 160 μm, further preferably less than 120 μm.In addition, when unstretching film has uneven thickness (deviation), may cause The phase difference of phase difference film is uneven, thus the thickness of the part used as phase difference film be preferably below setting thickness ± 3 μm, It more preferably sets below thickness ± 2 μm, be particularly preferably below setting thickness ± 1 μm.

The length of the length direction of unstretching film is preferably more than 500m, is more preferably more than 1000m, particularly preferably For more than 1500m.From productivity and quality aspect, in the phase difference film of the manufacture present invention, preferably continuously carry out Stretch, but usually stretch start when in order to, it is necessary to regularization condition, when the length of film is too short, be adjusted with the calibration of defined phase difference The amount of obtainable product is reduced after shelf-regulating Conditions.It should be noted that " length " refers in this specification, the width phase with film Than the size of length direction is sufficiently large, substantially refers to can be the shape of the degree with web-like when length direction is wound.More Specifically, the shape of big 10 times of the size of the size ratio width of the length direction of film or more is referred to.

The internal haze of the unstretching film obtained as described above is preferably less than 3%, is more preferably less than 2%, is especially excellent Elect less than 1% as.If the internal haze of unstretching film is more than above-mentioned upper limit value, the scattering of light can be occurred, for example, with polarization During element lamination, become the reason for generating depolarization sometimes.There is no special provision to the lower limiting value of internal haze, be usually More than 0.1%.In the measure of internal haze, the hyaline membrane with sticker for having carried out mist degree measure in advance is pasted and is not drawn The two sides of film is stretched, using the sample of the state for the influence for eliminating external mist degree, the haze value of the hyaline membrane with sticker is subtracted Value of the value as internal haze obtained from going the measured value of above-mentioned sample.

The b* values of unstretching film are preferably less than 3.When the b* values of film are excessive, the problems such as coloring can be generated.B* values are more preferable For less than 2, particularly preferably less than 1.

On unstretching film, no matter thickness, the total light transmittance of the film in itself is preferably more than 80%, further Preferably more than 90%, it is more preferably more than 91%, particularly preferably more than 92%.Transmitance is more than above-mentioned lower limit When, it can obtain colouring few film, when being bonded with polarizer, form degree of polarization and the high circular polarizing disk of transmitance, for scheming During as display device, high display grade can be realized.It should be noted that the upper limit of the total light transmittance of the film of the present invention It is not particularly limited, but usually less than 99%.

By reducing above-mentioned mist degree or b* values, and then the refractive index of resin is reduced, the reflection of film surface can also be inhibited, Improve total light transmittance.In the case of by the resin of the present invention for preventing the circular polarizing disk of external light reflection, improve Total light transmittance is related with the reflectivity for reducing exterior light.The refraction in sodium d lines (589nm) of resin used in the present invention Rate is preferably 1.49~1.56.In addition, above-mentioned refractive index is more preferably 1.50~1.55, further preferably 1.51~1.54, Particularly preferably 1.51~1.53.The resin used in the present invention contains oligomeric fluorene structural units, thus with entire aliphatic poly It closes object to raise compared to refractive index, but aromatic compound is not used in copolymer composition, it is above-mentioned so as to which refractive index is restricted to Scope.

The photoelastic coefficient of the resin of the present invention is preferably 25 × 10^-12Pa^-1Below, it is more preferably 20 × 10^-12Pa^-1Below, 15 × 10 are particularly preferably^-12Pa^-1Below.When photoelastic coefficient is excessive, when phase difference film is pasted polarizer, It may occur to whiten around picture, the reduction of fuzzy such image quality.Especially for the feelings of large-scale display device Under condition, which significantly occurs.

Preferably in aftermentioned crooked test brittle break does not occur for above-mentioned unstretching film.The film of brittle break occurs in film Film when or the when of stretching the fracture of film easily occurs, the yield rate of manufacture may be made to be deteriorated.It brittleness does not occur breaks to be made The molecular weight of resin used in the present invention or melt viscosity, glass transition temperature are designed to above-mentioned preferred by bad film Scope is critically important.In addition, the ingredient of flexibility can be assigned to adjust the method for the physical property of film be also to have by being copolymerized, being blended Effect.

The saturated water absorption of the resin of the present invention is preferably greater than 1.0 mass %.If saturated water absorption is more than 1.0 mass %, Then by the film with other films when being bonded, the tendency of cementability can be readily insured that by having.For example, it is bonded with polarizer When, since film is hydrophilic, thus the contact angle of water is also low, easily freely designs cement, can obtain higher bonding Design.In the case where saturated water absorption is below 1.0 mass %, film is hydrophobic, and the contact angle of water is also high, it is difficult to carry out The design of cementability.And film is easily charged, and being involved in etc. for foreign matter can be generated by, which having, is being assembled into circular polarizing disk, image display dress Open defect becomes the tendency of the problem of more when putting middle.On the other hand, if saturated water absorption is more than 3.0 mass %, humidity environment Under the durability of optical characteristics have the tendency of variation, it is thus not preferred.The saturated water absorption of the resin of the present invention is preferably greater than 1.0 mass %, more preferably more than 1.1 mass %, and preferably below 3.0 mass %, more preferably 2.5 mass % with Under.On the other hand, according to film or using film image display device use condition difference, saturated water absorption or Below 1.0 mass %.

By the way that above-mentioned unstretching film is carried out stretching orientation, phase difference film can be obtained.As drawing process, can use Longitudinal simple tension, biaxial tension using the horizontal simple tension of stenter etc. or while be combined to them, gradually Method well known to biaxial tension etc..Stretching can be carried out with batch-type, but be preferably carried out continuously from productivity aspect.Into And compared with batch-type, when continous way, can obtain the few phase difference film of deviation of the phase difference in film surface.

Compared with the glass transition temperature (Tg) of the resin as raw material, draft temperature is (Tg-20 DEG C)~(Tg+30 DEG C) scope, be preferably (Tg-10 DEG C)~(Tg+20 DEG C), further preferably in the range of (Tg-5 DEG C)~(Tg+15 DEG C). Stretching ratio determined by target phase difference, and longitudinal and transverse is respectively 1.2 times~4 times, more preferably 1.5 times~3.5 times, into one Step is preferably 2 times~3 times.When stretching ratio is too small, the effective range for obtaining the desired degree of orientation and the angle of orientation narrows.It is another Aspect, when stretching ratio is excessive, film may be broken or generate fold in stretching.

Tensile speed takes the circumstances into consideration to select also according to purpose, can be according to logical in terms of the strain rate represented by following mathematical expressions Often for 50%~2000%, be preferably 100%~1500%, more preferably 200%~1000%, particularly preferably 250%~ 500% mode selects.When tensile speed is excessive, the fracture or long-term under the high temperature conditions during stretching may be caused It may be increased using the variation of caused optical characteristics.In addition, if tensile speed is too small, not only productivity can reduce, but also Desired phase difference in order to obtain must make stretching ratio excessive sometimes.

Strain rate (%/minute)={ length (mm) of tensile speed (mm/ minutes)/base film } × 100

After stretched film, heat fixation processing can be carried out using heating furnace as needed, the width of stenter can also be controlled Degree adjusts roller peripheral speed to carry out mitigation process.As the temperature of heat fixation processing, compared with used in unstretching film The glass transition temperature (Tg) of resin, 60 DEG C~(Tg), preferably carried out in the 70 DEG C~scope of (Tg-5 DEG C).Heat treatment temperature It is disorderly by stretching obtained molecularly oriented, it is possible to be greatly reduced from desired phase difference when spending high.In addition, it is setting It puts in the case of mitigating process, the width of the film extended with respect to stretching is retracted to 95%~100%, so as to The stress generated in removal stretched film.It is identical with heat fixation treatment temperature to the treatment temperature of film application at this time.By carrying out such as The heat fixation processing mitigates process, can inhibit the change of the optical characteristics caused by long-time service under the high temperature conditions It is dynamic.

It can be by taking the circumstances into consideration to the treatment conditions in such stretching process using the phase difference film of the resin of the present invention It selects and adjusts to make.

Using the present invention resin phase difference film in the face of wavelength 550nm birefringence (Δ n) be preferably 0.002 with Above, more preferably more than 0.0025, particularly preferably more than 0.003.Phase difference and film thickness (d) and birefringence (Δ n) into Ratio, therefore, by making birefringence that can show the phase difference as design using film in above-mentioned specific scope, The film for being suitable for thin devices can easily be made.In order to show high birefringence, it is necessary to reduce draft temperature, improve stretching Multiplying power etc. is easily broken off to improve the degree of orientation of polymer molecule in this stretching condition lower film, therefore used resin Toughness it is more excellent then more favourable.

Additionally depend on the design load of phase difference, but using the phase difference film of the resin of the present invention thickness be preferably 60 μm with Under.In addition, the thickness of phase difference film be more preferably less than 50 μm, further preferably less than 45 μm, be particularly preferably 40 μm with Under.On the other hand, when thickness is excessively thin, the processing of film is difficult, can generate fold during manufacturing or be broken, therefore, as this The lower limit of the thickness of the phase difference film of invention is preferably 10 μm or more, more preferably 15 μm or more.

To use the present invention resin phase difference film for, wavelength 450nm measure phase difference (R450) compared with It is less than more than 0.75 0.93 in the ratio between phase difference (R550) that wavelength 550nm the is measured i.e. value of wavelength dispersion (R450/R550). More preferably less than more than 0.78 0.91, it is particularly preferably less than more than 0.80 0.89.If the value of above-mentioned wavelength dispersion is in the model It encloses, preferable phase difference characteristics can be obtained in the wide wave-length coverage of visibility region.Such as 1/4 wavelength plate, making has The phase difference film of such wavelength dependency is simultaneously bonded with polarizer, so as to make circular polarizing disk etc., can realize tone The few polarizer of wavelength dependency and display device.On the other hand, when aforementioned proportion is outside the scope, the wavelength of tone relies on Property become larger, optical compensation can not be carried out under all wavelengths of visibility region, light can be generated through polarizer or display device institute The problems such as coloring of cause or contrast reduce.

Above-mentioned phase difference film is bonded by carrying out lamination with well known light polarizing film, and cuts into desired size, so as to Form circular polarizing disk.The circular polarizing disk such as can be used for various display screens (liquid crystal display device, organic EL display, Gas ions display device, FED field emission display devices, SED surface fields display device) visual angle compensation use, prevent outside Light reflection is used, tone compensation is used, conversion of the circularly polarized light to linearly polarized photon is used etc..Particularly, if for organic el display panel The circular polarizing disk for preventing external light reflection, then can carry out clean black display, the reliability of quality is also excellent.And then Performance with the equipment slimming that can also correspond to from now on.

As above-mentioned light polarizing film, the either direction that may be employed in width or length direction has the inclined of absorption axiss Light film.Specifically, can enumerate makes polyvinyl alcohol mesentery, part formalizing polyvinyl alcohol mesentery, ethane-acetic acid ethyenyl ester The hydrophilic macromolecules films such as the partly-hydrolysed film of copolymer system adsorb the dichroic substances such as iodine or dichroic dye and have carried out unidirectional The film of stretching；Polyenoid system alignment films such as the dehydration object of polyvinyl alcohol or the desalination acid treatment object of polyvinyl chloride etc..These it In, make the dichroic substances such as polyvinyl alcohol mesentery absorption iodine and carry out the long light polarizing film of simple tension due to polarizing photodichroism Than high and particularly preferred.The thickness of these long light polarizing films is not particularly limited, is usually 1 μm~80 μm or so.

Make polyvinyl alcohol mesentery absorption iodine and carried out the light polarizing film of simple tension can for example to make as follows：By polyethylene Alcohol is impregnated into the aqueous solution of iodine and is dyed, and 3~7 times of former length is stretched to, so as to make the light polarizing film.It is above-mentioned water-soluble Liquid can include boric acid, zinc sulfate, zinc chloride etc. as needed.Alternatively, it is also possible to which polyvinyl alcohol is impregnated into potassium iodide etc. In aqueous solution.

In addition, polyvinyl alcohol mesentery can be impregnated into water before dyeing as needed, washed.By to poly- second Enol mesentery is washed, and can clean the dirt or anti-blocking agent of polyethenol series film surface.Further, since polyethenol series Film is swollen, thus also have prevent from dyeing unequal non-uniform effect.Stretching can carry out after with iodine staining, also may be used With an Edge Coloring while stretching, in addition can also be dyed after the stretch with iodine.It can also be in the water of boric acid or potassium iodide etc. It is stretched in solution or in water-bath.

In above-mentioned circular polarizing disk, the slow axis of above-mentioned phase difference film and the width angulation of above-mentioned light polarizing film are preferred For less than 38 ° or more 52 °, more preferably less than 40 ° or more 50 °, particularly preferably less than 42 ° or more 48 °.Outside above range When, aftermentioned external light reflection rate increases or reflection optical colour, thus the display quality of image is likely to decrease.

Above-mentioned phase difference film and above-mentioned light polarizing film can carry out lamination by bonding/adhesive.As bonding/adhesive, As long as the optical characteristics for not damaging above-mentioned laminated film uses well known bonding/adhesive.

As described above, above-mentioned circular polarizing disk is formed in the following manner：Possess sufficient optical characteristics, and can be suitble to For requiring accuracy, slim, homogenieity equipment.Therefore, above-mentioned circular polarizing disk can be suitable for for example in liquid crystal display Liquid crystal panel used, organic EL panel used in organic el display panel etc. in screen.Particularly organic EL panel possesses appearance The easily metal layer of reflection exterior light, therefore easily generate the problems such as external light reflection or background mirror.It is such outer in order to prevent Portion's light reflection etc., it is effective that above-mentioned circular polarizing disk is arranged at light-emitting surface.

《Invention 2》

In the following, to the three fluorenes diester of the present invention 2, the oligomeric fluorenes diester compositions comprising the three fluorenes diester and contain tool The resin combination for having the polymer of the repetitive unit in three new fluorenes diester sources, the stretching obtained using the resin combination Film, circular polarizing disk and image display device are described in detail.

It should be noted that (general formula) formula (1) recorded below, (1a)~(1e), (2)~(11), (21) are for illustrating Each structure in the present invention 2.

<1 three fluorenes diester>

The three fluorenes diester of the present invention include 3 fluorenes unit a with or without substituent group.

In three fluorenes diester, the carbon atom of 9 is bonded or directly with one another by with or without taking in fluorenes unit a The alkylidene of Dai Ji, the arlydene with or without substituent group or the sub- aralkyl with or without substituent group are with chain Shape is bonded.

In this way, the three fluorenes diester of the present invention make structure upright and outspoken by the laminated structure of fluorenes ring, it is thus regarded that with than two The good heat resistance of fluorene compound.

<1.1 alkylidenes, arlydene, sub- aralkyl>

In the three fluorenes diester of the present invention, the fluorenes unit a alkylidenes being bonded are not particularly limited, from the aftermentioned fluorenes ratio of raising The aspect of example is set out, carbon number is usually more than 1 and usually less than 10, be preferably less than 5, more preferably 3 with Under.

The concrete structure of above-mentioned alkylidene is enumerated below, but not limited to this, methylene, ethylidene, positive Asia third can be enumerated The alkylidene of the straight-chains such as base, positive butylidene, positive pentylidene, positive hexylidene；Methylmethylene, dimethylated methylene base, ethyl are sub- Methyl, propylmethylene, butyl methylene, (1- Methylethyls) methylene, 1- methyl ethylidene, 2- methyl ethylidene, 1- second Base ethylidene, 2- ethylethylene residues, 1- methyl propylenes, 2- methyl propylenes, 1,1- dimethylethylenes, 2,2- dimethyl are sub- Propyl, 3- methyl propylenes etc. include the alkylidene of branch (numerical value of the position of substitution is counted from the carbon of fluorenes ring side)；Following There is the ester ring type alkylene of the associative key of the alkylidene of straight-chain or branched at arbitrary the 2 of the alicyclic structure shown in [A] group Base

[changing 34]

[A]

(in each ring structure shown in above-mentioned [A] group, the position of substitution of 2 associative keys is arbitrary, and 2 associative keys can To be substituted on same carbon.)；There is straight-chain or branched at arbitrary the 2 of the heterocycle structure shown in following [B] groups The hetero ring type alkylidene of the associative key of alkylidene

[changing 35]

[B]

(in each ring structure shown in above-mentioned [B] group, the position of substitution of 2 associative keys is arbitrary, and 2 associative keys can To be substituted on same carbon.).

In the alicyclic structure shown in above-mentioned [A] group or the heterocycle structure shown in above-mentioned [B] group, have at arbitrary 2 Straight-chain or the concrete structure of associative key of alkylidene of branched can enumerate such as lower structure, but be not limited to these：It is sub- The alkylidene of the straight-chains such as methyl, ethylidene, n-propylene, positive butylidene, positive pentylidene, positive hexylidene；1- methyl ethylidene, 2- methyl ethylidene, 1- ethylethylene residues, 2- ethylethylene residues, 1- methyl propylenes, 2- methyl propylenes, 1,1- dimethyl are sub- Ethyl, 2,2- dimethylpropylidenes, 3- methyl propylenes etc. include branch alkylidene (herein the numerical value of the position of substitution from it is upper The carbon for stating ring structure bonding plays counting).

As the substituent group that the alkylidene can have, can enumerate halogen atom (such as fluorine atom, chlorine atom, bromine atoms, Iodine atom)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Carbon number is 1~10 acyl group (example Such as acetyl group, benzoyl)；Carbon number is 1~10 amide groups (such as acetamido, benzamido etc.)；Nitro； Cyano；With or without selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), carbon number be 1~10 Alkyl (such as methyl, ethyl, isopropyl etc.), carbon number be 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.), Acyl group (such as acetyl group, benzoyl etc.) that carbon number is 1~10, the amide groups that carbon number is 1~10 (such as acetyl Amido, benzamido etc.), nitro, the carbon number of 1~3 substituent group in cyano etc. be 6~10 aryl (such as benzene Base, naphthalene etc.) etc..The quantity of the substituent group is not particularly limited, preferably 1~3.In the case that substituent group is 2 or more, take The species of Dai Ji can be the same or different.It is preferably nothing in addition, from the aspect that can industrially manufacture at low cost Substitution.

As the concrete example of the alkylidene with or without substituent group, it is sub- that cyclobutyl methylene, cyclopenta can be enumerated The alkyl substituted alkylenes such as methyl, cyclohexylmethylene, 1- cyclohexylpropylenes；Phenylmethylene, 1- phenyl-ethylenes, 1- benzene The aryl substituted alkylene such as base propylidene；The halogen such as 1,1,2,2- tetrafluoros ethylidene, trichloromethyl methylene, trifluoromethyl methylene Atom substituted alkylene；(numerical value of the position of substitution is certainly for alkoxies substituted alkylenes such as 2- methoxy -2- methyl propylenes etc. The carbon of fluorenes ring side, which rises, to be counted).

In addition, in the three fluorenes diester of the present invention, the arlydene of bonding fluorenes unit a is not particularly limited, aftermentioned from improving Set out in terms of fluorenes ratio, carbon number is usually more than 4, and usually less than 10, be preferably less than 8, more preferably 6 Below.

The concrete structure of above-mentioned arlydene is enumerated below, and but it is not limited to this, can enumerate 1,2- phenylenes, 1,3- Asias benzene The phenylenes such as base, 1,4- phenylenes；The naphthylenes such as 1,5- naphthylenes, 2,6- naphthylenes；2,5- sub-pyridyl groups, 2,4- Asias thiophene The heteroarylidenes such as base, 2,4- furylidenes.

As the substituent group that the arlydene can have, can enumerate halogen atom (such as fluorine atom, chlorine atom, bromine atoms, Iodine atom)；Carbon number is 1~10 alkyl (such as methyl, ethyl, isopropyl etc.)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Carbon number is 1~10 acyl group (such as acetyl group, benzoyl etc.)；Carbon number is 1~10 amide groups (such as acetamido, benzamido etc.)；Nitro；Cyano etc..The quantity of the substituent group does not limit especially It is fixed, preferably 1~3.In the case that substituent group is 2 or more, the species of substituent group can be the same or different.In addition, from The aspect that can industrially manufacture at low cost is set out, preferably unsubstituted.

As the concrete example of the arlydene with or without substituent group, 2- methyl-1s, 4- phenylenes, 3- first can be enumerated Base -1,4- phenylenes, 3,5- dimethyl -1,4- phenylenes, 3- methoxyl group -1,4- phenylenes, 3- Trifluoromethyl-1s, 4- Asias benzene Base, 2,5- dimethoxy -1,4- phenylenes, tetra- fluoro- 1,4- phenylenes of 2,3,5,6-, tetra- chloro- 1,4- phenylenes of 2,3,5,6-, 3- Nitro -1,4- phenylenes, 3- cyano -1,4- phenylenes etc..

In addition, in the three fluorenes diester of the present invention, the sub- aralkyl of bonding fluorenes unit a is not particularly limited, aftermentioned from improving Fluorenes ratio in terms of set out, carbon number is usually more than 6, and usually less than 10, be preferably less than 9, more preferably For less than 8.

The concrete structure of above-mentioned sub- aralkyl is enumerated below, and but it is not limited to this, can enumerate the Asia shown in following [C] group Aralkyl.

[changing 36]

[C]

As the substituent group that the Asia aralkyl can have, can enumerating halogen atom, (such as fluorine atom, chlorine atom, bromine are former Son, iodine atom)；Carbon number is 1~10 alkyl (such as methyl, ethyl, isopropyl etc.)；Carbon number is 1~10 alkane Oxygroup (such as methoxyl group, ethyoxyl etc.)；Carbon number is 1~10 acyl group (such as acetyl group, benzoyl etc.)；Carbon atom Number is 1~10 amide groups (such as acetamido, benzamido etc.)；Nitro；Cyano；Have or do not have selected from halogen atom Alkyl (such as methyl, ethyl, the isopropyl that (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), carbon number are 1~10 Deng), the alkoxy (such as methoxyl group, ethyoxyl etc.) that carbon number is 1~10, acyl group that carbon number is 1~10 (such as second Acyl group, benzoyl etc.), carbon number be 1~10 amide groups (such as acetamido, benzamido etc.), nitro, cyano The carbon number of 1~3 substituted base in is 6~10 aryl (such as phenyl, naphthalene etc.) etc..The quantity of the substituent group It is not particularly limited, preferably 1~3.In the case that substituent group is 2 or more, the species of substituent group can it is identical can not also Together.In addition, from the aspect that can industrially manufacture at low cost, it is preferably unsubstituted.

As the concrete example of the sub- aralkyl with or without substituent group, 2- methyl-1s, 4- Asias dimethylbenzene can be enumerated Base, 2,5- dimethyl -1,4- xylylenes, 2- methoxyl group -1,4- xylylenes, 2,5- dimethoxy -1,4- Asias diformazan Phenyl, tetra- fluoro- 1,4- xylylenes of 2,3,5,6-, alpha, alpha-dimethyl -1,4- xylylenes, α, α, α ', α '-tetramethyl - 1,4- xylylenes etc..

Among these, from improving fluorenes ratio, being upright and outspoken aspect, it is preferably alkylidene, is more preferably methylene, Asia Ethyl, phenylene or Isosorbide-5-Nitrae-xylylene, further preferably methylene.Particularly in the case of for methylene, selection Property have there are one reactive functional groups oligomeric fluorenes synthesis it is easy, thus particularly preferably.

In the three fluorenes diester of the present invention, as the substituent group that above-mentioned fluorenes unit a can have, halogen atom can be enumerated (such as fluorine atom, chlorine atom, bromine atoms, iodine atom)；Alkyl (such as methyl, ethyl, the isopropyl that carbon number is 1~10 Deng)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Acyl group (such as the second that carbon number is 1~10 Acyl group, benzoyl etc.)；Carbon number is 1~10 amide groups (such as acetamido, benzamido etc.)；Nitro；Cyanogen Base；With or without being 1~10 selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), carbon number Alkyl (such as methyl, ethyl, isopropyl etc.), the alkoxy (such as methoxyl group, ethyoxyl etc.) that carbon number is 1~10, carbon Acyl group (such as acetyl group, benzoyl etc.) that atomicity is 1~10, the amide groups that carbon number is 1~10 (such as acetamide Base, benzamido etc.), nitro, the carbon number of 1~3 substituent group in cyano etc. be 6~10 aryl (such as phenyl, Naphthalene etc.) etc..The quantity of the substituent group is not particularly limited, preferably 1~3.In the case that substituent group is 2 or more, substitution The species of base can be the same or different.It is preferably that nothing takes in addition, from the aspect that can industrially manufacture at low cost Generation.

<1.3 ester group>

The present invention three fluorenes diester can be：In 3 fluorenes unit a, the carbon of 9 positioned at the fluorenes unit a of two ends is former Substituents alpha is bonded on son respectively¹And α², in the substituents alpha¹And α²On be bonded with ester group.In this case, α¹And α²It can phase It together can not also be same.In addition, substituents alpha¹And α²In include Direct Bonding, i.e. can be direct on the carbon atom of 9 of fluorenes unit a It is bonded with ester group.

As ester group possessed by the three fluorenes diester of the present invention, it is not particularly limited, from can industrially obtain at low cost The aspect obtained is set out, and preferably end group is the ester group for the organic substituent that carbon number is 1~10.

The concrete example for the organic substituent that carbon number is 1~10 is enumerated below, but is not limited to these, can enumerate first The alkyl of the straight-chains such as base, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, positive decyl；Isopropyl, 2- methyl-propyls, 2, 2- dimethyl propyls, 2- ethylhexyls etc. include the alkyl of branch；The isothrausmatic alkane of cyclopropyl, cyclopenta, cyclohexyl, cyclooctyl Base；The aryl such as phenyl, 1- naphthalenes, 2- naphthalenes；The heteroaryls such as 2- pyridyl groups, 2- thienyls, 2- furyls；Benzyl, 2- phenyl second Base, to aralkyl such as methoxy-benzyl etc..

It is preferably the alkane that carbon number is 1~6 from the aspect that can industrially obtain at low cost among these Base.In this case, easily hydrolyzed from synthesis, easily generate carboxylic acid aspect, carbon number be preferably 2 with On；In addition, from by removing the low-boiling alcohol generated in the transesterification with dihydroxy compounds, so as to efficiently closing It is preferably less than 4, more preferably less than 2 into from the aspect of polyester and polyestercarbonate.Particularly preferred substituent group is second Base.

On the other hand, carbon number be 6~8 aryl in the case of, ester exchange reaction easily carries out, thus pass through by The present invention diester compound and dihydroxy compounds, carbonic diester by add together input reactor in, so as to Polyestercarbonate of the one-step synthesis as preferred polymers, thus be preferred.In this case, from molecular weight is small, easy steaming The aspect that distillation is gone is set out, and carbon number is preferably less than 8, more preferably less than 6.Particularly, particularly preferably in polyester carbon The phenyl that can be removed after acid esters synthesis as phenol distillation.In addition, in the case of aryl, from the side of reactivity during polymerization Face is set out, and as carbonic diester it is preferable to use aftermentioned diaryl carbonate esters, is gone out in terms of it can easily remove by-product It sends out, the aryl in aryl and diaryl carbonate esters in more preferable ester group is identical.

<1.4 substituents alpha¹And α²>

As substituents alpha¹And α², it is not particularly limited, Direct Bonding, the carbon with or without substituent group can be enumerated Alkylidene that atomicity is 1~10, with or without substituent group carbon number be 4~10 arlydene or have or Carbon number without substituent group be 6~10 sub- aralkyl or selected from by the carbon atom with or without substituent group Arlydene that alkylidenes of the number for 1~10, the carbon number with or without substituent group are 4~10 and with or without taking The group of 2 or more in the group that the sub- aralkyl that the carbon number of Dai Ji is 6~10 forms by oxygen atom, have or do not have The group that the sulphur atom of substituted base, nitrogen-atoms or carbonyl with or without substituent group are formed by connecting.

As " alkylidene that the carbon number with or without substituent group is 1~10 ", it is preferable to use as key Close the group illustrated in the alkylidene of fluorenes unit a.In this case, from the aspect for showing inverse wave length dispersiveness, preferably Use the alkylidene that carbon number is more than 2.On the other hand, from the aspect for showing flat dispersiveness, its carbon is preferably made Atomicity is 1.In addition, in the case where showing inverse wave length dispersiveness, from the orientation of fluorenes ring is made to be easily fixed compared with main chain, It sets out in terms of inverse wave length dispersing characteristic can be efficiently obtained, carbon number is preferably less than 5, is more preferably less than 4, further Preferably less than 3, less than 2 are particularly preferably.On the other hand, to resin combination imparting flexibility aspect, carbon Atomicity is preferably more than 2, more preferably more than 3, further preferably more than 4.

As " arlydene that the carbon number with or without substituent group is 4~10 ", it is preferable to use as key Close the group illustrated in the arlydene of fluorenes unit a.Similarly, as " carbon number with or without substituent group is 6~10 Sub- aralkyl " it is preferable to use as bonding fluorenes unit a sub- aralkyl illustrated in group.

Enumerate below " be selected from by be 1~10 with or without the carbon number of substituent group alkylidene, have or do not have The Asia virtue that arlydene that the carbon number of substituted base is 4~10 and carbon number with or without substituent group are 6~10 The group of 2 or more in the group of alkyl composition by oxygen atom, with or without substituent group sulphur atom, have or do not have The concrete structure of the group that the nitrogen-atoms or carbonyl of substituted base are formed by connecting ", but these are not limited to, it can enumerate following Divalent group shown in [D] group.

[changing 37]

[D]

Among these, preferably can keep the transparency of resin combination and assign while stability flexibility, The group that the group of 2 or more in alkylidene, arlydene or sub- aralkyl is formed by connecting by oxygen atom, more preferably may be used The alkylidene shown in following [E] group of the glass transition temperature of resin combination is improved while flexibility is assigned and passes through oxygen The group that atom is formed by connecting.

[changing 38]

[E]

In addition, from raising fluorenes ratio aspect, in the case of for these groups through being formed by connecting, carbon atom Number is preferably more than 2, and preferably less than 6, more preferably less than 4.

Among these, in substituents alpha¹And α²In at least one be Direct Bonding or substituents alpha¹And α²In at least 1 In the case that a carbon number is more than 2, due to fluorenes ring, (fluorenes unit a) is generally perpendicularly orientated compared with main chain, thus is Just the ratio of three fluorenes of the divalent in resin combination is few, it may have easily shows the tendency of inverse wave length dispersiveness.The latter's In the case of, from same aspect, preferably make α¹And α²The carbon number of the two is more than 2.On the other hand, substituent group is made α¹And α²In the case that the carbon number of the two is 1 (that is, with or without the methylene of substituent group), fluorenes ring (fluorenes unit) phase It is not generally perpendicularly to be orientated for main chain, and is significantly obliquely orientated, so even changes in wide scope in resin combination Divalent three fluorenes ratio, it may have be easily formed in the tendency of the small flat dispersiveness of difference of phase difference in wide band.

Among these, be preferably Direct Bonding, with or without substituent group carbon number be 1~10 alkylidene, With or without substituent group carbon number be 4~10 arlydene or selected from by the carbon with or without substituent group Alkylidene that atomicity is 1~10, with or without substituent group carbon number be 4~10 arlydene and have or do not have The carbon number of substituted base be 6~10 sub- aralkyl form group in the group of 2 or more by oxygen atom, have or The group that sulphur atom without substituent group, nitrogen-atoms or carbonyl with or without substituent group are formed by connecting.

More preferably Direct Bonding, the alkylidene of straight-chain, the alkylidene comprising branch, above-mentioned [A] group shown in fat At arbitrary the 2 of ring structure have straight-chain either the ester ring type alkylidene of the associative key of the alkylidene of branched, phenylene or Selected from the alkylidene by the carbon number 1~10 with or without substituent group, the carbon number 4 with or without substituent group ~10 arlydene and with or without substituent group carbon number 6~10 sub- aralkyl form group in 2 or more The group that is formed by connecting by oxygen atom of group.

It may further be preferable that due to not having an aromatic rings and with the low photoelasticity system that can be realized required by optical film Several tendency, Direct Bondings, methylene, ethylidene, n-propylene, positive butylidene, methylmethylene, 1- methyl ethylidene, Alicyclic ring shown in 2- methyl ethylidene, 2,2- dimethylpropylidenes, 2- methoxy -2- methyl propylenes or following [F] group Formula alkylidene.

[changing 39]

[F]

(the position of substitution of 2 associative keys in each ring structure shown in above-mentioned [F] group is arbitrary, and 2 associative keys can To be substituted on same carbon.)

Still more preferably Direct Bonding, methylene, ethylidene, n-propylene, positive butylidene, methylmethylene, 1- first Base ethylidene, 2- methyl ethylidene or 2,2- dimethylpropylidenes.Particularly preferred methylene, ethylidene or n-propylene.

Due to the tendency reduced when chain length is longer with glass transition temperature, thus preferably shorter chain-like groups, example Such as the group that preferred carbon number is less than 2.Further, since molecular structure becomes smaller, thus with repetition list can be improved The tendency of the concentration (fluorenes ratio) of fluorenes ring in member, desired optics physical property is shown so as to efficiency well.In addition, Preferably methylene, even if the group is contained compared with the quality of resin combination entirety with arbitrary quality, it may have available The small flat scattered tendency of the wavelength dispersibility of phase difference, and then also have can be with shorter process and industrial low cost The superiority that ground is imported.

On the other hand, for the purpose of the reliability under the mechanical strength of the obtained film of improvement, high temperature, it is preferably able to carry The glass transition temperature of high resin composition, carbon number be 4~10 arlydene or selected from by with or without Alkylidene that the carbon number of substituent group is 1~10 and with or without substituent group carbon number be 4~10 arlydene The group that 2 or more groups in the group of composition are formed by connecting by oxygen atom, more preferably Isosorbide-5-Nitrae-phenylene, 1,5- Asias naphthalene The divalent group shown in base, 2,6- naphthylenes or following [D2] groups.

[changing 40]

[D2]

In addition, in the case of applied to the phase difference film with inverse wave length dispersiveness, substituents alpha is suitably selected¹And α²It is Important.For example, due to low with unexpected inverse wave length dispersiveness as 1 group by the carbon number represented of methylene Tendency, thus R¹And R²Preferably Direct Bonding or its at least any one be carbon number be more than 2 group.

Alkylidene that more preferably Direct Bonding, the carbon number with or without substituent group are 2~10 has or not Arlydene that carbon number with substituent group is 4~10 or selected from by being 1 with or without the carbon number of substituent group ~10 alkylidene, with or without substituent group carbon number be 4~10 arlydene and with or without substituent group Carbon number be 6~10 the group that forms of sub- aralkyl in the group of 2 or more by oxygen atom, with or without taking The group that the sulphur atom of Dai Ji, nitrogen-atoms or carbonyl with or without substituent group are formed by connecting.

Further preferably Direct Bonding, the alkylidene of straight-chain, the alkylidene comprising branch, shown in above-mentioned [A] group Alicyclic structure arbitrary 2 at have straight-chain or branched alkylidene associative key ester ring type alkylidene, phenylene, Or for selected from by be 1~10 with or without the carbon number of substituent group alkylidene, with or without substituent group Arlydene that carbon number is 4~10 and with or without substituent group carbon number be 6~10 sub- aralkyl form The group that the group of 2 or more in group is formed by connecting by oxygen atom.

It is even furthermore preferable that due to do not have aromatic rings and low photoelastic coefficient required by can realizing optical film , Direct Bonding, ethylidene, n-propylene, positive butylidene, methylmethylene, 1- methyl ethylidene, 2- methyl ethylidene, 2, The ester ring type alkylidene shown in 2- dimethylpropylidenes, 2- methoxy -2- methyl propylenes or above-mentioned [F] group；Or The glass transition temperature of resin combination, 1,4- phenylenes can be increased, selected from by the carbon with or without substituent group Alkylidene that atomicity is 1~10 and with or without substituent group carbon number be 4~10 the group that forms of arlydene in The group that is formed by connecting by oxygen atom of the group of 2 or more.

Particularly preferably Direct Bonding, ethylidene, n-propylene, positive butylidene, methylmethylene, 1- methyl ethylidene, 2- methyl ethylidene or 2,2- dimethylpropylidenes.

Most preferably ethylidene or n-propylene.Due to inclining when chain length is longer with what glass transition temperature reduced To, thus preferably shorter chain-like groups, such as the group that carbon number is less than 3.Further, since molecular structure subtracts It is small, it is thus possible to improve the concentration (fluorenes ratio) of the fluorenes ring in repetitive unit, be shown well so as to efficiency desired Optics physical property.

In addition, for the reason for easy to manufacture, preferred substituents α¹And α²It is identical.

<1.5 concrete structure>

As the three fluorenes diester of the present invention, the substance represented by specifically it is preferable to use the following general formula (1).

[changing 41]

(in formula,

R¹⁰It is the organic substituent that carbon number is 1~10.)

It should be noted that the R in general formula (1)^3aAnd R^3bIt can be the same or different respectively.In addition, in general formula (1) In be respectively provided with the R of 3⁴~R⁹It can be the same or different respectively.Similarly, there is the R of 2 in general formula (1)¹⁰Respectively It can be the same or different.

R in above-mentioned general formula (1)¹And R²In, as " the alkylene that the carbon number with or without substituent group is 1~4 It is preferable to use above-mentioned for base "《Invention 1》R¹And R²The base in illustrated group.

Similarly, as R^3aAnd R^3bIt is preferable to use<1.1 alkylidenes, arlydene, sub- aralkyl>In it is illustrated Group.It should be noted that sometimes by R in this specification^3aAnd R^3bR is denoted as together³。

In addition, as R¹⁰It is preferable to use<1.3 ester group>It is middle as carbon number be 1~10 organic substituent Illustrated group.

It is enumerated below in R⁴~R⁹In " with or without substituent group carbon number be 1~10 alkyl " specific knot Structure, but these are not limited to, the straight chains such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, positive decyl can be enumerated The alkyl of shape；Isopropyl, 2- methyl-propyls, 2,2- dimethyl propyls, 2- ethylhexyls etc. include the alkyl of branch；Cyclopropyl, The isothrausmatic alkyl of cyclopenta, cyclohexyl, cyclooctyl.

With or without substituent group carbon number be 1~10 alkyl in carbon number be preferably less than 4, it is more excellent Elect less than 2 as.If in the range of this, then fluorenes ring is difficult to generate steric hindrance each other, has and obtains from the desired of fluorenes ring The tendency of optical characteristics.

As the substituent group that the alkyl can have, halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine can be enumerated Atom)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Carbon number be 1~10 acyl group (such as Acetyl group, benzoyl etc.)；Carbon number is 1~10 amide groups (such as acetamido, benzamido etc.)；Nitro；Cyanogen Base；With or without being 1~10 selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), carbon number Alkyl (such as methyl, ethyl, isopropyl etc.), the alkoxy (such as methoxyl group, ethyoxyl etc.) that carbon number is 1~10, carbon Acyl group (such as acetyl group, benzoyl etc.) that atomicity is 1~10, the amide groups that carbon number is 1~10 (such as acetamide Base, benzamido etc.), nitro, the carbon number of 1~3 substituent group in cyano etc. be 6~10 aryl (such as phenyl, Naphthalene etc.) etc..The quantity of the substituent group is not particularly limited, preferably 1~3.In the case that substituent group is 2 or more, substitution The species of base can be the same or different.It is preferably that nothing takes in addition, from the aspect that can industrially manufacture at low cost Generation.

As the concrete example of the alkyl with or without substituent group, trifluoromethyl, benzyl, 4- methoxybenzyls can be enumerated Base, methoxy etc..

R is enumerated below⁴~R⁹In " with or without substituent group carbon number be 4~10 aryl " concrete structure, But these are not limited to, the aryl such as phenyl, 1- naphthalenes, 2- naphthalenes can be enumerated；2- pyridyl groups, 2- thienyls, 2- furyls etc. Heteroaryl.

With or without substituent group carbon number be 4~10 aryl in carbon number be preferably less than 8, it is more excellent Elect less than 7 as.If in the range of this, then fluorenes ring is difficult to generate steric hindrance each other, has and obtains from the desired of fluorenes ring The tendency of optical characteristics.

As the substituent group that the aryl can have, halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine can be enumerated Atom)；Carbon number is 1~10 alkyl (such as methyl, ethyl, isopropyl etc.)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Carbon number is 1~10 acyl group (such as acetyl group, benzoyl etc.)；Carbon number is 1~10 amide groups (such as acetamido, benzamido etc.)；Nitro；Cyano etc..The quantity of the substituent group does not limit especially It is fixed, preferably 1~3.In the case that substituent group is 2 or more, the species of substituent group can be the same or different.In addition, from The aspect that can industrially manufacture at low cost is set out, preferably unsubstituted.

As the concrete example of the aryl with or without substituent group, 2- aminomethyl phenyls, 4- aminomethyl phenyls, 3 can be enumerated, 5- 3,5-dimethylphenyls, 4- benzoylphenyls, 4- methoxyphenyls, 4- nitrobenzophenones, 4- cyano-phenyls, 3- trifluoromethylbenzenes Base, 3,4- Dimethoxyphenyls, 3,4- methylene dihydroxyphenyl, 2,3,4,5,6- pentafluorophenyl groups, 4- methylfuran bases etc..

R is enumerated below⁴~R⁹In " with or without substituent group carbon number be 1~10 acyl group " concrete structure, But these are not limited to, formoxyl, acetyl group, propiono, 2- methylpropionyls, 2,2- Dimethylpropanoyls, 2- can be enumerated The aliphatic acyl radicals such as ethyl hexyl；The aromatic series acyls such as benzoyl, 1- naphthyl carbonyls, 2- naphthyl carbonyls, 2- furyl carbonyls Base.

With or without substituent group carbon number be 1~10 acyl group in carbon number be preferably less than 4, it is more excellent Elect less than 2 as.If in the range of this, then fluorenes ring is difficult to generate steric hindrance each other, has and obtains from the desired of fluorenes ring The tendency of optical characteristics.

As the substituent group that the acyl group can have, halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine can be enumerated Atom)；Carbon number is 1~10 alkyl (such as methyl, ethyl, isopropyl etc.)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Carbon number is 1~10 amide groups (such as acetamido, benzamido etc.)；Nitre Base；Cyano；With or without selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), carbon number for 1~ 10 alkyl (such as methyl, ethyl, isopropyl etc.), the alkoxy that carbon number is 1~10 (such as methoxyl group, ethyoxyl Deng), the acyl group (such as acetyl group, benzoyl etc.) that carbon number is 1~10, amide groups that carbon number is 1~10 (such as Acetamido, benzamido etc.), nitro, the carbon number of 1~3 substituent group in cyano etc. be 6~10 aryl (example Such as phenyl, naphthalene) etc..The quantity of the substituent group is not particularly limited, preferably 1~3.Substituent group is the situation of 2 or more Under, the species of substituent group can be the same or different.In addition, from the aspect that can industrially manufacture at low cost, it is excellent It elects as unsubstituted.

As the concrete example of the acyl group with or without substituent group, chloracetyl, trifluoroacetyl group, methoxy can be enumerated Base acetyl group, nitrophenoxyacetyl, 4- methoxybenzoyls base, 4- nitro benzoyls, 4- cyanobenzoyls, 4- fluoroforms Base benzoyl etc..

R is enumerated below⁴~R⁹In " with or without substituent group carbon number be 1~10 alkoxy or aryloxy group " Concrete structure, but be not limited to these, can enumerate methoxyl group, ethyoxyl, isopropoxy, tert-butoxy, trifluoromethoxy, The alkoxies such as phenoxy group；The aryloxy group such as phenoxy group.

In the alkoxy or aryloxy group for being 1~10 with or without the carbon number of substituent group, preferred alkoxy, alkane The carbon number of oxygroup is preferably less than 4, more preferably less than 2.If in the range of this, then fluorenes ring is difficult to generate space bit each other Resistance has and obtains the tendency of the desired optical characteristics from fluorenes ring.

R is enumerated below⁴~R⁹In concrete structure " with or without the amino of substituent group ", but be not limited to these, can To enumerate amino；N- methylaminos, N, N- dimethylaminos, N- ethylaminos, N, N- diethylaminos, N, N- Methylethyl ammonia Base, N- propylcarbamics, N, N- dipropylaminos, N- isopropylaminos, the aliphatic amines such as N, N- diisopropylaminoethyls；N- phenyl The aromatic series amino such as amino, N, N- diphenyl aminos；Formamido, acetamido, caprinoyl amido, benzamido, chloracetyl The amide groups such as amido；Alkoxycarbonyl amidos such as Benzyoxycarbonylamino, tertbutyloxycarbonylamino etc..

Among these, the high proton of acid degree, molecular weight are small, have and can improve the tendency of fluorenes ratio due to not having, excellent Elect N, more preferably N- dimethylaminos, N- ethylaminos or N, N- diethylamino, N, N- dimethylaminos as.

R is enumerated below⁴~R⁹In the sulphur atom of substituent group " have " concrete structure, but be not limited to these, can enumerate Sulfo group；The alkyl sulphonyls such as methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, isopropelsulfonyl；Benzenesulfonyl, to first The aryl sulfonyls such as phenyl sulfonyl；Methylsulfinyl, ethylsulfinyl, propylsulfenyl, isopropylsulphinyl Wait alkyl sulphinyls；The aryl sulfonyl kias such as phenylsufinyl, p-methylphenyl sulfinyl；The alkane such as methyl mercapto, ethylmercapto group Sulfenyl；The arylthios such as thiophenyl, p-methylphenyl sulfenyl；The alkyloxysulfonyls such as methoxysulfonyl, ethoxysulfonyl；Benzene oxygen The aryloxy sulfonyls such as base sulfonyl；Amino-sulfonyl；N- methylaminosulfonyls, N- ethylaminosulfonyls, N- tertiary butyls The alkyl sulphonyls such as amino-sulfonyl, N, N- dimethylamino-sulfonyls, N, N- diethylamino sulfonyls；N- phenyl amino sulphurs N-aryl sulfonyls such as acyl group, N, N- diphenyl amino sulfonyls etc..It should be noted that sulfo group can also with lithium, sodium, The forming salts such as potassium, magnesium, ammonium.

Among these, the high proton of acid degree, molecular weight are small, have and can improve the tendency of fluorenes ratio due to not having, excellent Elect methylsulfinyl, ethylsulfinyl or phenylsufinyl as, more preferably methylsulfinyl.

As R⁴~R⁹In " halogen atom ", fluorine atom, chlorine atom, bromine atoms, iodine atom can be enumerated.

Among these, for be easier import, due to for electron-withdrawing substituent group thus with improve fluorenes 9 it is anti- The reason for tendency of answering property, preferably fluorine atom, chlorine atom or bromine atoms, more preferably chlorine atom or bromine atoms.

In this way, by making R⁴~R⁹For specific atom as described above or substituent group, between main chain and fluorenes ring, fluorenes ring Steric hindrance each other is few, has the tendency that can obtain the desired optical characteristics from fluorenes ring.

These R⁴~R⁹In, preferably all hydrogen atoms or R⁴And/or R⁹To select free halogen, acyl group, nitro, cyanogen Any one in the group of base and sulfo group composition and R⁵~R⁸For hydrogen atom.In the case of all hydrogen atoms, in industry On also can by low cost fluorenes derive.In addition, in R⁴And/or R⁹To select free halogen, acyl group, nitro, cyano and sulphur Any one of group of base composition and R⁵~R⁸In the case of for hydrogen atom, since the fluorenes reactivity of 9 improves, thus with energy Enough adapt to the tendency of various induced reactions.More preferable all hydrogen atoms or R⁴And/or R⁹It is former by fluorine atom, chlorine to be selected from Any one in the group of son, bromine atoms and nitro composition and R⁵~R⁸For hydrogen atom, particularly preferred all hydrogen atoms Situation.In addition, by the way that for above-mentioned group, fluorenes ratio can be improved, and fluorenes ring is difficult to generate steric hindrance each other, and also having can Obtain the tendency of the desired optical characteristics from fluorenes ring.

The concrete example of the three fluorenes diester as the present invention can enumerate the structure shown in following [H] group.

[changing 42]

[changing 43]

<1.7 the physical property of three fluorenes diester>

The physics value of the three fluorenes diester of the present invention is not particularly limited, and preferably satisfies physics value illustrated below.

Chlorine content ratio in the three fluorenes diester of the present invention is preferably below 100 mass ppm in terms of Cl reduced masses.Into one Step is preferably below 10 mass ppm.It in the case that the content ratio of chlorine component is more, can lose catalyst used in polymerisation Living, polymerization can not be carried out to desired molecular weight, and reaction has the possibility that productivity is deteriorated in destabilization.And Also there is chlorine component remaining in obtained polymer, the thermal stability of polymer may be made reduce.

The content ratio of three fluorenes monoesters in the three fluorenes diester of the present invention is preferably the quality of whole three fluorene compounds Below 10 mass %.Further preferably below 2 mass %.The meeting when the aggregated reaction of three fluorenes monoesters is introduced into polymer Formed end envelope chain group, if thus three fluorenes monoesters increase, polymerize progress less than desired molecular weight or polymer In the remaining quantities of the low molecular compositions such as oligomer increase, the mechanical strength of obtained polymer or heat resistance drop may be made It is low.In addition it is believed that also low molecular composition such as oozes out at the possibility for reducing the quality of product from formed body.It needs to illustrate , monoester refers to object of any one in the end ester group of three fluorenes diester for the group beyond polymerisation reactivity group Matter.

In the three fluorenes diester of the present invention, it may contain from the sodium of following processes or the isometric preiodic type periodic table of potassium the The group II metals such as 1 race's metal or calcium, the process are formaldehydes to be made to have an effect to carry out the work of hydroxymethylation in the presence of a base Sequence；The content ratio of these metals is preferably below 500 mass ppm, is more preferably below 200 mass ppm, is more preferably Below 50 mass ppm, particularly preferably below 10 mass ppm.If metal ingredient is more, when polymerisation or resin are processed, Polymer may become easy coloring.In addition, contained metal ingredient shows catalyst action or catalyst inactivation effect, It is in destabilization that may make polymerization.

Three fluorenes diester in the present invention, particularly in three fluorene diaryl esters, may contain brought by following processes titanium, 12nd races such as group II metals, zinc, the cadmiums such as isometric the 1st race of preiodic type periodic table of the transition metal such as copper, iron, sodium, potassium, magnesium, calcium gold 14th race's metal such as category or tin, the process are that diaryl carbonates esters is made to have an effect in the presence of catalyst for ester exchange reaction To carry out the process of transesterification；The content ratio of these metals is preferably below 500 mass ppm, is more preferably 200 mass ppm Below, it is more preferably below 50 mass ppm, particularly preferably below 10 mass ppm.If metal ingredient is more, it is polymerizeing When reaction or resin are processed, polymer may become easy coloring.In addition, contained metal ingredient show catalyst action or Catalyst inactivation acts on, it is also possible to which it is in destabilization to make polymerization.

The tone of the tetrahydrofuran solution of 10 mass % of the three fluorenes diester of the present invention is preferably less than 50.Further preferably For less than 10.The absorption edge of three fluorenes diester extends close to the region of visible ray, has and is exposed due to because polymerization or resin processing The property easily coloured when high temperature.The good polymer of tone in order to obtain, three fluorenes diester used in preferred polymeric reaction Coloring is few as far as possible.Since tone is proportional to concentration, thus can be that 10 are measured and be standardized as under various concentration Value obtained from quality % concentration.Herein, the tone (APHA values) of three fluorenes diester can be measured：According to JIS-K0071-1 (1998), by (1000 degree) of the color standard liquid dilution of Kishida Chemical societies manufacture, by made dilution and Three fluorenes diester are encased in the colorimetric cylinder of internal diameter 20mm and are compared, and thus measure the tone.

5% weightless temperature of the three fluorenes diester of the present invention in thermogravimetric measure is preferably 230 DEG C or more, is more preferably 250 DEG C or more.Further it is particularly preferably 270 DEG C or more.Fluorenes is the structure very rich in electronics, the substituent group being bonded in fluorenes ring Reactivity it is high, easily generate thermal decomposition.If in the polymerization using three low fluorenes diester of heat decomposition temperature, in polymerization Thermal decomposition can be generated, polymerization may be coloured less than desired molecular weight or obtained polymer.

In addition, the decomposition temperature that measures in a nitrogen atmosphere of three fluorenes diester of the present invention be preferably more than 250 DEG C, it is more preferable For 300 DEG C or more, further preferably 330 DEG C or more, usually less than 380 DEG C.The three fluorenes diester of the present invention pass through fluorenes ring Laminated structure and make structure upright and outspoken, therefore meet the tendency of above range with decomposition temperature.Decomposition temperature meets by doing so Above range, have can improve the polyester obtained by three fluorenes diester, makrolon thermal stability tendency.Decomposition temperature is for example It can be measured by TG-DTA.

In addition, the fusing point (m.p.) of the three fluorenes diester of the present invention be preferably more than 120 DEG C, be more preferably 130 DEG C or more, into One step is preferably 150 DEG C or more, is usually less than 200 DEG C.The three fluorenes diester of the present invention make knot by the laminated structure of fluorenes ring Structure is upright and outspoken, therefore meets the tendency of above range with fusing point.Fusing point meets above range by doing so, and having can improve by three Polyester that fluorenes diester obtains, the tendency of the glass transition temperature of makrolon.Fusing point can for example be surveyed by TG-DTA It is fixed.

Three fluorenes diester used in the present invention, three fluorenes diester particularly represented by above-mentioned general formula (1) manufacturing method simultaneously Without any restriction, such as can be manufactured by the methods of autofrettage A or autofrettage B for being shown in following formula.

It should be noted that on two fluorenes diester, according to the autofrettage of three fluorene compounds (II), pair and R³Corresponding reagent After amount is adjusted and obtains two fluorene compounds, with autofrettage C it is same under the conditions of can manufacture.

[changing 44]

In formula, R¹And R²It is 1~4 to be each independently Direct Bonding or the carbon number with or without substituent group Alkylidene.

R^3aAnd R^3bBe each independently with or without substituent group carbon number be 1~10 alkylidene, have or The arlydene or be 6~10 with or without the carbon number of substituent group that carbon number without substituent group is 4~10 Sub- aralkyl,

R⁴~R⁹It is each independently hydrogen atom, the alkyl that the carbon number with or without substituent group is 1~10, tool Have or aryl that the carbon number without substituent group is 4~10, with or without the carbon number of substituent group be 1~10 Alkoxy, the carbon number with or without substituent group that acyl group, the carbon number with or without substituent group are 1~10 Aryloxy group for 1~10, the amino with or without substituent group, sulphur atom, halogen atom, nitro or the cyanogen with substituent group Base.Wherein, in R⁴~R⁹In, adjacent at least two group can be mutually bonded to form ring.

R¹⁰It is the organic substituent that carbon number is 1~10.

<1.8.1 autofrettage A>

Autofrettage A is following methods：Using fluorenes class (I) as raw material, 9- hydroxymethyl fluorenes classes (IV) are converted to, are passed through afterwards Dehydration synthesis alkene body (V), makes alkene body (V) react with fluorenyl anion, the mixing by oligomeric fluorenes such as refines by column It is refined in object, manufactures R³For three fluorene compounds (IIa) of methylene.It should be noted that unsubstituted 9- hydroxymethyls Fluorenes can be bought as reagent.Also can three fluorene compounds (II) that thus place obtains import ester group according to the process (ii) of autofrettage C Three fluorenes diester (1) are made.

It is such as low it has been known that there is 9- hydroxymethyl fluorenes to be converted into after 9- methylene -9H- fluorenes synthesizing by anionic polymerisation The method (J.Am.Chem.Soc., 123,2001,9182-9183.) of the mixture of polyfluorene.These methods are may be referred to, by mixing It closes and is refined in object, so as to manufacture three fluorene compounds (II).

<1.8.2 autofrettage B>

Autofrettage B is following methods：Three fluorenes are synthesized by carrying out the cross-linking reaction (process (i)) of raw material fluorenes class (I) Object (II) is closed, three fluorenes diester (1) are manufactured thereafter by ester group (process (ii)) is imported.

[changing 45]

In formula, R¹~R¹⁰With the R in formula (1)¹~R¹⁰Meaning is identical.

Autofrettage B is divided into the three fluorenes diester (1) of autofrettage and process (ii) of three fluorene compound of process (i) (II) below Autofrettage is recorded.

<1.8.3 process (i)：The manufacturing method of three fluorene compounds (II)>

[changing 46]

In formula, R³~R⁹With the R in formula (1)³~R⁹Meaning is identical.

The manufacturing method of three fluorene compounds (II) in process (i) is divided into R below³Situation recorded.

<1.8.3.1R³For the situation of Direct Bonding：9,9’：The manufacturing method of 9 ', 9 "-three difluorenes>

9,9’：The synthetic method of 9 ', 9 "-three difluorenes is known, can be synthesized by Fluorenone (Eur.J.Org.Chem.1999,1979-1984.)。

<1.8.3.2 process (ia)：R³For the manufacturing method of the situation of methylene>

Represented by the following general formula (IIa) there are three methylene-crosslinked fluorene compounds can be existed by fluorenes class (I) and formaldehydes Reaction represented according to the following formula is manufactured in the presence of alkali.

[changing 47]

In formula, R⁴~R⁹With the R in formula (1)⁴~R⁹Meaning is identical.

<1.8.3.2.1 formaldehydes>

The formaldehydes used in process (ia) into reaction system as long as that can supply the substance of formaldehyde without special It limits, paraformaldehyde, trioxane that gaseous formaldehyde, formalin, oxymethylene polymerization form etc. can be enumerated.From work Industry it is at low cost and due to for it is powdered thus it is operational easily, can be from the aspect of accurate weighing, more preferably paraformaldehyde. On the other hand, from the aspect of low from the industrial cost and danger due to being exposed when thus being added for liquid is few, it is more preferably first Aldehyde.

(definition of theoretical amount)

Manufacture as three fluorene compounds (IIa) of target in the case of, formaldehydes compared with raw material fluorenes class (I) theory (molar ratio) is measured to be represented by 2/3.

(the reasons why being preferably more than theoretical amount)

In the case of using more than the formaldehydes of theoretical amount compared with fluorenes class (I), having can generate and three as target Fluorene compound (IIa) is further crosslinked the tendency of the Oligofluorenylene compounds formed compared to fluorenes.Due to the fluorenes ring of Oligofluorenylene compounds Number, which more increases dissolubility, can more reduce, thus there are the Oligofluorenylene compounds that 4 or more fluorenes ring crosslinkings form in purpose thing In the case of, it is known that there is the increased tendency of refined load.Therefore it is usually preferred to the dosage of formaldehydes is as goal theory amount Less than 2/3 times mole.

(the reasons why not preferably being significantly less than theoretical amount)

In addition, if the dosage of formaldehydes is significantly less than theoretical amount 2/3, with three fluorene compounds (IIa) phase as target Two fluorene compounds fewer than the number of crosslinks of fluorenes ring have residual for main product or raw material fluorenes class (I) unreacted, it will be appreciated that The tendency being greatly reduced with yield.

Optimum amount on formaldehydes as a result, is usually 0.5 times mole compared with raw material fluorenes class (I) specifically Above, preferably 0.55 times mole or more, further preferably 0.6 times mole or more, in addition usually less than 0.67 times mole, Preferably less than 0.65 times mole, further preferably less than 0.63 times mole.So understand, it is main according to the dosage of formaldehydes Great changes have taken place for the structure of product and the ratio of product, by being used under conditions of formaldehydes dosage is limited, has There are three fluorene compounds (IIa) that can be to obtain in high yield as target.

<1.8.3.2.2 alkali>

As the alkali used in process (ia), the alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide are used Object；The hydroxide of the alkaline-earth metal such as calcium hydroxide, barium hydroxide；The carbonic acid of the alkali metal such as sodium carbonate, sodium acid carbonate, potassium carbonate Salt；The carbonate of the alkaline-earth metal such as magnesium carbonate, calcium carbonate；The alkali metal salt of the phosphoric acid such as sodium phosphate, dibastic sodium phosphate, potassium phosphate；Just The organic lithium salts such as butyl lithium, tert-butyl lithium；The alkali alcoholates such as sodium methoxide, sodium ethoxide, potassium tert-butoxide；Sodium hydride, hydrofining Wait hydrogenated alkali metals salt；The tertiary amines such as triethylamine, diazabicyclo endecatylene；Tetramethylammonium hydroxide, tetrabutylammonium hydroxide Wait quaternary ammonium hydroxides etc..They can be used alone, and can also share two or more.

It is preferably that there is the fully alkali metal of alkalescence in the reaction when being reacted using homogeneous system, among these Alkoxide, more preferable industrial cost low sodium methoxide and sodium ethoxide.Alkali alcoholate herein can use the substance of powdery, The liquids such as alcoholic solution can be used.And alkali metal can be made to react to prepare with alcohol.

On the other hand, it is preferably that there is fully alkalescence in the reaction when being reacted using two coating systems, among these Alkali metal hydroxide aqueous solution, the more preferably aqueous solution of the low sodium hydroxide of industrial cost or potassium hydroxide, into One step is preferably the aqueous solution of sodium hydroxide.

In addition, the concentration on aqueous solution, in the case where using particularly preferred sodium hydrate aqueous solution, when concentration is low Reaction speed significantly reduces, thus usually using more than 10wt/wt%, preferably more than 25wt/wt%, more preferably 40wt/ The aqueous solution of more than wt%.

When being reacted using homogeneous system, the dosage of alkali has no the special upper limit compared with raw material fluorenes class (I), if but dosage Excessively, then there is the increased tendency of refined load after stirring or reaction, thus usually less than 10 times moles of fluorenes class (I), Preferably less than 5 times moles, further preferably less than 1 times mole.On the other hand, if the dosage of alkali is very few, there is reaction The slow tendency of progress, thus as lower limit, be commonly angled relative to raw material fluorenes class (I) for more than 0.01 times mole, preferably 0.1 It is times mole above, be more preferably 0.2 times mole or more.

On the other hand, when being reacted using two coating systems, the dosage of alkali is had no compared with raw material fluorenes class (I) on especially Limit, if but dosage it is excessive, there are the increased tendency of refined load after stirring or reaction, thus usually the 10 of fluorenes class (I) It is times mole following, be preferably less than 5 times moles, be more preferably less than 2 times moles.On the other hand, if the dosage of alkali is very few, Then there is the slow tendency of progress of reaction, thus as lower limit, be commonly angled relative to raw material fluorenes class (I) for 0.1 times mole or more, Preferably 0.3 times mole or more, further preferably 0.4 times mole or more.

<1.8.3.2.3 solvent>

It is preferable to use solvent progress for process (ia).As the concrete example for the solvent that can be used, can enumerate：As alkyl Acetonitrile, propionitrile of nitrile series solvent etc.；As the diethyl ether of ether series solvent, tetrahydrofuran, 1,4- dioxane, methylcyclopentyl Ether, t-butyl methyl ether etc.；As the 1,2- dichloroethanes of halogen-based solvent, dichloromethane, chloroform, 1,1,2,2- tetrachloroethanes Deng；Chlorobenzene, 1,2- dichloro-benzenes as halogen system aromatic hydrocarbon etc.；N,N-dimethylformamide, N as acid amides series solvent, N- dimethyl acetamides, N-Methyl pyrrolidone etc.；Dimethyl sulfoxide (DMSO), sulfolane as sulfoxide series solvent etc.；As ring type The monocyclic aliphatic hydrocarbons such as pentamethylene, hexamethylene, cycloheptane, the cyclooctane of aliphatic hydrocarbon, be its derivative methyl cyclopentane, Ethyl cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2- dimethyl cyclohexanes, 1,3- dimethyl cyclohexanes, 1,4- dimethyl Hexamethylene, isopropyl cyclohexane, n-propyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl butylcyclohexane, 1,2, 4- trimethyl-cyclohexanes, 1,3,5- trimethyl-cyclohexanes etc.；The polycycles aliphatic hydrocarbon such as decahydronaphthalenes；Pentane, n-hexane, just The non-ring type aliphatic hydrocarbon such as heptane, normal octane, isooctane, n -nonane, n-decane, n-dodecane, n-tetradecane；As aromatic series Toluene, paraxylene, ortho-xylene, meta-xylene of hydrocarbon etc.；As the methanol of alcohol series solvent, ethyl alcohol, isopropanol, n-butanol, The tert-butyl alcohol, hexanol, octanol, cyclohexanol etc..

In the reaction of homogeneous system, since the dissolubility of the anion generated by fluorenes class (I) is high, it is good that there is reaction to carry out Good tendency, thus the preferably acid amides series solvent of polar solvent or sulfoxide series solvent.Wherein, N, N- bis- are particularly preferably Methylformamide.This is because, dissolubility of three fluorene compounds (IIa) in n,N-Dimethylformamide is low, given birth in purpose thing Into rear rapid precipitation, inhibit the progress of the reaction more than it, there is the tendency that the selectivity of purpose thing increases.

In the reaction of two coating systems, 2 layers are formed with alkaline aqueous solution, by the dissolubility of the anion of fluorenes class (I) generation There is height reaction to carry out good tendency, thus the preferably ether series solvent or halogen-based solvent of polar solvent.It is wherein special It You Xuanwei not tetrahydrofuran.This is because, dissolubility of three fluorene compounds (IIa) in tetrahydrofuran is low, generated in purpose thing It is rapid afterwards to be precipitated, inhibit the progress of the reaction more than it, there is the tendency that the selectivity of purpose thing increases.

These solvents can be used alone, and two or more may be used in combination.

The upper limit of dosage as solvent, usually using 10 times of volumes, the preferably 7 times of bodies for reaching raw material fluorenes class (I) The amount of accumulated amount, further preferably 4 times of volumes.On the other hand, if the dosage of solvent is very few, stir change hardly possible while have The progress of reaction is slowly inclined to, thus as lower limit, usually used 1 times of volume for reaching raw material fluorenes class (I) is preferably 2 The amount of times volume, further preferably 3 times of volumes.

<1.8.3.2.4 reaction formation>

When carrying out process (ia), the form of reaction may be employed batch-type reaction, circulation type reaction or they combine and Into form, its form is not particularly limited.

<1.8.3.2.5 reaction condition>

For process (ia), in order to inhibit the generation for the compound that fluorenes ring crosslinking forms compared with three fluorene compounds (IIa), It is preferred that it is reacted at low temperature as far as possible.On the other hand, if temperature is too low, sufficient reaction speed may be cannot get.

Therefore, as specific reaction temperature, usually it is 40 DEG C, is preferably 30 DEG C, more preferably 20 DEG C of temperature in the upper limit Under implemented.On the other hand, within the range having a lower limit of -50 DEG C, be preferably -20 DEG C, more preferably 0 DEG C or more implemented.

General reactions time usual lower limit in process (ia) is 30 minutes, be preferably 60 minutes, further preferably 2 small When, the upper limit is not particularly limited, but usually 20 it is small when, be preferably 10 it is small when, further preferably 5 it is small when.

<1.8.3.2.6 the separation and purification of purpose thing>

After termination of the reaction, reaction solution can be added in the acid waters such as dilute hydrochloric acid or adds the acid waters such as dilute hydrochloric acid It is added in reaction solution, three fluorene compound of purpose thing (IIa) is precipitated, thus separated.

In addition, after termination of the reaction, the solvent of dissolvable three fluorene compound of purpose thing (IIa) and water can be also added to instead It answers in liquid, extracts.The purpose thing gone out using solvent extraction can be by by the method for solvent concentration or addition poor solvent Method etc. separated.But since three fluorene compounds (IIa) are low-down with dissolubility in a solvent at room temperature Tendency, thus the method that it is precipitated generally preferably is contacted with acid water.

Obtained three fluorene compound (IIa) can also use directly as the raw material of process (ii), can also refined Afterwards in process (ii).As method for refining, common method for refining, such as recrystallization, reprecipitation method, extraction essence may be employed System, column chromatography etc., there is no restriction.

<1.8.3.3 process (ib)：R³For the manufacturing method of the situation beyond Direct Bonding>

Three fluorene compounds represented by the following general formula (IIb) can be using fluorenes class (I) as raw material, at alkylating agent (VIIIa) It is manufactured in the presence of alkali according to the reaction represented by following processes (ib).

[changing 48]

In formula, R³、R^3a、R^3bFor be 1~10 with or without the carbon number of substituent group alkylidene, have or do not have Arlydene that the carbon number of substituted base is 4~10 or with or without substituent group carbon number be 6~10 Asia Aralkyl, R⁴~R⁹With the R in formula (1)⁴~R⁹Meaning is identical.X represents leaving group.As the example of leaving group, Ke Yiju Go out halogen atom (not including fluorine wherein), mesyl or p-toluenesulfonyl etc..

Three fluorene compounds (IIb) may be referred to following methods and be synthesized：N-BuLi is used as alkali, is generating fluorenes class (I) after anion, it is made to be coupled (J.Am.Chem.Soc., 2007,129,8458.) with alkylating agent (VIIIa).But It is, when carrying out industry manufacture using the method for n-BuLi using these, to have in terms of secure context, cost extremely difficult Tendency.

As the alkylating agent used in process (ib), diiodomethane, 1,2- ethylidene periodides, 1,3- diiodo-s third can be enumerated Alkane, bis- iodobutanes of 1,4-, bis- iodopentanes of 1,5-, bis- iodohexanes of 1,6-, methylene bromide, glycol dibromide, 1,3- dibromopropanes, 1,4- dibromobutanes, pentamethylene bromide, 1,6- dibromo-hexanes, dichloromethane, 1,2- dichloroethanes, 1,3- dichloropropanes, 1, The alkyl dihalide of the straight-chains such as the bromo- 3- chloropropanes of 4- dichloroetane, 1,5- dichloropentane, 1,6- dichloro hexanes, 1- (does not wrap Include fluorine atom)；2,2- dimethyl -1,3- dichloropropanes etc. include the alkyl dihalide of branch (not including fluorine atom)；1,4- The aralkyl dihalide (not including fluorine atom) such as double (bromomethyl) benzene of double (bromomethyl) benzene, 1,3-；Glycol dinitrate sulphonic acid ester, Disulfonates of glycol such as glycol dinitrate benzene sulfonate, propylene glycol bis-mesylate, tetramethylene glycol bis-mesylate etc..

<1.8.4 the manufacturing method of three fluorenes diester (1)>

Hereinafter, by the manufacturing method of three fluorenes diester (1) in the process (ii) represented by following formula according to R¹Species point It is not recorded.

[changing 49]

In formula, R¹~R¹⁰With the R in formula (1)¹~R¹⁰Meaning is identical.R_i、R_iiAnd R_iiiIt is each independently hydrogen atom, tool Have or alkyl that the carbon number without substituent group is 1~10, with or without the carbon number of substituent group be 4~10 Aryl or with or without substituent group carbon number be 6~10 aralkyl.

<1.8.4.1 process (iia)：Autofrettage based on Michael (Michael) addition>

Three fluorenes diester represented by the following general formula (1a) can in the presence of a base according to following processes (iia) represented by it is anti- Ying Yousan fluorene compounds (II) and α, beta-unsaturated esters (VI) are manufactured.

[changing 50]

In formula, R³~R¹⁰With the R in formula (1)³~R¹⁰Meaning is identical.R_i、R_iiAnd R_iiiEach independently represent hydrogen atom, Alkyl that carbon number with or without substituent group is 1~10 with or without the carbon number of substituent group is 4~10 Aryl or with or without substituent group carbon number be 6~10 aralkyl.

<1.8.4.1.1 α, beta-unsaturated esters>

Alpha, beta-unsaturated esters as reaction reagent are represented by the logical formula (VI) in process (iia), in logical formula (VI), R_i、R_iiAnd R_iiiEach independently represent hydrogen atom, the alkyl that carbon number is 1~10, the carbon original with or without substituent group Aryl that subnumber is 4~10 or with or without substituent group carbon number be 6~10 aralkyl.Specifically, may be used To enumerate methyl, ethyl, n-propyl, isopropyl, cyclohexyl etc. (can be straight chain or branch) alkyl, phenyl, 1- naphthalenes The aryl such as base, 2- naphthalenes, 2- thienyls, benzyl, 2- phenylethyls, to aralkyl such as methoxy-benzyls.

As alpha, beta-unsaturated esters (VI), methyl acrylate, ethyl acrylate, phenyl acrylate, acrylic acid can be enumerated Allyl ester, glycidyl acrylate, 2-Hydroxy ethyl acrylate, acrylic acid 4- hydroxybutyls, 1,4 cyclohexane dimethanol list The esters of acrylic acid such as acrylate, methyl methacrylate, ethyl methacrylate, phenyl methacrylate, methacrylic acid Methyl acrylic esters, the 2- ethyl propylenes such as allyl ester, glycidyl methacrylate, methacrylic acid -2- hydroxy methacrylates Alpha-substituted unsaturation esters, methyl cinnamate, ethyl cinnamate, M Cr, the fourths such as sour methyl esters, 2- phenylacrylic acid methyl esters The β such as olefin(e) acid ethyl ester-substitution unsaturation esters.Wherein, it is preferably able to be introduced directly into the following general formula (VI- of polymerisation reactivity group 1) esters of unsaturated carboxylic acids represented by

[changing 51]

(in formula, R¹⁰Represent the organic substituent that carbon number is 1~10, R_iiiRepresent hydrogen atom, with or without taking Alkyl that the carbon number of Dai Ji is 1~10, with or without substituent group carbon number be 4~10 aryl or tool Have or aralkyl that carbon number without substituent group is 6~10.), esters of acrylic acid, the methyl being more preferably included in Esters of acrylic acid or alpha-substituted unsaturation esters, from reaction speed and reaction selectivity aspect, further preferred R_iiiFor The esters of acrylic acid or methyl acrylic ester of hydrogen atom or methyl.Due to R¹⁰For smaller group when, industrial cost it is low and Distillation is refined easily, reactivity is also high, thus particularly preferably methyl acrylate, methyl methacrylate, ethyl acrylate, methyl Ethyl acrylate, phenyl acrylate or phenyl methacrylate.

On the other hand, esters of unsaturated carboxylic acids (VI-1) for 2-Hydroxy ethyl acrylate, acrylic acid -4- hydroxybutyls, Isosorbide-5-Nitrae - In the case that cyclohexanedimethanol mono acrylic ester etc. has the esters of hydroxy alkyl, can polyester carbonic acid be obtained by a step The raw material of ester, polyester, thus particularly preferably.

Two or more different alpha, beta-unsaturated esters (VI) can also be used, but from the aspect of refined simplicity, preferably Use a kind of α, beta-unsaturated esters (VI).

The polymerization activities of alpha, beta-unsaturated esters (VI) is high, thus in the presence of with high concentration, have easily due to light, heat, The outside stimulus such as soda acid and the tendency polymerizeing.At this point, it is highly exothermic due to being accompanied by, thus may can be very dangerous. Therefore, from security aspect, the dosage of alpha, beta-unsaturated esters (VI) is preferred with being less excessively used.It is commonly angled relative to original Expect three fluorene compounds (II) for less than 10 times moles, preferably less than 5 times moles, further preferably less than 3 times moles.On Lower limit, due to being calculated as 2 times moles compared with raw material with theoretical amount, thus lower limit is usually 2 times moles or more.In order to accelerate to react It carries out, not retained material or intermediate, the dosages of alpha, beta-unsaturated esters (VI) is 2.2 times compared with three fluorene compound of raw material (II) Mole or more, further preferably 2.5 times moles or more.

<1.8.4.1.2 alkali>

As alkali, the alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide are used；Calcium hydroxide, hydroxide The hydroxide of the alkaline-earth metal such as barium；The carbonate of the alkali metal such as sodium carbonate, sodium acid carbonate, potassium carbonate；Magnesium carbonate, calcium carbonate etc. The carbonate of alkaline-earth metal；The alkali metal salt of the phosphoric acid such as sodium phosphate, dibastic sodium phosphate, potassium phosphate；N-BuLi, tert-butyl lithium etc. have Machine lithium salts；The alkali alcoholates such as sodium methoxide, sodium ethoxide, potassium tert-butoxide；The hydrogenated alkali metals salt such as sodium hydride, hydrofining；Three second The tertiary amines such as amine, diazabicyclo endecatylene；Tetramethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide Wait quaternary ammonium hydroxides.They can be used alone, and can also share two or more.

In R³For methylene situation in addition in the case of, have three fluorene compounds (II) reactivity have it is larger The tendency of difference.Therefore, it is divided into R³It is recorded for the situation and situation in addition of methylene.

In R³In the case of for methylene, three fluorene compounds (II) easily carry out decomposing in a solvent anti-in the presence of a base It should.Therefore, it is secondary anti-for decomposition reaction etc. can be inhibited in the case where being reacted using 2 coating systems of organic layer and water layer The reason for answering, it is preferable to use water-soluble inorganic bases.Wherein from the aspect of cost, reactivity, the hydrogen-oxygen of preferred as alkali The aqueous solution of compound, the particularly aqueous solution of the aqueous solution of more preferable sodium hydroxide or potassium hydroxide, further preferred hydroxide The aqueous solution of sodium.

In addition, the concentration on aqueous solution, in the case where using particularly preferred sodium hydrate aqueous solution, due to having If concentration is low reaction speed can significantly reduced tendency, thus particularly preferably using be usually more than 10wt/wt%, be preferably The aqueous solution of more than 30wt/wt%, more preferably more than 40wt/wt%.

In R³In the case of beyond methylene, can also it be reacted even with 2 coating systems of organic layer and water layer, but It is excellent due to having reaction be rapidly inclined in the case where the organic base being dissolved in organic layer is used to be reacted Choosing uses organic base.Wherein preferably there is the alkali alcoholate of fully alkalescence in the reaction, more preferable industrial cost is low Sodium methoxide or sodium ethoxide.Alkali alcoholate herein can use the substance of powdery, can also use the liquid objects such as alcoholic solution Matter.And alkali metal can be made to react to prepare with alcohol.

In R³In the case of for methylene, on the dosage of alkali, compared with three fluorene compound of raw material (II), the upper limit does not have Especially limitation, but when the dosage of alkali is excessive, the refined load after stirring or reaction may increase, thus used as spy In the case of the sodium hydrate aqueous solution of more than the 40wt/wt% of not preferred alkali, three fluorenes (II) are commonly angled relative to as 10 times of bodies Below accumulated amount, below preferably 5 times of volumes, below further preferably 2 times of volumes.When alkali number is very few, reaction speed It significantly reduces, thus alkali is usually more than 0.1 times of volume compared with three fluorene compound of raw material (II).Preferably 0.2 times of volume Amount is above, more than more preferably 0.5 times of volume.

In R³In the case of beyond methylene, on the dosage of alkali, compared with three fluorene compound of raw material (II), the upper limit It is not particularly limited, but when the dosage of alkali is excessive, the refined load after stirring or reaction may increase, thus make using In the case of sodium methoxide or sodium ethoxide for particularly preferred alkali, be commonly angled relative to three fluorene compounds (II) for less than 5 times moles, Preferably less than 2 times moles, further preferably less than 1 times mole, particularly preferably less than 0.5 times mole.It is very few in alkali number When, reaction speed significantly reduces, thus alkali is usually 0.005 times mole or more compared with three fluorene compound of raw material (II).It is excellent Elect 0.01 times mole or more, more preferably 0.05 times mole or more, particularly preferably 0.1 times mole or more as.

<1.8.4.1.3 phase transfer catalyst>

It is anti-in order to improve in process (iia) in the case where being reacted using 2 coating systems of organic layer and water layer Speed is answered, it is preferable to use phase transfer catalysts.

As phase transfer catalyst, can enumerate tetramethyl ammonium chloride, tetrabutylammonium bromide, methyl tricapryl ammonium chloride, Three decyl ammonium chloride of methyl, benzyltrimethylammonium chloride, tri-n-octyl methyl ammonium chloride, tetrabutylammonium iodide, acetyl group trimethyl The halide of the quaternary ammonium salts such as ammonium bromide, benzyltriethylammoinium chloride (not including fluorine atom)；N, N- dimethyl pyrrolidine chlorination Object, N- ethyl-N-methyl pyrrolidines iodide, N- butyl-N- crassitudes bromide, N- Benzyl-N-methyl pyrroles The halide of the seasons pyrrolidinium such as alkane chloride, N- ethyl-N-methyl pyrrolidines bromides (not including fluorine atom)；N- Butyl-N-methylmorpholine bromide, N- butyl-N-methylmorpholine iodide, N- pi-allyls-N-methylmorpholine bromide Wait the halide of seasons alkylbenzyldimethylasaltsum saltsum (not including fluorine atom)；N- methyl-N-benzyls piperidinium chloride, N- methyl-N-benzyl piperazines Pyridine bromide, N, N- lupetidines iodide, N- methyl-N ethyl Piperidineacetic acids salt, N- methyl-N ethyl piperidines The halide of the seasons piperidinium salt such as iodide (not including fluorine)；Crown ether-like etc..It is preferred that quaternary ammonium salt, further preferred tetrabutyl bromine Change ammonium, benzyltrimethylammonium chloride or benzyltriethylammoinium chloride.

These phase transfer catalysts can be used alone, and can also share two or more.

The dosage of phase transfer catalyst compared with three fluorene compound of raw material (II) it is excessive when, have and ester hydrolysis or step step by step The tendency that the side reactions such as Ke Er (Michael) reactions significantly carry out, and from cost aspect, it is commonly angled relative to three fluorenes Object (II) is closed also to be less than 5 times moles, be preferably less than 2 times moles, further preferably less than 1 times mole.Phase transfer catalysis (PTC) When the dosage of agent is very few, there is the significantly reduced tendency of reaction speed, thus the dosage of phase transfer catalyst is compared with three fluorenes of raw material Compound (II) is usually 0.01 times mole or more.Preferably 0.1 times mole or more, more preferably 0.5 times mole or more.

<1.8.4.1.4 solvent>

It is preferable to use solvent progress for process (iia).

Specifically, workable solvent can be enumerated：Acetonitrile, propionitrile as alkyl nitrile series solvent etc.；As ketone system Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) of solvent etc.；As the methyl acetate of ester series solvent, ethyl acetate, acetic acid third Ester, phenylacetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, 3- methoxy methyl propionates, 3- ethoxy-propionic acids The ring-type esters such as the esters of the straight-chains such as methyl esters, methyl lactate, ethyl lactate, gamma-butyrolacton, caprolactone, ethylene glycol monomethyl Ether acetic acid ester, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol -1- methyl ether acetates, the third two Ether-ethers classes such as alcohol -1- monoethyl ether acetates etc.；As the diethyl ether of ether series solvent, tetrahydrofuran, 1,4- dioxane, methyl ring Amyl ether, t-butyl methyl ether etc.；As the 1,2- dichloroethanes of halogen-based solvent, dichloromethane, chloroform, tetra- chloroethenes of 1,1,2,2- Alkane etc.；Chlorobenzene, 1,2- dichloro-benzenes as halogen system aromatic hydrocarbon etc.；N,N-dimethylformamide as acid amides series solvent, DMAC N,N' dimethyl acetamide etc.；Dimethyl sulfoxide (DMSO), sulfolane as sulfoxide series solvent etc.；Ring penta as ring type aliphatic hydrocarbon The monocyclic aliphatic hydrocarbons such as alkane, hexamethylene, cycloheptane, cyclooctane are the methyl cyclopentane, ethyl cyclopentane, first of its derivative Butylcyclohexane, ethyl cyclohexane, 1,2- dimethyl cyclohexanes, 1,3- dimethyl cyclohexanes, 1,4- dimethyl cyclohexanes, isopropyl Hexamethylene, n-propyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl butylcyclohexane, 1,2,4- 3-methyl cyclohexanols Alkane, 1,3,5- trimethyl-cyclohexanes etc.；The polycycles aliphatic hydrocarbon such as decahydronaphthalenes；Pentane, n-hexane, normal heptane, normal octane, The non-ring type aliphatic hydrocarbon such as isooctane, n -nonane, n-decane, n-dodecane, n-tetradecane；It is toluene as aromatic hydrocarbon, right Dimethylbenzene, ortho-xylene, meta-xylene etc.；Pyridine as heteroaromatic etc.；As the methanol of alcohol series solvent, ethyl alcohol, different Propyl alcohol, n-butanol, the tert-butyl alcohol, hexanol, octanol, cyclohexanol etc..

In R³In the case of for methylene, by using the solvent being separated with water, it is known that three can be inhibited by having The tendency of the side reactions such as the decomposition reaction of fluorene compound (II).Further, three fluorenes chemical combination of raw material can preferably be dissolved using In the case of the solvent of object (II), from carrying out good tendency aspect with reaction, it is preferable to use three fluorenes chemical combination of raw material The solubility of object (II) is the solvent of more than 0.5 mass %, is more than 1.0 mass % more preferably using the solubility, especially excellent Choosing uses the solvent that the solubility is more than 1.5 mass %.In particular, it is preferred that halogen system aliphatic hydrocarbon, halogen system aromatic series Hydrocarbon, aromatic hydrocarbon or ether series solvent, particularly preferred dichloromethane, chlorobenzene, chloroform, 1,2- dichloro-benzenes, tetrahydrofuran, Isosorbide-5-Nitrae- Dioxane or methylcyclopentyl ether.

These solvents can be used alone, and two or more may be used in combination.

On the dosage of solvent, the upper limit is not particularly limited, if the generation in view of the purpose thing in each reactor is imitated Rate, then usually using reach three fluorene compound of raw material (II) 20 times of volumes, be preferably 15 times of volumes, further preferably The amount of 10 times of volumes.On the other hand, if the dosage of solvent is very few, the dissolubility of reagent is deteriorated, stirs change hardly possible, has simultaneously The progress of reaction is slowly inclined to, thus is used as lower limit, usually used 1 times of volume for reaching three fluorene compound of raw material (II), The amount of preferably 2 times of volumes, further preferably 4 times of volumes.

In R³In the case of beyond methylene, it is known that there is the dissolubility of organic base and three fluorene compounds (II) to reaction Speed band carrys out the tendency of larger impact, and in order to ensure the dissolubility, it is preferable to use with the molten of dielectric constant more than certain value Agent.As the solvent that can preferably dissolve organic base and three fluorene compounds (II), optimization aromatic heterocycle, alkyl nitrile series solvent, Acid amides series solvent, sulfoxide series solvent, particularly preferred pyridine, acetonitrile, n,N-Dimethylformamide, n,N-dimethylacetamide, two Methyl sulfoxide, sulfolane.

These solvents can be used alone, and two or more may be used in combination.

On the dosage of solvent, the upper limit is not particularly limited, if the generation in view of the purpose thing in each reactor is imitated Rate, then usually using 20 times of volumes, further preferably preferably 15 times of volumes, the 10 times of bodies for reaching three fluorenes of raw material (II) The amount of accumulated amount.On the other hand, if the dosage of solvent is very few, the dissolubility of reagent is deteriorated, stirs change hardly possible, while has reaction Slowly it is inclined to, thus as lower limit, usually used 1 times of volume for reaching three fluorenes of raw material (II) is preferably 2 times of volumes The amount of amount, further preferably 4 times of volumes.

<1.8.4.1.5 reaction formation>

When carrying out process (iia), batch-type reaction, circulation type reaction or their combinations may be employed in the form of reaction Its form is not particularly limited in the form formed.

It, will when reacting and starting in putting into reaction reagent in the input method in reactor in the case of batch-type Alpha, beta-unsaturated esters (VI) are by the case of disposably adding and being fed intake, since alpha, beta-unsaturated esters (VI) are deposited with high concentration , thus the polymerisation of side reaction easily carries out.So as to preferably in addition three fluorene compound of raw material (II), phase transfer catalysis (PTC) α, beta-unsaturated esters (VI) are gradually added after agent, solvent and alkali on a small quantity every time.

<1.8.4.1.6 reaction condition>

Process (iia) if in temperature it is too low, cannot get sufficient reaction speed, if otherwise temperature it is excessively high, have The polymerisation tendency easy to perform of alpha, beta-unsaturated esters (VI), thus temperature treatment is critically important.Therefore, as reaction temperature Degree, specifically, usually within the range having a lower limit of 0 DEG C, preferably 10 DEG C, more preferably 15 DEG C is implemented.On the other hand, usually upper 40 DEG C, preferably 30 DEG C, more preferably 20 DEG C are limited to be implemented.

On the General reactions time in process (iia), when usual lower limit is 30 minutes, preferably 1 is small, further preferably For 2 it is small when, the upper limit is not particularly limited, be usually 20 it is small when, be preferably 10 it is small when, further preferably 5 it is small when.

<1.8.4.1.7 the separation and purification of purpose thing>

After termination of the reaction, following methods, which can be used, is precipitated three fluorenes diester (1a) of purpose thing, so as to carry out purpose thing three The separation of fluorenes diester (1a), the method are by filtering byproduct metal halide and the inorganic base of remaining from reaction solution The method that the method for solvent concentration or the poor solvent of adding purpose object are carried out after middle removing；Etc..

In addition, after termination of the reaction, acid water and dissolvable three fluorenes diester of purpose thing can also be added into reaction solution The solvent of (1a) extracts.The purpose thing gone out using solvent extraction can pass through the method concentrated to solvent or addition Method of poor solvent etc. is separated.

As the solvent that can be used in extraction, as long as can dissolve three fluorenes diester (1a) of purpose thing, without special Limitation, but it is adapted in use to a kind in halogen-based solvents such as the aromatic hydrocarbon compounds such as toluene, dimethylbenzene, dichloromethane, chloroform etc. Or two or more.

The three fluorenes diester (1a) obtained herein can be used directly by polyester or in the form of polyestercarbonate starting monomer, Or can also be used etc. in the form of the precursor of polycarbonate starting material monomer, but can also be used after refine. As method for refining, common method for refining may be employed, such as recrystallization or reprecipitation method, Hydrolysis kinetics, column chromatography, and it is unlimited System.Three fluorenes diester (1a) can be additionally dissolved in appropriate solvent, be handled using activated carbon.It can use at this time Solvent is identical with the solvent that can be used during extraction.

<1.8.4.2 process (iib)：Based on alkylated autofrettage>

Three fluorenes diester (1b) can be by by three fluorene compounds (II) and alkylating agent (VIIIb) and the alkane of (VIIIc) The method of glycosylation reaction is manufactured.

[changing 52]

In formula, R¹~R⁹With the R in formula (1)¹~R⁹Meaning is identical.X represents leaving group.As the example of leaving group, Halogen atom (not including fluorine wherein), mesyl or p-toluenesulfonyl etc. can be enumerated.

The alkylated reaction of fluorenes class is widely known by the people, for example, there have report to propose double (bromine hexyl) fluorenes of 9,9-, 9,9- to be double Double (alkylhalide group) fluorenes (J.Org.Chem., 2010,75,2714.) of the 9,9- such as (iodine hexyl) fluorenes.It, can according to these technological thoughts Three fluorenes diester (1b) are synthesized using three fluorene compounds (II) as raw material.

As the alkylating agent used in process (iib), methyl chloroacetate, methyl bromoacetate, iodoacetic acid first can be enumerated Ester, ethyl chloroacetate, bromoacetate, ethyl iodoacetate, propyl chloroacetate, Solid acid n-butyl chloroacete, chloroacetic acid tert-butyl ester, bromine second Tert-butyl acrylate, the iodoacetic acid tert-butyl ester, 2- methyl chloropropionates, 2 bromopropionic acid methyl esters, 2- iodopropionic acids methyl esters, 2- chloropropionates, 2- The chloropropionic acid tert-butyl ester, the 2 bromopropionic acid tert-butyl ester, 2 bromopropionic acid ethyl ester, 2- iodopropionic acids ethyl ester, 3- chlorobutanoates, 3- bromo-butyric acid first The halogenated chains such as ester, 3- iodine methyl butyrate, 3- neoprene acid ethyl esters, 3- neoprene acid ethyl esters, 3- iodine ethyl butyrate, the 2- iodopropionic acid tert-butyl esters Alkanoic acid Arrcostab；The halogenated-chain acids aryl esters such as phenyl chloroacetate, phenyl bromoacetate, iodoacetic acid phenyl ester；4- chloromethyl benzoic acids Methyl esters, 4- bromomethyl-benzoic acid methyl esters, 4- chloromethyl benzoic acids ethyl ester, 4- bromomethyl-benzoic acid ethyl esters, 3- chloromethyl benzoic acids Halogenated alkyls benzoic acid alkyl base ester such as methyl esters, 3- bromomethyl-benzoic acid methyl esters etc..

<1.8.4.3 three fluorene diaryl esters of general formula (1c) manufacturing method (after the synthesis of three fluorenes diester compounds (1), Utilize the autofrettage of three fluorene diaryl ester compounds (1c) of ester exchange reaction)>

Three fluorene diaryl ester compounds (1c) can pass through the process (process via three fluorenes diester compounds (1) of synthesis (iia) or the side of process (iib) and the subsequent ester exchange reaction (process (iic)) with diaryl carbonate esters (11a) Method is manufactured.

[changing 53]

In formula, R¹~R¹⁰With the R in formula (1)¹~R¹⁰Meaning is identical.Ar¹Represent the carbon original with or without substituent group Subnumber is 4~10 aryl.

<1.8.4.3.1 the manufacturing method of three fluorene diaryl esters of general formula (1c) (utilizes three fluorene diaryls of ester exchange reaction The autofrettage of ester compounds (1c))>

Ar¹For be 4~10 with or without the carbon number of substituent group aryl three fluorene diaryl ester compounds (1c) can be fragrant by three fluorenes diester compounds (1) and two according to the reaction represented by process (iic) in the presence of ester exchange catalyst Base carbonates (11a) are manufactured.

<1.8.4.3.1.1 diaryl carbonate esters>

Diaryl carbonate esters as reaction reagent can enumerate diphenyl carbonate, carboxylol ester, double (chlorobenzenes Base) carbonic ester, m-cresyl, carbonic acid dinaphthyl ester, double (biphenyl) esters of carbonic acid etc..Wherein preferred low cost and can industry obtain The diphenyl carbonate obtained.These diaryl carbonates can be used alone, and can also be used in mixed way two or more.

On the dosage of diaryl carbonate esters, the special upper limit is had no compared with three fluorenes diester (1) of raw material, if but dosage mistake It is more, then there is the increased tendency of refined load after reaction, thus usually less than 20 times moles of three fluorenes diester, preferably 10 It is times mole following, be more preferably less than 5 times moles.

On the other hand, if the dosage of alkali is very few, three fluorenes diester (1) of raw material or three fluorenes as follows as intermediate Single aryl ester (1e) might have residual, thus as lower limit, be commonly angled relative to three fluorenes diester (1) of raw material for 1 times mole or more, Preferably 1.5 times moles or more, further preferably 2 times moles or more.

[changing 54]

<1.8.4.3.1.2 catalyst for ester exchange reaction>

As catalyst for ester exchange reaction, can enumerate：It is four titanium butoxides, four isobutoxy titaniums, titanium tetramethoxide, four different Titanium propanolate, purity titanium tetraethoxide, four (2- ethyl hexyl oxies) titaniums, four (octadecyl) orthotitanates, four phenoxide titaniums, levulinic The titanium compounds such as double (acetylacetone,2,4-pentanedione) titaniums (IV) of ketone titanium (IV), diisopropoxy；Lithium carbonate, dibutylamino lithium, acetylacetone,2,4-pentanedione The alkali metal compounds such as lithium, phenoxy group sodium, phenoxy group potassium；The cadmium compounds such as acetylacetone,2,4-pentanedione cadmium, cadmium carbonate；Acetylacetone,2,4-pentanedione zirconium, two The zirconium compounds such as luxuriant zirconium；Vulcanized lead, lead hydroxide, plumbite, zincate, ceruse, lead acetate, tetrabutyl lead, tetraphernl-lead, The lead compounds such as triphenyl lead, dimethoxy lead, two phenoxy group lead；Copper acetate, bis-acetylacetonate copper, copper oleate, cupric dibutyldithiocarbamate, two The copper compounds such as methoxyl group copper, copper chloride；Iron hydroxide, ferric carbonate, triacetoxyl group iron, trimethoxy iron, triple phenoxyl iron Wait iron compounds；The zinc impregnations such as bis-acetylacetonate zinc, diacetoxy zinc, dimethoxy zinc, diethoxy zinc, two phenoxy group zinc are closed Object；Di-nbutyltin oxide, diphenyl tin oxide, di-n-octyl tin oxide, dimethoxy di-n-butyl tin, di-n-butyl tin two Acrylate, di-n-butyl tin dimethylacrylate, di-n-butyl tin dilaurate, tetramethoxy tin, four phenoxy group tin, The organo-tin compounds such as the tetrabutyl -1,3- diacetoxy distannoxanes；Aluminium acetate, aluminum methoxide, aluminum ethoxide, phenoxy group aluminium Wait aluminium compounds；The vfanadium compound such as vanadium dichloride, vanadium trichloride, vanadium tetrachloride, vanadic sulfate；Phenoxy group tetraphenylphosphonium Deng phosphonium salts Deng.They can be used alone, and can also share two or more.

Among these, for industrial cost it is low, have operation on superiority the reason for, You selects Shi Yong phosphonium salts, lithium Compound, zirconium compounds, organo-tin compound or titanium compound etc., wherein particularly preferred organo-tin compound or titanizing are closed Object.

On the dosage of catalyst for ester exchange reaction, the special upper limit is had no compared with three fluorenes diester (1) of raw material, if but dosage Excessively, then there is the increased tendency of refined load after reaction, thus usually 20 moles of below % of fluorenes, be preferably 10 to rub You are below %, further preferably 5 moles of below %.

On the other hand, when the dosage of catalyst for ester exchange reaction is very few, the reaction time may be long, thus under conduct Limit is commonly angled relative to three fluorenes diester of raw material and is 0.1 mole of more than %, is preferably 0.5 mole of more than %, further preferably 1 rubs You are more than %.

<1.8.4.3.1.3 solvent>

Reaction dissolvent can be used in process (iic), but preferably without using reaction dissolvent, merely with three fluorenes diester of raw material (1), diaryl carbonate esters and catalyst for ester exchange reaction are reacted.But in three fluorenes diester (1) of raw material, diaryl Carbonates room temperature is solid, is difficult in the case of stirring, and can also use reaction dissolvent.Using the situation of reaction dissolvent Under, as long as can suitably to dissolve and/or disperse three fluorenes diester (1) of above-mentioned raw materials, diaryl carbonate esters and transesterification The solvent of catalysts, species are arbitrary.

Specifically, the solvent that can be used can be enumerated：Acetonitrile, propionitrile as alkyl nitrile series solvent etc.；As ketone Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) of series solvent etc.；As the diethyl ether of ether series solvent, tetrahydrofuran, 1,4- dioxies Six rings, methylcyclopentyl ether, t-butyl methyl ether etc.；As the 1,2- dichloroethanes of halogen-based solvent, dichloromethane, chloroform, 1, 1,2,2- tetrachloroethanes etc.；Chlorobenzene, 1,2- dichloro-benzenes as halogen system aromatic hydrocarbon etc.；As the N of acid amides series solvent, N- bis- Methylformamide, DMAC N,N' dimethyl acetamide etc.；Dimethyl sulfoxide (DMSO), sulfolane as sulfoxide series solvent etc.；As ring type fat The monocyclic aliphatic hydrocarbons such as pentamethylene, hexamethylene, cycloheptane, the cyclooctane of fat race hydrocarbon are methyl cyclopentane, the second of its derivative Cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2- dimethyl cyclohexanes, 1,3- dimethyl cyclohexanes, 1,4- diformazan basic rings Hexane, isopropyl cyclohexane, n-propyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl butylcyclohexane, 1,2,4- Trimethyl-cyclohexane, 1,3,5- trimethyl-cyclohexanes etc.；The polycycles aliphatic hydrocarbon such as decahydronaphthalenes；Pentane, n-hexane, positive heptan The non-ring type aliphatic hydrocarbon such as alkane, normal octane, isooctane, n -nonane, n-decane, n-dodecane, n-tetradecane；As aromatic hydrocarbon Toluene, paraxylene, ortho-xylene, meta-xylene, 1,3,5- trimethylbenzenes, 1,2,4- trimethylbenzenes, 1,2,3,4- tetrahydrochysenes Naphthalene etc.；Pyridine as heteroaromatic etc..

Since the reaction preferably carries out at a high temperature of usually 100 DEG C or more, thus in above-mentioned solvent, preferred boiling point Chlorobenzene, 1,2- dichloro-benzenes, trichloro-benzenes, toluene, paraxylene, ortho-xylene, meta-xylene for 100 DEG C or more of solvent, 1, 3,5- trimethylbenzenes, 1,2,4- trimethylbenzenes, 1,2,3,4- naphthanes, decahydronaphthalenes, N,N-dimethylformamide, N, N- diformazans Yl acetamide, dimethyl sulfoxide (DMSO) or sulfolane, for can suitably dissolve three fluorenes diester (1) of raw material, boiling point for 130 DEG C with Above, can carry out the reason for reaction under higher temperature, particularly preferred 1,2- dichloro-benzenes, dimethylbenzene, 1,3,5- trimethylbenzenes, 1, 2,4- trimethylbenzenes or 1,2,3,4- naphthanes, decahydronaphthalenes.

These solvents can be used alone, and two or more may be used in combination.

On the dosage of solvent, the upper limit is not particularly limited, if the generation in view of the purpose thing in each reactor is imitated Rate, then usually using reach three fluorenes diester (1) of raw material 15 times of volumes, be preferably 10 times of volumes, further preferably 5 times The amount of volume.On the other hand, if the dosage of solvent is very few, the dissolubility of reagent is deteriorated, stirs change hardly possible, while has reaction Progress be slowly inclined to, thus as lower limit, usually using reaching 1 times of volume of three fluorenes diester (1) of raw material, be preferably 2 The amount of times volume, further preferably 4 times of volumes.

<1.8.4.3.1.4 reaction formation>

When carrying out process (iic), batch-type reaction, circulation type reaction or their combinations may be employed in the form of reaction Its form is not particularly limited in the form formed.

<1.8.4.3.1.5 reaction condition>

In process (iic), if temperature is too low, there is the tendency that cannot get sufficient reaction speed, thus usually exist Lower limit, which is 50 DEG C, preferably 70 DEG C, more preferably 100 DEG C, to be implemented.On the other hand, it is usually 250 DEG C, is preferably in the upper limit 200 DEG C, more preferably 180 DEG C are implemented.

On the General reactions time in process (iic), usual lower limit for 1 it is small when, be preferably 2 it is small when, further preferably For 3 it is small when, the upper limit is not particularly limited, be usually 30 it is small when, be preferably 20 it is small when, further preferably 10 it is small when.

In process (iic), in order to make balance to product side deviate, can be distilled off under reduced pressure by-product simultaneously into Row reaction.In the case of being depressurized, pressure be usually below 20kPa, be preferably below 10kPa, more preferably 5kPa with Under implemented.On the other hand, if vacuum degree is excessively high, possible continuous cropping also rises for the diaryl carbonate esters that reagent uses China, thus implemented in usually more than 0.1kPa, preferably more than 0.5kPa, more preferably more than 1.0kPa.

<1.8.4.3.1.6 the separation and purification of purpose thing>

After termination of the reaction, poor solvent can be added into reaction solution, three fluorene diaryl ester (1c) of purpose thing is precipitated, by This is separated.

In addition, after termination of the reaction, the solvent of dissolvable three fluorene diaryl ester (Ic) of purpose thing can be also added to water In reaction solution, extract.The purpose thing gone out using solvent extraction can be by the method that is concentrated to solvent or addition not Method of good solvent etc. is separated.

Obtained three fluorene diaryls ester (1c) also can be former as the polycarbonate starting material containing polyestercarbonate or polyester Material is directly used in polymerization.As method for refining, common method for refining, such as recrystallization, reprecipitation method, extraction essence may be employed System, column chromatography etc., there is no restriction.

<2 oligomeric fluorenes diester compositions>

The oligomeric fluorenes diester compositions of the present invention include above-mentioned three fluorenes diester and two fluorenes diester.By not only including three Fluorenes diester also comprising two fluorenes diester, has the tendency that heat resistance or optical characteristics can be easily adjusted to desired situation.

<2.1 2 fluorenes diester>

Two fluorenes diester contained by the oligomeric fluorenes diester compositions of the present invention include 2 fluorenes with or without substituent group Unit b, the carbon atom of 9 of fluorenes unit b be bonded directly with one another or by with or without substituent group alkylidene, It arlydene with or without substituent group or is bonded with or without the sub- aralkyl of substituent group with chain.

As fluorenes unit b, it is preferable to use the fluorenes units illustrated in as fluorenes unit a.Oligomeric fluorenes diester compositions institute The fluorenes unit b and fluorenes unit a in three contained fluorenes diester in the two fluorenes diester contained can be the same or different.

Asia of the alkylidene illustrated in it is preferable to use the alkylidene as bonding fluorenes unit a as bonding fluorenes unit b Alkyl.The alkylidene and three contained fluorenes two of bonding fluorenes unit b in two fluorenes diester contained by oligomeric fluorenes diester compositions The alkylidene of bonding fluorenes unit a in ester can be the same or different.

Similarly, as bonding fluorenes unit b arlydene it is preferable to use as bonding fluorenes unit a arlydene institute The arlydene of illustration.The arlydene of bonding fluorenes unit b in two fluorenes diester contained by oligomeric fluorenes diester compositions with it is contained Three fluorenes diester in the arlydene of bonding fluorenes unit a can be the same or different.

In addition, as bonding fluorenes unit b sub- aralkyl it is preferable to use as bonding fluorenes unit a sub- aralkyl Illustrated sub- aralkyl.The sub- aralkyl of bonding fluorenes unit b in two fluorenes diester contained by oligomeric fluorenes diester compositions with The sub- aralkyl of bonding fluorenes unit a in three contained fluorenes diester can be the same or different.

The present invention oligomeric fluorenes diester compositions contained by two fluorenes diester can be：In the fluorenes unit b positioned at two ends The carbon atom of 9 on be bonded with substituents alpha respectively³And α⁴, in the substituents alpha³And α⁴On be bonded with ester group.In this case, α³And α⁴It can be the same or different.In addition, substituents alpha³And α⁴In include Direct Bonding, i.e. in the carbon of 9 of fluorenes unit a There can be ester group with Direct Bonding on atom.As substituents alpha³And α⁴It is preferable to use as substituents alpha¹And α²Illustrated Substituent group.Similarly, as ester group, it is preferable to use the ester groups illustrated in as the ester group in three fluorenes diester.

As two fluorenes diester contained by the oligomeric fluorenes diester compositions of the present invention, specifically it is preferable to use under State the substance represented by general formula (2).

[changing 55]

R³Alkylidene that the carbon number being each independently with or without substituent group is 1~10 has or does not have Arlydene that the carbon number of substituted base is 4~10 or with or without substituent group carbon number be 6~10 Asia Aralkyl,

R⁴~R⁹It is each independently hydrogen atom, the alkyl that the carbon number with or without substituent group is 1~10, tool Have or aryl that the carbon number without substituent group is 4~10, with or without the carbon number of substituent group be 1~10 Acyloxy, the carbon number with or without substituent group that acyl group, the carbon number with or without substituent group are 1~10 Alkoxy for 1~10, with or without substituent group carbon number be 1~10 aryloxy group, with or without substitution The amino of base, sulphur atom, halogen atom, nitro or the cyano with substituent group.Wherein, in R⁴~R⁹In, adjacent at least two base Group can be mutually bonded to form ring.

R¹⁰It is the organic substituent that carbon number is 1~10.

It should be noted that the R of 2 is respectively provided in formula (2)⁴~R⁹It can be the same or different respectively.Similarly, There is the R of 2 in formula (2)¹⁰It can be the same or different respectively.

As the R in above-mentioned formula (2)¹~R¹⁰It is preferable to use as the R in above-mentioned formula (1)¹~R¹⁰Illustrated base Group.

As the concrete example of two fluorenes diester contained by the oligomeric fluorenes diester compositions of the present invention, can enumerate following [I] Structure shown in group.

[changing 56]

[changing 57]

The physics value of two fluorenes diester contained by the oligomeric fluorenes diester compositions of the present invention is not particularly limited, and preferably satisfies Physics value illustrated below.

The decomposition temperature that the two fluorenes diester of the present invention measure in a nitrogen atmosphere is preferably 250 DEG C or more, is more preferably 270 DEG C or more, further preferably more than 290 DEG C, usually less than 300 DEG C.The lamination knot that the two fluorenes diester of the present invention pass through fluorenes ring Structure and make structure upright and outspoken, therefore meet the tendency of above range with decomposition temperature.Decomposition temperature meets above-mentioned model by doing so Enclose, have can improve the polyester obtained by two fluorenes diester, makrolon thermal stability tendency.Decomposition temperature can for example lead to TG-DTA is crossed to be measured.

In addition, the fusing point (m.p.) of the two fluorenes diester of the present invention be preferably more than 100 DEG C, be more preferably 120 DEG C or more, into One step is preferably 140 DEG C or more, is usually less than 150 DEG C.The two fluorenes diester of the present invention make knot by the laminated structure of fluorenes ring Structure is upright and outspoken, therefore meets the tendency of above range with fusing point.Fusing point meets above range by doing so, and having can improve by two Polyester that fluorenes diester obtains, the tendency of the thermal stability of makrolon.Fusing point can be for example measured by TG-DTA.

It is not particularly limited for the content ratio of three fluorenes diester contained by the oligomeric fluorenes diester compositions of the present invention, from It improves heat resistance and then is set out with lesser amount of for the use of it can obtain desired optical characteristics, compared with composition Gross mass be preferably more than 0.1 mass %, more preferably more than 0.5 mass %, further preferably more than 1 mass %, more Further preferably more than 3 mass %, particularly preferably more than 5 mass %, and usually below 30 mass %.

On the other hand, it is not particularly limited for the content ratio of two fluorenes diester contained by oligomeric fluorenes diester compositions, From flexibility and the adjustment aspect of optical characteristics, compared with the gross mass of composition, be preferably more than 0.1 mass %, More preferably more than 0.3 mass %, further preferably more than 1 mass %, it is still more preferably more than 3 mass %, especially Preferably more than 5 mass %, and be preferably below 50 mass %, more preferably 40 matter from the aspect of heat resistance is improved Measure below %, further preferably below 30 mass %.

It is in addition, not special for the content ratio of two fluorenes diester and three fluorenes diester contained by oligomeric fluorenes diester compositions It limits, the two fluorenes diester and three fluorenes diester contained by from flexibility and the adjustment aspect of optical characteristics, composition Molar ratio (molal quantity of the fluorenes diester of the molal quantity of two fluorenes diester/tri-) is preferably more than 0.001, more preferably more than 0.003, into One step is preferably more than 0.01, is still more preferably more than 0.03, is particularly preferably more than 0.05, in addition from raising heat resistance From the aspect of, it is preferably less than 0.5, more preferably less than 0.4, further preferably less than 0.3.

On two fluorenes diester contained in oligomeric fluorenes diester compositions, the molal quantity of three fluorenes diester, such as can utilize Area % that calibration curve is analyzed by HPLC estimates.

<3 resin combinations>

The resin combination of the present invention is the resin combination for containing three fluorenes with divalent as the polymer of repetitive unit Object.

In this way, for the resin combination of the present invention, except containing three fluorenes with divalent as the poly- of repetitive unit Beyond the region of objective existence is closed, aftermentioned other polymer can also be contained, in addition can also contain additive etc..Also, the resin group of the present invention Closing object can also be formed by three fluorenes with divalent as the polymer of repetitive unit.

Polymer contained by the resin combination of the present invention has three fluorenes of divalent as repetitive unit.In this way, pass through tool There are three fluorenes of divalent as repetitive unit, can in addition have by obtaining desired optical characteristics using three fluorenes on a small quantity It can show the tendency of good heat resistance.

It should be noted that the polymer contained by the resin combination of the present invention can also further have as described later Two fluorenes of divalent are as repetitive unit.Sometimes both three fluorenes and two fluorenes are referred to as oligomeric fluorenes.

Three fluorenes of divalent include 3 fluorenes unit a with or without substituent group, and the carbon of 9 of fluorenes unit a is former Son be bonded directly with one another or the carbon atom of 9 of fluorenes unit a each other by with or without substituent group alkylidene, It arlydene with or without substituent group or is bonded with or without the sub- aralkyl of substituent group with chain.

As fluorenes unit a it is preferable to use the fluorenes unit a as three fluorenes diester illustrated in fluorenes unit.

Similarly, as bonding fluorenes unit a alkylidene it is preferable to use the bonding fluorenes unit a as three fluorenes diester Alkylidene illustrated in alkylidene.In addition, as bonding fluorenes unit a arlydene it is preferable to use as three fluorenes diester Bonding fluorenes unit a arlydene illustrated in arlydene.In addition, the sub- aralkyl as bonding fluorenes unit a, can preferably make It is used as the sub- aralkyl illustrated in the sub- aralkyl of the bonding fluorenes unit a of three fluorenes diester.

Three fluorenes of above-mentioned divalent or：In 3 fluorenes unit a, positioned at the carbon atom of 9 of the fluorenes unit a of two ends It is upper to be bonded with substituents alpha respectively¹And α², make the substituents alpha¹And α²For divalent group.In this case, α¹And α²It can be identical It can be different.In addition, substituents alpha¹And α²In include Direct Bonding, i.e. can also make fluorenes unit a the carbon atom of 9 be divalent Group.As substituents alpha¹And α²It is preferable to use as the substituents alpha in three fluorenes diester¹And α²Illustrated substituent group.

Particularly, in the carbon atom of 9 for making the fluorenes unit a positioned at two ends in the case of divalent group or to make position In the substituents alpha being bonded respectively on the carbon atom of 9 of the fluorenes unit a of two ends¹And α²For divalent group and make α¹And α²In The carbon number of at least one be more than 2 in the case of, due to fluorenes ring (fluorenes unit a) is generally perpendicularly orientated compared with main chain, because And even if the ratio of the oligomeric fluorenes of the divalent in resin combination is few, it may have easily shows the tendency of inverse wave length dispersiveness. In the case of the latter, from same aspect, preferably make α¹And α²The carbon number of the two is more than 2.On the other hand, make The α being bonded respectively on the carbon atom of 9 of the fluorenes unit a of two ends¹And α²For divalent group and make α¹And α²The carbon atom of the two In the case that number is 1 (that is, with or without the methylene of substituent group), (fluorenes unit a) is not big compared with main chain to fluorenes ring Cause is vertically oriented, and is significantly obliquely orientated, so even change the oligomeric fluorenes of the divalent in resin combination in wide scope Ratio, it may have be easily formed in the tendency of the small flat dispersiveness of difference of phase difference in wide band.

In this way, the resin combination of the present invention has the carbon atom of 9 of 3 fluorenes unit a by containing each other with spy The polymer for the repetitive unit that fixed carbon-carbon bond is formed by connecting, so as to more effectively obtain the optical characteristics from fluorenes ring.

As three fluorenes of above-mentioned divalent, the substance represented by specifically it is preferable to use the following general formula (11).

[changing 58]

In formula, R¹And R²It is 1~4 to be each independently Direct Bonding or the carbon number with or without substituent group Alkylidene,

It should be noted that the R in formula (11)^3aAnd R^3bIt can be the same or different respectively.In addition, divide in formula (11) R that Ju You be 3⁴~R⁹It can be the same or different respectively.

As the R in above-mentioned formula (11)¹~R⁹It is preferable to use as the R in above-mentioned formula (1)¹~R⁹Illustrated base Group.

Polymer in the resin combination of the present invention can further have two fluorenes of divalent as repetitive unit.Pass through Two fluorenes in addition to three fluorenes of divalent also containing divalent, have easily to be adjusted to desired feelings by heat resistance or optical characteristics The tendency of condition.

Two fluorenes of divalent include 2 fluorenes unit b with or without substituent group, and the carbon of 9 of fluorenes unit b is former Son be bonded directly with one another or the carbon atom of 9 of fluorenes unit b each other by with or without substituent group alkylidene, It arlydene with or without substituent group or is bonded with or without the sub- aralkyl of substituent group with chain.

As fluorenes unit b it is preferable to use the fluorenes unit b as two fluorenes diester illustrated in fluorenes unit.

Similarly, as bonding fluorenes unit b alkylidene it is preferable to use the bonding fluorenes unit b as two fluorenes diester Alkylidene illustrated in alkylidene.In addition, as bonding fluorenes unit b arlydene it is preferable to use as two fluorenes diester Bonding fluorenes unit b arlydene illustrated in arlydene.In addition, the sub- aralkyl as bonding fluorenes unit b, can preferably make It is used as the sub- aralkyl illustrated in the sub- aralkyl of the bonding fluorenes unit b of two fluorenes diester.

Two fluorenes of above-mentioned divalent or：It is bonded with respectively on the carbon atom of 9 positioned at the fluorenes unit b of two ends Substituents alpha³And α⁴, make the substituents alpha³And α⁴For divalent group.In this case, α³And α⁴It can be the same or different.Separately Outside, substituents alpha³And α⁴In include Direct Bonding, i.e. can also make fluorenes unit b the carbon atom of 9 be divalent group.As taking For base α³And α⁴It is preferable to use as the substituents alpha in two fluorenes diester³And α⁴Illustrated group.

Particularly, in the carbon atom of 9 for making the fluorenes unit b positioned at two ends in the case of divalent group or to make position In the substituents alpha being bonded respectively on the carbon atom of 9 of the fluorenes unit b of two ends³And α⁴For divalent group and make α³And α⁴In The carbon number of at least one be more than 2 in the case of, due to fluorenes ring (fluorenes unit b) is generally perpendicularly orientated compared with main chain, because And even if the ratio of the oligomeric fluorenes of the divalent in resin combination is few, it may have easily shows the tendency of inverse wave length dispersiveness. In the case of the latter, from same aspect, preferably make α³And α⁴The carbon number of the two is more than 2.On the other hand, exist Make the α being bonded respectively on the carbon atom of 9 of the fluorenes unit b of two ends³And α⁴For divalent group and make α³And α⁴The carbon of the two is former In the case that subnumber is 1 (that is, with or without the methylene of substituent group), (fluorenes unit b) is not fluorenes ring compared with main chain It is generally perpendicularly orientated, and is significantly obliquely orientated, so even changing the oligomeric fluorenes of the divalent in resin combination in wide scope Ratio, it may have be easily formed in the tendency of the small flat dispersiveness of difference of phase difference in wide band.

As two fluorenes of above-mentioned divalent, the substance represented by specifically it is preferable to use the following general formula (21).

[changing 59]

As the R in above-mentioned formula (21)¹~R⁹It is preferable to use as the R in above-mentioned formula (2)¹~R⁹Illustrated base Group.

It should be noted that the R of 2 is respectively provided in formula (21)⁴~R⁹It can be the same or different respectively.

<3.3 polymer>

Contained polymer has three fluorenes of divalent as repetitive unit in the resin combination of the present invention.For example, can be with Enumerate the polymer that three fluorenes of divalent are formed by connecting each other by arbitrary linking group.In addition, the polymer or having The copolymer of two fluorenes of divalent, the arbitrary repetitive unit beyond them.

<3.4 linking group>

The concrete structure of linking group used in above-mentioned polymer is enumerated below, but is not limited to these, Ke Yiju Go out the linking group shown in following [J] groups

[changing 60]

[J]

(in each linking group shown in above-mentioned [J] group, Z represents the position that is connected of repetitive unit, Y represent with it is other The position that the arbitrary structures unit that the position of linking group bonding or expression make linking group bond together is connected.), it can Two or more in these linking groups to be shared.In addition, in linking group to be asymmetrical, linking group can be with It is attached compared with repetitive unit with any direction.Among them, heat resistance and melt processable, mechanical strength are preferably comprised The polyester of balancing good, makrolon, polyestercarbonate, the linking group that is shown in following [K] groups.

[changing 61]

[K]

In each linking group shown in above-mentioned [K] group, Z represents the position that repetitive unit is connected.

Linking group can be used alone group, can also share two or more linking groups.

As the polymer for being attached repetitive unit through linking group, specifically, can enumerate comprising poly- Alkene, polyester, makrolon, polyamide, polyimides, polyurethane, epoxy resin, polyacrylate, polymethacrylates Or polysulfones polymer and the polymer that shares them, preferably comprise usually the polyolefin of high transparency, polyester, The polymer of makrolon, epoxy resin or polyacrylate, particularly preferably comprising heat resistance and melt processable, mechanical strength The polyester of balancing good or the polymer of makrolon, it is particularly preferably excellent comprising usual heat resistance, chemical resistance The polymer of makrolon.

In the case where the polymer for sharing two or more linking groups is made, the combination on linking group is without spy Do not limit, for example, share structural carbonate and ester structure as linking group polymer, share structural carbonate With carbamate structures as linking group polymer, share ester structure and polymer of the amide as linking group etc., Structural carbonate and polymer of the ester structure as linking group are shared it is preferred that can enumerate.Herein, it is two or more as sharing Linking group polymer concrete example, can enumerate polyestercarbonate, have the polyurethane of carbonic acid ester bond, polyesteramide, Polyesterimide etc., among them, preferably heat resistance and melt processable, the polyestercarbonate of the balancing good of mechanical strength. In this specification, the polymer with carbonic acid ester bond is known as makrolon, except only there is carbonic acid ester bond as linking group Polymer outside, also comprising polyestercarbonate (polymer with ester bond and carbonic acid ester bond), the polyurethane with carbonic acid ester bond Deng.Herein, the ratio of the carbonic acid ester bond in the polymer comprising makrolon can be arbitrary value, but in order to resin combination The excellent characteristics such as heat resistance, the chemical resistance brought by carbonic acid ester bond are assigned, are preferably more than certain proportion, carbonic acid Molar fraction of the ester bond in whole linking groups is preferably more than 30%, is more preferably more than 50%, further preferably More than 60%, more than 70% is particularly preferably, is usually less than 100%.

<3.5 copolymer>

Three fluorenes with divalent can be further to contain arbitrary divalent organic group (its as the polymer of repetitive unit In, two fluorenes of three fluorenes and divalent not including divalent) copolymer as repetitive unit.In this case, preferred repeat units that This is attached by above-mentioned linking group.

In copolymer, as the arbitrary divalent organic group that can be shared with three fluorenes of divalent, from control in resin combination The divalent to set out in object in terms of the scope of required optical characteristics and physical property represented by it is preferable to use the following general formula (3) Organic group.In this case, as arbitrary divalent organic group, can further share the divalent represented by general formula (3) has Divalent organic group beyond machine group.

[changing 62]

In formula, R²⁰Represent that the carbon number with or without substituent group is 2~20 alkylidene, with or without taking Arlydene that the carbon number of Dai Ji is 4~20, with or without substituent group carbon number be 2~100 alkylene ether Organic group with alicyclic structure that base, the carbon number with or without substituent group are 4~20 or with or do not have The carbon number of substituted base is 4~20 organic group with heterocycle structure.

In the case that polymer contains the divalent organic group represented by above-mentioned general formula (3), except that can undertake to resin group Object is closed to assign beyond the anisotropic function of positive refracting power, it can also be by the wavelength dispersibility of phase difference or photoelastic coefficient etc The various resin characteristics controls such as optics physical property and mechanical strength, heat resistance, melt processable have in preferred scope etc. The tendency of the physical property of resin combination can arbitrarily be controlled.

It should be noted that without compared with the vertical orientated aromatic rings of main chain or even if with such fragrance Also less resin combination usually shows positive refracting power anisotropy for ring its ratio in entirety, this is well-known 's.In the repetitive unit of divalent organic group represented by above-mentioned general formula (3), in addition to there is the structure of aromatic rings in side chain, It is all to show the anisotropic structure of positive refracting power, thus, it can be said that above-mentioned general formula (3) institute containing 50 moles of more than % The resin combination of the divalent organic group of expression shows positive refracting power anisotropy.

As described above, the R in general formula (3)²⁰The alkylene that expression is 2~20 with or without the carbon number of substituent group Arlydene that base, the carbon number with or without substituent group are 4~20, the carbon number with or without substituent group are The organic group with alicyclic structure that 2~100 alkylidene ether, the carbon number with or without substituent group are 4~20 Group or with or without substituent group carbon number be 4~20 the organic group with heterocycle structure.

The concrete structure of " alkylidene that the carbon number with or without substituent group is 2~20 " is enumerated below, but simultaneously These are not limited to, the alkylene of the straight-chains such as ethylidene, n-propylene, positive butylidene, positive pentylidene, positive hexylidene can be enumerated Base；1- methyl ethylidene, 2- methyl ethylidene, 1- ethylethylene residues, 2- ethylethylene residues, 1- methyl propylenes, 2- methyl are sub- Propyl, 2,2- dimethylpropylidenes, 3- methyl propylenes etc. include the alkylidene of branch.Its carbon number is more than 2 and excellent Elect less than 12, more preferably less than 6 as.Among them, appropriate hydrophobicity is preferably had with flexibility and with the low light of imparting The alkylidene of straight-chain represented by the tendency of coefficient of elasticity, the following general formula (5).

[changing 63]

(in formula, R^2-11The straight-chain alkylidene that expression is 0~18 with or without the carbon number of substituent group.)

The specific knot of " the straight-chain alkylidene that the carbon number with or without substituent group is 0~18 " is enumerated below Structure, but these are not limited to, ethylidene, n-propylene, positive butylidene, positive pentylidene, positive hexylidene etc. can be enumerated.Its carbon is former Subnumber is preferably more than 2, and preferably less than 10, more preferably less than 4.

The concrete structure of " arlydene that the carbon number with or without substituent group is 4~20 " is enumerated below, but simultaneously These are not limited to, the phenylenes such as 1,2- phenylenes, 1,3- phenylenes, Isosorbide-5-Nitrae-phenylene can be enumerated；1,5- naphthylenes, 2,6- are sub- The naphthylenes such as naphthalene；The heteroarylidenes such as 2,5- sub-pyridyl groups, 2,4- Asias thienyl, 2,4- furylidenes.Its carbon number is preferred For more than 4 and be less than 8, more preferably less than 6.Among them, go out in terms of it can industrially obtain at low cost Hair, preferably 1,2- phenylenes, 1,3- phenylenes or Isosorbide-5-Nitrae-phenylene.

As " alkylidene that the carbon number with or without substituent group is 2~20 ", " with or without substituent group Carbon number be 0~18 straight-chain alkylidene " and " carbon number with or without substituent group be 4~20 Asia virtue The substituent group that base " can have can be enumerated：Halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom)；Carbon number For 1~10 alkyl (such as methyl, ethyl, isopropyl etc.)；Alkoxy (such as methoxyl group, the ethoxy that carbon number is 1~10 Base etc.)；Carbon number is 1~10 acyl group (such as acetyl group, benzoyl etc.)；Carbon number is 1~10 amide groups (example Such as acetamido, benzamido)；Nitro；Cyano；With or without selected from halogen atom (such as fluorine atom, chlorine atom, Bromine atoms, iodine atom), the alkyl (such as methyl, ethyl, isopropyl etc.) that carbon number is 1~10, carbon number be 1~10 Alkoxy (such as methoxyl group, ethyoxyl etc.), carbon number be 1~10 acyl group (such as acetyl group, benzoyl etc.), carbon Atomicity is 1~3 substituent group in 1~10 amide groups (such as acetamido, benzamido etc.), nitro, cyano etc. Carbon number be 6~10 aryl (such as phenyl, naphthalene etc.) etc..The quantity of the substituent group is not particularly limited, preferably 1~ 3.In the case that substituent group is 2 or more, the species of substituent group can be the same or different.In addition, from industrially can The aspect manufactured at low cost is set out, preferably unsubstituted.

As the concrete example of the alkylidene with substituent group, phenyl-ethylene, 1- phenylpropylenes, 1- hexamethylenes can be enumerated Base propylidene, 1,1,2,2- tetrafluoro ethylidene etc..

As the concrete example of the arlydene with substituent group, 2- methyl-1s, 4- phenylenes, 5- methyl-1s, 3- can be enumerated Phenylene, 2,5- dimethyl -1,4- phenylenes, 2- methoxyl group -1,4- phenylenes, 2- Trifluoromethyl-1s, 4- phenylenes, 2,5- bis- Methoxyl group -1,4- phenylenes, tetra- fluoro- 1,4- phenylenes of 2,3,5,6- etc. substitute arlydene.

The concrete structure of " the sub- aralkyl that the carbon number with or without substituent group is 6~20 " is enumerated below, but These are not limited to, the sub- aralkyl shown in following [L] group can be enumerated.

[changing 64]

[L]

Its carbon number is preferably more than 6 and is less than 10, and more preferably less than 8.Among them, from industrial energy Enough aspects obtained at low cost are set out, and are preferably adjacent xylylene, xylylene or to xylylene.

As " the sub- aralkyl that the carbon number with or without substituent group is 6~20 " substituent group that can have, It can enumerate：Halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom)；Alkyl (such as the first that carbon number is 1~10 Base, ethyl, isopropyl etc.)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Carbon number for 1~ 10 acyl group (such as acetyl group, benzoyl etc.)；Amide groups (such as acetamido, the benzamide that carbon number is 1~10 Base etc.)；Nitro；Cyano；With or without former selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), carbon Alkyl (such as methyl, ethyl, isopropyl etc.) that subnumber is 1~10, the alkoxy that carbon number is 1~10 (such as methoxyl group, Ethyoxyl etc.), the acyl group (such as acetyl group, benzoyl etc.) that carbon number is 1~10, the amide that carbon number is 1~10 The carbon number of 1~3 substituent group in base (such as acetamido, benzamido etc.), nitro, cyano etc. is 6~10 Aryl (such as phenyl, naphthalene etc.) etc..The quantity of the substituent group is not particularly limited, preferably 1~3.Substituent group is 2 or more In the case of, the species of substituent group can be the same or different.In addition, go out in terms of it can industrially manufacture at low cost Hair, it is preferably unsubstituted.

" the alkylidene ether that the carbon number with or without substituent group is 2~100 " refers to the Asia of 1 or more The divalent group of alkyl and etheric oxygen atom.Its carbon number is preferably more than 4, more preferably more than 6, and preferably 60 with Under, more preferably less than 50, further preferably less than 40, particularly preferably less than 30.More specifically, can enumerate：Under State general formula (7)

[changing 65]

(in formula, R^2-13The alkylidene that expression is 2~10 with or without the carbon number of substituent group, p are 1~40 Integer.) represented by group or the following general formula (8)

[changing 66]

(in formula, R^2-14Represent to be 2~10 alkylidene, R with or without the carbon number of substituent group^2-15Expression has Or the arlydene that the carbon number without substituent group is 12~30.) represented by group.

In general formula (7) and general formula (8), R^2-13And R^2-14Represent to be 2~10 with or without the carbon number of substituent group Alkylidene.Its concrete structure is enumerated below, but is not limited to these, can be enumerated：Ethylidene, n-propylene, positive butylidene, just The alkylidene of the straight-chains such as pentylidene, positive hexylidene；1- methyl ethylidene, 2- methyl ethylidene, 1- ethylethylene residues, 2- ethyls Ethylidene, 1- methyl propylenes, 2- methyl propylenes, 2,2- dimethylpropylidenes, 3- methyl propylenes etc. include the Asia of branch Alkyl (numerical value of the position of substitution is counted from the carbon of end side herein) etc..

Its carbon number is preferably more than 2 and is less than 8, and more preferably less than 4.

As " with or without substituent group carbon number be 2~100 alkylidene ether " and " with or without The carbon number of substituent group is 2~10 alkylidene " substituent group that can have, it can enumerate：Halogen atom (such as fluorine atom, Chlorine atom, bromine atoms, iodine atom)；Carbon number is 1~10 alkyl (such as methyl, ethyl, isopropyl etc.)；Carbon number For 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Acyl group (such as acetyl group, the benzoyl that carbon number is 1~10 Base etc.)；Carbon number is 1~10 amide groups (such as acetamido, benzamido etc.)；Nitro；Cyano；Have or do not have Have selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), carbon number be 1~10 alkyl (such as methyl, Ethyl, isopropyl etc.), the alkoxy (such as methoxyl group, ethyoxyl etc.) that carbon number is 1~10, carbon number be 1~10 Acyl group (such as acetyl group, benzoyl etc.), amide groups (such as acetamido, the benzamido that carbon number is 1~10 Deng), nitro, 1~3 substituent group in cyano etc. carbon number be 6~10 aryl (such as phenyl, naphthalene etc.) etc..It should The quantity of substituent group is not particularly limited, preferably 1~3.In the case that substituent group is 2 or more, the species of substituent group can be with It is identical can not also be same.In addition, from the aspect that can industrially manufacture at low cost, it is preferably unsubstituted.

These R^2-13And R^2-14In, the preferred alkylidene of straight-chain, the alkylidene of straight-chain due to do not have asymmetric point because And the qualitative control of monomer is easily carried out, it more preferably can industrially import at low cost, flexibility and water imbibition can be assigned Ethylidene.

In general formula (7), p is 1~40 integer, preferably more than 1, more preferably more than 2, and preferably less than 30, More preferably less than 20.

In general formula (8), R^2-15The arlydene that expression is 12~30 with or without the carbon number of substituent group.It names Go out its concrete structure, but be not limited to these, it is excellent from the glass transition temperature aspect that can improve resin combination Choosing can enumerate the arlydene shown in following [M] groups.

[changing 67]

[M]

It, can as the substituent group that " arlydene that the carbon number with or without substituent group is 12~30 " can have To enumerate：Halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom)；Alkyl (such as the first that carbon number is 1~10 Base, ethyl, isopropyl etc.)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Carbon number for 1~ 10 acyl group (such as acetyl group, benzoyl etc.)；Amide groups (such as acetamido, the benzamide that carbon number is 1~10 Base etc.)；Nitro；Cyano；With or without former selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), carbon Alkyl (such as methyl, ethyl, isopropyl etc.) that subnumber is 1~10, the alkoxy that carbon number is 1~10 (such as methoxyl group, Ethyoxyl etc.), the acyl group (such as acetyl group, benzoyl etc.) that carbon number is 1~10, the amide that carbon number is 1~10 The carbon number of 1~3 substituent group in base (such as acetamido, benzamido etc.), nitro, cyano etc. is 6~10 Aryl (such as phenyl, naphthalene etc.) etc..The quantity of the substituent group is not particularly limited, preferably 1~3.Substituent group is 2 or more In the case of, the species of substituent group can be the same or different.In addition, go out in terms of it can industrially manufacture at low cost Hair, it is preferably unsubstituted.

The concrete structure of formula (7) is enumerated below, but is not limited to these, can enumerate the alkylidene shown in following [N] group Ether.

[changing 68]

[N]

(can be any one diastereomer on the structure that may be diastereomer in above-mentioned [N] group, or Non-enantiomer mixture.)

The concrete structure of formula (8) is enumerated below, but is not limited to these, can be enumerated：Alkylidene shown in following [O] group Ether.

[changing 69]

[o]

(can be any one diastereomer on the structure that may be diastereomer in above-mentioned [O] group, or Non-enantiomer mixture.)

" the organic group with alicyclic structure that the carbon number with or without substituent group is 4~20 is enumerated below Or with or without substituent group carbon number be 4~20 the organic group with heterocycle structure " concrete structure, but These are not limited to, it is excellent for can improve glass transition temperature, can reduce the reason for tendency of photoelastic coefficient Choosing can enumerate the Asia at the alicyclic structure or arbitrary the 2 of heterocycle structure shown in following [P] group with straight-chain or branched The organic group of the associative key of alkyl.

[changing 70]

[P]

(the position of substitution of 2 associative keys in each ring structure shown in above-mentioned [P] group is arbitrary, and 2 associative keys can To be substituted on same carbon.) associative key herein for Direct Bonding or be carbon number 1~5 straight-chain or branch The alkylidene of shape, 2 combination key lengths can be different.Preferred associative key for glass transition temperature few direct of reduction Bonding or methylene.

As " the organic group or tool with alicyclic structure that the carbon number with or without substituent group is 4~20 Have or the organic group with heterocycle structure that carbon number without substituent group is 4~20 " can with substituent group, can To enumerate：Halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom)；Alkyl (such as the first that carbon number is 1~10 Base, ethyl, isopropyl etc.)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Carbon number for 1~ 10 acyl group (such as acetyl group, benzoyl etc.)；Amide groups (such as acetamido, the benzamide that carbon number is 1~10 Base etc.)；Nitro；Cyano；With or without former selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), carbon Alkyl (such as methyl, ethyl, isopropyl etc.) that subnumber is 1~10, the alkoxy that carbon number is 1~10 (such as methoxyl group, Ethyoxyl etc.), the acyl group (such as acetyl group, benzoyl etc.) that carbon number is 1~10, the amide that carbon number is 1~10 The carbon number of 1~3 substituent group in base (such as acetamido, benzamido etc.), nitro, cyano etc. is 6~10 Aryl (such as phenyl, naphthalene etc.) etc..The quantity of the substituent group is not particularly limited, preferably 1~3.Substituent group is 2 or more In the case of, the species of substituent group can be the same or different.In addition, go out in terms of it can industrially manufacture at low cost Hair, it is preferably unsubstituted.

" the organic group with alicyclic structure that the carbon number with or without substituent group is 4~20 is enumerated below Or with or without substituent group carbon number be 4~20 the organic group with heterocycle structure " preferred specific knot Structure, but these are not limited to, it can enumerate：With can assign high transparency and glass transition temperature, water imbibition, birefringence, The tendency of low photoelastic coefficient, the following general formula (4)

[changing 71]

Represented group, the following general formula (6)

[changing 72]

(in formula, R^2-12The ring alkylidene that expression is 4~20 with or without the carbon number of substituent group.) represented by Group or the following general formula (9)

[changing 73]

(in formula, R^2-16The base with acetal ring that expression is 2~20 with or without the carbon number of substituent group Group.) represented by group.

In general formula (6), R^2-12The ring alkylidene that expression is 4~20 with or without the carbon number of substituent group.Below Its concrete structure is enumerated, but is not limited to these, for can improve glass transition temperature, photoelasticity system can be reduced The reason for several tendency, it can preferably enumerate the ring alkylidene shown in following [Q] groups.

[changing 74]

[Q]

(can be any one diastereomer on the structure that may be diastereomer in above-mentioned [Q] group, or Non-enantiomer mixture.)

As " the ring alkylidene that the carbon number with or without substituent group is 4~20 " substituent group that can have, It can enumerate：Halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom)；Alkyl (such as the first that carbon number is 1~10 Base, ethyl, isopropyl etc.)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Carbon number for 1~ 10 acyl group (such as acetyl group, benzoyl etc.)；Amide groups (such as acetamido, the benzamide that carbon number is 1~10 Base etc.)；Nitro；Cyano；With or without former selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), carbon Alkyl (such as methyl, ethyl, isopropyl etc.) that subnumber is 1~10, the alkoxy that carbon number is 1~10 (such as methoxyl group, Ethyoxyl etc.), the acyl group (such as acetyl group, benzoyl etc.) that carbon number is 1~10, the amide that carbon number is 1~10 The carbon number of 1~3 substituent group in base (such as acetamido, benzamido etc.), nitro, cyano etc. is 6~10 Aryl (such as phenyl, naphthalene etc.) etc..The quantity of the substituent group is not particularly limited, preferably 1~3.Substituent group is 2 or more In the case of, the species of substituent group can be the same or different.In addition, go out in terms of it can industrially manufacture at low cost Hair, it is preferably unsubstituted.

The concrete structure of general formula (6) is enumerated below, but is not limited to these, can enumerate having shown in following [R] group The organic group of alicyclic structure

[changing 75]

[R]

(can be any one diastereomer on the structure that may be diastereomer in above-mentioned [R] group, or Non-enantiomer mixture.).Among these, from the aspect that can industrially obtain at low cost, preferably following [R-2] groups In the organic group with alicyclic structure that shows.

[changing 76]

[R-2]

In general formula (9), R^2-16It represents to be 2~20 with or without the carbon number of substituent group with acetal ring Group.Enumerate its concrete structure below, but be not limited to these, for can improve glass transition temperature with it is two-fold Penetrate, can reduce the reason for tendency of photoelastic coefficient, can preferably enumerate show in following [S] groups there is acetal ring Group.

[changing 77]

[S]

(can be any one diastereomer on the structure that may be diastereomer in above-mentioned [S] group.)

As " the acetal ring that the carbon number with or without substituent group is 2~20 " substituent group that can have, It can enumerate：Halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom)；Alkyl (such as the first that carbon number is 1~10 Base, ethyl, isopropyl etc.)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Carbon number for 1~ 10 acyl group (such as acetyl group, benzoyl etc.)；Amide groups (such as acetamido, the benzamide that carbon number is 1~10 Base etc.)；Nitro；Cyano；With or without former selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), carbon Alkyl (such as methyl, ethyl, isopropyl etc.) that subnumber is 1~10, the alkoxy that carbon number is 1~10 (such as methoxyl group, Ethyoxyl etc.), the acyl group (such as acetyl group, benzoyl etc.) that carbon number is 1~10, the amide that carbon number is 1~10 The carbon number of 1~3 substituent group in base (such as acetamido, benzamido etc.), nitro, cyano etc. is 6~10 Aryl (such as phenyl, naphthalene etc.) etc..The quantity of the substituent group is not particularly limited, preferably 1~3.Substituent group is 2 or more In the case of, the species of substituent group can be the same or different.In addition, go out in terms of it can industrially manufacture at low cost Hair, it is preferably unsubstituted.

The preferred group in divalent organic group represented by general formula (3) is alkylidene, the tool with or without substituent group Have or the alkylidene ether without substituent group, the organic group or tool with alicyclic structure with or without substituent group Have or the organic group with heterocycle structure without substituent group, these preferred groups do not have in main chain aromatic rings or Largely containing the part-structure beyond aromatic rings in main chain, thus with the low photoelasticity required by can realizing in optical film The tendency of coefficient.More preferably selected from least one of following radicals：

With the tendency that can assign high transparency and glass transition temperature, water imbibition, birefringence, low photoelastic coefficient The following general formula (4),

[changing 78]

Or hydrophobicity and flexibility, the following general formula (5) with the tendency that can assign low photoelastic coefficient with appropriateness

[changing 79]

(in formula, R^2-11The straight-chain alkylidene that expression is 0~18 with or without the carbon number of substituent group.) or Person have can assign high transparency and glass transition temperature, appropriateness flexibility tendency the following general formula (6)

[changing 80]

(in formula, R^2-12The ring alkylidene that expression is 4~20 with or without the carbon number of substituent group.) or tool Have the tendency of that flexibility and water imbibition, the following general formula (7) of low photoelastic coefficient can be assigned

[changing 81]

(in formula, R^2-13The alkylidene that expression is 2~10 with or without the carbon number of substituent group, p are 1~40 Integer.) or with can assign high transparency and glass transition temperature tendency the following general formula (8)

[changing 82]

(in formula, R^2-14Represent to be 2~10 alkylidene, R with or without the carbon number of substituent group^2-15Expression has Or the arlydene that the carbon number without substituent group is 12~30.) or with high transparency and glass transition can be assigned Temperature, the following general formula (9) of birefringent tendency

[changing 83]

(in formula, R^2-16The base with acetal ring that expression is 2~20 with or without the carbon number of substituent group Group.).Group represented by further preferred above-mentioned general formula (4), the group represented by above-mentioned general formula (4) is by assigning high transparency Property with glass transition temperature, water imbibition, low photoelastic coefficient and with inclining for the physical property excellent as phase difference film can be assigned To.

Divalent organic group represented by general formula (3) can be used alone, and also can share to use by two or more. Between batch is reduced optics physical property, mechanical properties fluctuation or the like qualitative control aspect, be preferably used alone one Kind.On the other hand, from taking into account optical characteristics, mechanical properties aspect, preferably share to use by two or more, and lead to Often it is less than 4 kinds, preferably used below with 3 kinds.

By the divalent organic group represented by general formula (3) share it is two or more in the case of, do not limited especially on its combination It is fixed.For example, for assigning high transparency and glass transition temperature, birefringent purpose, represented by preferably above-mentioned general formula (4) Organic group represented by organic group or above-mentioned general formula (9), for the purpose for assigning flexibility, preferably above-mentioned general formula (5) institute Organic group represented by the organic group of expression or above-mentioned general formula (7), on the other hand, for imparting high transparency and glass Change transition temperature, appropriateness flexibility purpose, the organic group represented by preferably above-mentioned general formula (6), among them, according to institute It is required that the combination of purpose select the combination of corresponding organic group.It is in particular, it is preferred that above-mentioned to be equivalent to The repetitive unit in ISB (isobide) source of the organic group represented by general formula (4) is represented with being equivalent to above-mentioned general formula (6) Organic group CHDM (1,4 cyclohexane dimethanol) source repetitive unit combination or be equivalent to above-mentioned general formula (9) The repetitive unit in SPG (the spiroglycol) source of represented organic group is organic represented by above-mentioned general formula (6) with being equivalent to The combination of the repetitive unit in the CHDM sources of group.

<3.7 copolymerization compositions>

In this way, using two fluorenes of three fluorenes at least containing divalent, divalent and the divalent organic group represented by general formula (3) In the case of copolymer as repetitive unit, as long as in the range of it can show aftermentioned optics physical property, you can above-mentioned Three fluorenes of divalent, two fluorenes of divalent, the divalent organic group represented by general formula (3) are contained with arbitrary quality in copolymer.

The summation of the content ratio of two fluorenes of three fluorenes and divalent on divalent, in order to show inverse wave length dispersiveness and ensure Melt processable, mechanical strength are preferably more than 5 mass %, more preferably 10 matter compared with the quality of above-mentioned copolymer entirety Measure more than %, further preferably more than 12 mass %, particularly preferably more than 15 mass %, and preferably 90 mass % with Under, more preferably below 80 mass %, further preferably below 70 mass %, particularly preferably below 60 mass %.

In addition, from by lesser amount of, using desired optical characteristics aspect is obtained, three fluorenes of divalent contain The proportional quality compared with copolymer entirety is preferably more than 1 mass %, is more preferably more than 3 mass %, is further preferred For more than 5 mass %, it is particularly preferably more than 10 mass %, and preferably below 50 mass %, more preferably 40 mass % Below, it is more preferably below 30 mass %.

In addition, from the aspect of positive refracting power anisotropy is assigned, divalent organic group represented by general formula (3) it is excellent Select content ratio be preferably more than 10 mass % compared with the quality of above-mentioned copolymer entirety, more preferably more than 20 mass %, Further preferably more than 30 mass %, particularly preferably more than 40 mass %, and preferably below 95 mass %, more preferably For below 90 mass %, further preferably below 88 mass %, particularly preferably below 85 mass %, most preferably 80 matter Measure below %.

<3.8 polymer are blended>

The resin combination of the present invention contains polymer of three fluorenes as repetitive unit with divalent.In addition, the present invention Resin combination can also further contain other ingredients in addition to containing the polymer.

In the resin combination of the present invention, expectation shows other effects as caused by blending, can also contain arbitrary Polymer as other ingredients.That is, in addition to three fluorenes with divalent are as the polymer of repetitive unit, can also coexist There is arbitrary polymer.

Described herein coexist refers to that the method coexisted is unlimited there are polymer of more than two kinds in resin combination, Can enumerate polymer of more than two kinds is mixed with the state of the state of solution or melting method, containing a kind or more Polymer solution in or molten liquid in the method that is polymerize etc..

For example, can be blended with polymer of the divalent organic group represented by general formula (3) as repetitive unit, also may be used The polymer with arbitrary repetitive unit is blended.It should be noted that with the divalent organic group represented by general formula (3) Polymer as repetitive unit can further have the divalent organic group beyond general formula (3) as repetitive unit, can also With the divalent organic group represented by two or more general formulas (3) as repetitive unit.Herein, as represented by general formula (3) Divalent organic group can use the group preferably exemplified in the copolymer.

Particularly from the aspect suitable for being used as phase difference film, preferably coexist and show positive refracting power anisotropy Polymer or oligomer blend or copolymer；For optical property it is good, have and can carry out melted masking or molten The reason for tendency of liquid cast film, thermoplastic resin more preferably coexists.As concurrent, specifically, polycondensation can be enumerated Based polymer, olefin polymer or addition polymerization based polymer, preferably polycondensation based polymer.As polycondensation based polymer, Polyester, polyamide, polyestercarbonate, polyamide, polyimides etc. can be enumerated, wherein it is preferred that polyester or makrolon.

More specifically, can enumerate：The olefin polymers such as polyethylene, polypropylene；With from bisphenol-A or bis-phenol Z, the makrolon of the structural unit of isobide etc.；Polyethylene terephthalate, polybutylene terephthalate (PBT) gather Naphthalate, polycyclic hexane Dimethylenecyclohexacompound dicarboxylic ester, poly terephthalic acid -1,4 cyclohexane dimethanol ester etc. are poly- Ester etc. can share the polymer of more than two kinds among them.

In the case of molding to the resin combination progress film of the present invention, since preferred film is optically transparent thus excellent Select the polymer that is blended and three fluorenes with divalent as the refractive index close of the polymer of repetitive unit or select with The combination of compatibility.

From showing inverse wave length dispersiveness and ensure melt processable, mechanical strength aspect, resin combination In three fluorenes of divalent and the summation of content ratio of two fluorenes of divalent compared with the quality of resin combination entirety be preferably 5 matter Measure more than %, more preferably more than 10 mass %, further preferably more than 12 mass %, particularly preferably 15 mass % with It is upper, be most preferably more than 20 mass %, it is and preferably below 90 mass %, more preferably below 80 mass %, further excellent It elects as below 70 mass %, particularly preferably below 60 mass %.In addition from same aspect, 2 represented by general formula (3) The ratio that preferably comprises of the organic group of valency is preferably more than 10 mass %, more preferably compared with the quality of resin combination entirety For more than 20 mass %, further preferably more than 30 mass %, particularly preferably more than 40 mass %, and preferably 95 matter Measure below %, more preferably below 90 mass %, further preferably below 88 mass %, particularly preferably 85 mass % with Under, be most preferably below 80 mass %.

In addition, the resin combination of the present invention can contain the divalent organic group represented by two or more above-mentioned general formulas (3) Group, for example, the weight in the repetitive unit in ISB (isobide) source and CHDM (1,4-CHDM) source is being applied in combination It in the case of multiple unit, is not particularly limited on its content ratio, from high glass-transition temperature and birefringence, water absorption rate Aspect is set out, and the repetitive unit in ISB sources is preferably more than 20 mass %, is more excellent with molar fraction compared with resin combination It elects as more than 30 mass %, further preferably more than 40 mass %, and preferably below 95 mass %, more preferably 90 matter Measure below %, further preferably below 80 mass %.

In addition, in the case of the repetitive unit and the repetitive unit in CHDM sources that ISB sources are applied in combination, contain on it Proportional to be not particularly limited, from flexibility aspect, the repetitive unit in CHDM sources is compared with resin combination to rub Your fraction meter is preferably more than 5 mass %, is more preferably more than 10 mass %, further preferably more than 15 mass %, and Preferably below 60 mass %, more preferably below 50 mass %, further preferably below 40 mass %.

In the case of the repetitive unit and the repetitive unit in CHDM sources that SPG (the spiroglycol) source is applied in combination, close It is not particularly limited in its content ratio, from high glass-transition temperature and birefringence, water absorption rate aspect, SPG sources Repetitive unit compared with resin combination with molar fraction be preferably 30 moles of more than %, more preferably 40 moles of % with Upper, further preferably 50 moles of more than %, and preferably 95 moles of below %, more preferably 90 moles of below %, into one Step is preferably 85 moles of below %.

In addition, in the case of the repetitive unit and the repetitive unit in CHDM sources that SPG sources are applied in combination, contain on it Proportional to be not particularly limited, from flexibility aspect, the repetitive unit in CHDM sources is compared with resin combination to rub Your fraction meter is preferably more than 5 mass %, is more preferably more than 10 mass %, further preferably more than 15 mass %, and Preferably below 60 mass %, more preferably below 50 mass %, further preferably below 40 mass %.

<3.10 physics value>

The physics value of the resin combination of the present invention is not particularly limited, and preferably satisfies physics value illustrated below.

<3.20 Abbe number>

In the resin combination of the present invention, it is being assumed to be the feelings of the wide bands zero birefraction material such as camera system optical lens Under condition, preferably Abbe number is less than 35.In order to use the present invention resin combination design camera system optical lens, preferably Ah Shellfish value is relatively low.Thus, Abbe number is more preferably less than 30, particularly preferably less than 25, is usually more than 15.

In the resin combination of the present invention, the 740cm of fluorenes ring orientation is come from^-1Absorption in draw direction and vertical direction Intensity ratio is preferably more than 1.2, more preferably more than 1.3, further preferably more than 1.4, and usually less than 2.0.It will In the case that the resin combination of the present invention is used as inverse wave length dispersion membrane purposes, the 740cm of fluorenes ring orientation is being come from^-1Absorption exist When the intensity ratio of draw direction and vertical direction is high, even if the repetitive unit with fluorenes ring contained in the resin combination Ratio is reduced, it may have shows the tendency of inverse wave length dispersiveness.It should be noted that above-mentioned intensity ratio can be by the following method It is measured.

Stretched film is made by the resin combination of the present invention first, implements polarisation ATR analyses.In the analysis result, source In the 1245cm of carbonyl orientation^-1Absorption in the intensity ratio of draw direction and vertical direction (2 color ratios：The intensity of draw direction/hang down Nogata to intensity) for more than 1.2, confirm main chain and be orientated in draw direction.Then calculate and come from fluorenes ring orientation 740cm^-1Absorption in draw direction and the intensity ratio of vertical direction.

<3.22 main chains and fluorenes angulation>

On the resin combination of the present invention, the specific conformations (configuration) of three fluorenes of divalent is not using gauche conformation to stablize structure As in the case of, it is 50 ° or more, is preferably 60 ° or more, more preferably in main chain and the fluorenes ring angulation of anti conformation At 70 ° or more, it is contemplated that inverse wave length dispersiveness can be shown.

Fluorenes ring and main chain angulation in the energy balane and the conformation of the specific conformation (configuration) of three fluorenes of divalent Calculating can such as get off to calculate.

For AM1 methods, software uses the PC Spartan Pro 1.0.5 that Wavefunction societies of the U.S. manufacture (32 versions of Windows (registered trademark)).It should be noted that it is complete with the relevant input value of computational accuracy to focus on decision content etc. Portion uses the default value of the software.

Herein, three fluorenes on divalent, in the case of poly carbonate resin composition, for last by the two of repetitive unit End carries out the structure that methyl carbonate forms and is calculated；In the case of polyester or polyestercarbonate resins composition, for The structure that the two ends progress methyl-esterified of repetitive unit forms is calculated.

Using AM1 methods, the two for 2 side chains present in each monomer is anti conformation and the two is two kinds The energy difference of the rotamer of gauche conformation is calculated.In addition, for anti conformation and gauche conformation (two kinds of gauche conformations Middle Stable conformation), carry out the calculating of main chain and fluorenes ring angulation.

It should be noted that main chain is identified below with fluorenes ring angulation.First, by the carbon atom of the methyl of two ends The straight line being connected to each other as main chain direction, using through the plane of the 3 of fluorenes, 6,9 carbon atoms as fluorenes plane.This When, although the straight line in the fluorenes plane intersected with main chain direction is unlimited existing, the fluorenes with the angle minimum in main chain direction Straight line in plane uniquely determines.Using the angle as main chain and fluorenes ring angulation.

As the divalent organic group imported in the resin combination of the present invention represented by above-mentioned general formula (3) as repetition The method of unit, the transparency, preferably uniformity aspect, following methods from obtained resin combination：

1. by the dihydroxy compounds with three fluorenes and the following formula with the organic group represented by above-mentioned general formula (3) (21) method of the dihydroxy compounds copolymerization represented by；

2. three fluorenes diester compounds are utilized into following formula (21) institute table with the organic group represented by above-mentioned general formula (3) After the dihydroxy compounds shown carries out transesterification, with following formula (21) institute with the organic group represented by above-mentioned general formula (3) The dihydroxy compounds of expression is copolymerized, the method imported by two steps；

3. by three fluorene diaryl ester compounds and following formula (21) institute with the organic group represented by above-mentioned general formula (3) The method of the dihydroxy compounds copolymerization of expression；

4. by the hydroxy compounds with three fluorenes, the following general formula with the organic group represented by above-mentioned general formula (3) (28) dicarboxylic acid compound represented by and the following general formula (21) institute with the organic group represented by above-mentioned general formula (3) The method of the dihydroxy compounds copolymerization of expression.

HO-R²⁰-OH (21)

HOCOR²⁰-COOH (28)

In formula (21) and formula (28), R²⁰With the R of above-mentioned general formula (3)²⁰It is identical.

Herein, the divalent organic group represented by above-mentioned general formula (3) can use the group of single kind, also can be by two kinds More than different organic group be applied in combination.Be applied in combination two or more different organic groups can by using it is two or more not With above-mentioned general formula (21) represented by dihydroxy compounds and/or dicarboxylic acid compound represented by above-mentioned general formula (28) reach Into.

<3.24 phase difference ratio>

The resin combination of the present invention is measured in the case where being assumed to be phase difference film purposes preferably at wavelength 450nm Phase difference (Re450) with wavelength 550nm at the ratio between phase difference (Re550) of measure, i.e. phase difference ratio meet following formula (20)。

Re450/Re550≤1.0 (20)

Herein, " the phase difference ratio of resin combination of the invention meets above-mentioned formula (20) " refers to, is being shaped to stretched film When, in following determination conditions, the phase difference (Re450) measured at wavelength 450nm and the phase difference measured at wavelength 550nm The ratio between (Re550) above-mentioned formula (20) is met.

Phase difference ratio measures as follows.Resin combination is suppressed using hot press, makes film.The film is cut Into defined size, free end simple tension is carried out, makes stretched film.Using measuring difference of phases device, (prince measures machine society Manufacture KOBRA-WPR), for phase difference (Re450) of the stretched film in wavelength 450nm and the phase difference in wavelength 550nm (Re550) it is measured.For draw direction, in the case that phase difference ratio (Re450/Re550) meets above-mentioned formula (20), the tree Oil/fat composition shows the wavelength dispersibility useful as phase difference film.

The resin combination of the present invention is in the case of the inverse wave length dispersion membrane purposes being assumed in phase difference film, phase difference The upper limit than (Re450/Re550) is preferably less than 1.0, more preferably less than 1.0, further preferably less than 0.95, more into one Step is preferably less than 0.93, particularly preferably less than 0.91.In addition, the lower limit of phase difference ratio (Re450/Re550) be preferably 0 with It is upper, more preferably more than 0.50, further preferably more than 0.50, be still more preferably more than 0.70, particularly preferably 0.75 Above, it is most preferably more than 0.80.

As long as the value of phase difference ratio (Re450/Re550) is in above range, then wavelength is longer, can more show phase Difference can obtain preferable phase difference characteristics under each wavelength of visibility region.For example, as so that shaking in mutually perpendicular direction The phase of dynamic polarised light carries out 1/4 λ plates of (90 °) variations of 1/4 wavelength, can be used by having the sheet of such wavelength dispersibility The phase difference film that invention resin combination obtains by itself and polarizing plate sticking, so as to make circular polarizing disk etc., can be realized complete There is the circular polarizing disk and image display device that prevent the black of external light reflection excellent under portion's wavelength.On the other hand, In the case where the value of phase difference ratio (Re450/Re550) is outer for above range, the decoloration (Se order け caused by wavelength) become larger, have Have the tendency of generating coloring problem in circular polarizing disk or image display device.

《Invention 3》

Hereinafter, obtained to 3 oligomeric fluorenes, the oligomeric fluorenes composition comprising the oligomeric fluorenes of the invention and using the oligomeric fluorenes To resin combination be described in detail.

It should be noted that (general formula) formula (1)~(5) recorded below, (4-1), (2a), (2b), (2c-1), (2c- 2), (2d), (7)~(9), (11), (A), (A-1), (B) are used to illustrate each structure in the present invention 3.

<1 has the Oligofluorenylene compounds A1 of 1 reactive functional groups>

The oligomeric fluorenes (hereinafter sometimes called " oligomeric fluorenes A1 ") with 1 reactive functional groups of the present invention includes tool Have or the carbon atom of 9 of the fluorenes unit a of 2 or more without substituent group is each other by the Asia with or without substituent group Alkyl, the arlydene with or without substituent group or the sub- aralkyl with or without substituent group with chain be bonded and Into oligomeric fluorene structural units a, also,

There is following formula on the carbon atom of 9 of the fluorenes unit a of any one end in the oligomeric fluorene structural units a (A) reactive functional groups represented by have hydrogen atom on the carbon atom of 9 of the fluorenes unit a of another end.

[changing 84]

In formula (A), R^a~R^cIt is each independently hydrogen atom, the carbon number with or without substituent group is 1~10 The aryl or the carbon atom with or without substituent group that alkyl, the carbon number with or without substituent group are 4~10 Number is 6~10 aralkyl, and X is ester group, amide groups, carboxyl, cyano or nitro.* it is the carbon atom with 9 of fluorenes unit a With reference to associative key.

In this way, by making reactive functional groups for specific structure, so as to can industrially obtain, furthermore, it is possible to be suitble to The raw material of the monomer of resin combination as optical applications.

<1.1 alkylidenes, arlydene, sub- aralkyl>

With above-mentioned《Invention 2》's<1.1 alkylidenes, arlydene, sub- aralkyl>Item in the group that illustrates it is identical.

With above-mentioned《Invention 2》's<The substituent group that 1.2 fluorenes unit a can have>Item in the substituent group that illustrates it is identical.

<1.3 reactive functional groups>

The oligomeric fluorenes A1 of the present invention has following formula (A) institute on the carbon atom of 9 of the fluorenes unit a of any one end The reactive functional groups of expression.Reactive functional groups refer not only to be used directly for the group of polymerisation, also refer to by conversion It reacts and can be used in the group of polymerisation.

[changing 85]

Above-mentioned R is enumerated below^a~R^cIn " with or without substituent group carbon number be 1~10 alkyl " it is specific Structure, but these are not limited to, it is straight that methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, positive decyl etc. can be enumerated The alkyl of chain；Isopropyl, 2- methyl-propyls, 2,2- dimethyl propyls, 2- ethylhexyls etc. include the alkyl of branch；Ring third The isothrausmatic alkyl of base, cyclopenta, cyclohexyl, cyclooctyl.

With or without substituent group carbon number be 1~10 alkyl in carbon number be preferably less than 4 and More preferably more than 2.If in the range of this, the importing with reactive functional groups is readily inclined to.

As the concrete example of substituted alkyl, trifluoromethyl, benzyl, 4- methoxy-benzyls, methoxy methyl can be enumerated Base etc..

Above-mentioned R is enumerated below^a~R^cIn " with or without substituent group carbon number be 4~10 aryl " it is specific Structure, but these are not limited to, the aryl such as phenyl, 1- naphthalenes, 2- naphthalenes can be enumerated；2- pyridyl groups, 2- thienyls, 2- furans The heteroaryls such as base.

With or without substituent group carbon number be 4~10 aryl in carbon number be preferably less than 8, it is more excellent Elect less than 7, and preferably more than 4, more preferably more than 5 as.Hold if the importing in the range of this, with reactive functional groups Easy tendency.

As the concrete example of substituted aryl, 2- aminomethyl phenyls, 4- aminomethyl phenyls, 4- chlorphenyls, 3,5- can be enumerated 3,5-dimethylphenyl, 4- benzoylphenyls, 4- methoxyphenyls, 4- nitrobenzophenones, 4- cyano-phenyls, 3- trifluoromethyls, 3,4- Dimethoxyphenyls, 3,4- methylene dihydroxyphenyl, 2,3,4,5,6- pentafluorophenyl groups, 4- methylfuran bases etc..

Above-mentioned R is enumerated below^a~R^cIn " with or without substituent group carbon number be 6~10 aralkyl " tool Body structure, but these are not limited to, benzyl, 2- phenylethyls can be enumerated, to methoxy-benzyl etc..

Carbon number with or without substituent group is that the carbon number in 6~10 aralkyl is preferably less than 9, more Preferably less than 8, and preferably more than 6, more preferably more than 7.If in the range of this, there is the importing of reactive functional groups Readily tendency.

As the substituent group that the aralkyl can have, can enumerate halogen atom (such as fluorine atom, chlorine atom, bromine atoms, Iodine atom)；Carbon number is 1~10 alkyl (such as methyl, ethyl, isopropyl etc.)；Carbon number is 1~10 alkoxy (such as methoxyl group, ethyoxyl etc.)；Carbon number is 1~10 acyl group (such as acetyl group, benzoyl etc.)；Carbon number is 1~10 amide groups (such as acetamido, benzamido etc.)；Nitro；Cyano etc..The quantity of the substituent group does not limit especially It is fixed, preferably 1~3.In the case that substituent group is 2 or more, the species of substituent group can be the same or different.In addition, from The aspect that can industrially manufacture at low cost is set out, preferably unsubstituted.

As the concrete example of substituted aralkyl, benzyl, 2- phenylethyls can be enumerated, to methoxy-benzyl etc..

Among these, since the importing with reactive functional groups is readily inclined to, thus preferred R^aAnd R^bFor hydrogen atom The following general formula (A-1).In addition, from the aspect of it industrially can obtain raw material at low cost, R^cPreferably hydrogen atom or first Base, more preferably hydrogen atom.

[changing 86]

In addition, the concrete structure of " ester group " is not particularly limited in X, for example, end group is carbon number is The ester group of 1~10 organic substituent.

Among these, from the aspect that can industrially obtain at low cost, preferably carbon number is 1~6 alkyl. In this case, easily hydrolyzed from synthesis, easily generate carboxylic acid aspect, carbon number is preferably more than 2, separately Outside, it is efficiently synthesized polyester from by removing the low-boiling point alcohol generated in the transesterification with dihydroxy compounds and gathers It is preferably less than 4, more preferably less than 2 from the aspect of ester carbonic ester.Particularly preferred substituent group is ethyl.

On the other hand, carbon number be 6~8 aryl in the case of, ester exchange reaction easily carries out, thus pass through by Aryl ester compound and dihydroxy compounds, carbonic diester are added together in input reactor, so as to be gone out with one-step synthesis As the polyestercarbonate of preferred polymers, thus it is preferred.Particularly, be particularly preferably molecular weight it is small, in polyester carbonic acid The phenyl that can be removed after Lipase absobed as phenol distillation.In addition, in the case of aryl, in terms of reactivity when polymerization It sets out, as carbonic diester it is preferable to use aftermentioned diaryl carbonate esters, from can easily remove by-product aspect, The aryl in aryl and diaryl carbonate esters in more preferable ester group is identical.

In addition, ester group, which can be converted to by carrying out reduction, is used as the useful alcohol of raw material of makrolon or polyester.

The concrete structure of " amide groups " is not particularly limited in X, for example,：(i) there are 2 hydrogen originals on nitrogen-atoms The primary amide base of son；(ii) there is the secondary amide base of hydrogen atom and carbon number for 1~10 organic substituent on nitrogen-atoms； (iii) there is the teritary amide base for the organic substituent that 2 carbon numbers are 1~10 independently on nitrogen-atoms.It is former as carbon It is preferable to use as the organic substituent that the carbon number in " ester group " is 1~10 for the organic substituent that subnumber is 1~10 Illustrated group.

Amide groups becomes " amino " by being reduced, can be as polyamide or the raw material of polyimides.These it In, it is more excellent from the aspect of the reactivity of amino of the reduction easily and after reduction, preferably primary amide base and secondary amide base Elect primary amide base as.

It is excellent among these from the aspect that can be used directly as the raw material of polyester or polyestercarbonate as X Elect ester group or carboxyl as, more preferably methyl ester group, ethyl ester, phenyl ester group or carboxyl.

<1.4 concrete structure>

As the oligomeric fluorenes A1 of the present invention, the substance represented by specifically it is preferable to use the following general formula (1).

[changing 87]

In formula (1),

R⁴~R⁹It is each independently hydrogen atom, the alkyl that the carbon number with or without substituent group is 1~10, tool Have or aryl that the carbon number without substituent group is 4~10, with or without the carbon number of substituent group be 1~10 Acyloxy, the carbon number with or without substituent group that acyl group, the carbon number with or without substituent group are 1~10 Alkoxy for 1~10, with or without substituent group carbon number be 1~10 aryloxy group, with or without substitution The amino of base, vinyl of the carbon number for 1~10 with or without substituent group, the original of the carbon with or without substituent group Subnumber is 1~10 acetenyl, the sulphur atom with substituent group, the silicon atom with substituent group, halogen atom, nitro or cyanogen Base.Wherein, in R⁴~R⁹In, adjacent at least two group can be mutually bonded to form ring.

X is ester group, amide groups, carboxyl, cyano or nitro.

N represents 1~5 integer value.

In above-mentioned formula (1), as R³And R⁴~R⁹It is preferable to use above-mentioned《Invention 1》The group in it is illustrated Group.

<1.5 have the concrete example of the oligomeric fluorenes A1 of 1 reactive functional groups>

The concrete example of oligomeric fluorenes A1 as the present invention can enumerate the structure shown in following [E] group.

[changing 88]

[changing 89]

<1.6 have the physical property of the oligomeric fluorenes A1 of 1 reactive functional groups>

The physics value of the oligomeric fluorenes A1 of the present invention is not particularly limited, and preferably satisfies physics value illustrated below.

Chlorine content ratio in the oligomeric fluorenes A1 of the present invention is preferably below 100 mass ppm in terms of Cl reduced masses.Into one Step is preferably below 10 mass ppm.In the case that the content ratio of chlorine component is more, obtained from using oligomeric fluorenes A1 as raw material Also it can largely contain chlorine component in monomer, catalyst inactivation used in polymerisation can be made, polymerization can not be carried out to desired Molecular weight or reaction in destabilization, there is the possibility that productivity is deteriorated.And also have in obtained polymer Chlorine component remaining, may make the thermal stability of polymer reduce.

In the oligomeric fluorenes A1 of the present invention, it may contain from the sodium of following processes or the isometric preiodic type periodic table of potassium The group II metals such as the 1st race's metal or calcium, the process are that formaldehydes is made to have an effect be crosslinked instead with fluorenes class in the presence of a base The process answered；The content ratio of these metals is preferably below 500 mass ppm, is more preferably below 200 mass ppm, is further Preferably below 50 mass ppm, particularly preferably below 10 mass ppm.If metal ingredient is more, using oligomeric fluorenes A1 as original Also metal ingredient can largely be contained in monomer obtained from material, when polymerisation or resin are processed, polymer may become easy Coloring.In addition, contained metal ingredient shows catalyst action or catalyst inactivation effect, it is also possible to make polymerization in not It stabilizes.

In oligomeric fluorenes A1 of the invention, particularly oligomeric fluorenes list aryl ester, it may contain what is brought by following processes 12nd races such as group II metals, zinc, the cadmiums such as isometric the 1st race of preiodic type periodic table of the transition metal such as titanium, copper, iron, sodium, potassium, magnesium, calcium 14th race's metal such as metal or tin, the process are to make diaryl carbonates esters in the presence of catalyst for ester exchange reaction For carrying out the process of transesterification；The content ratio of these metals is preferably below 500 mass ppm, is more preferably 200 mass Below ppm, further preferably below 50 mass ppm, particularly preferably below 10 mass ppm.If metal ingredient is more, with Oligomeric fluorenes, when polymerisation or resin are processed, polymerize as also can largely contain metal ingredient in monomer obtained from raw material Object may become easy coloring.In addition, contained metal ingredient shows catalyst action or catalyst inactivation effect, it is also possible to It is in destabilization that can make polymerization.

The tone of the tetrahydrofuran solution of the 10 mass % of the oligomeric fluorenes A1 of the present invention is preferably less than 50.Further preferably For less than 10.The absorption edge of oligomeric fluorenes A1 extends close to the region of visible ray, has and is exposed due to because polymerization or resin processing The property easily coloured when high temperature.The good polymer of tone in order to obtain, monomer used to the greatest extent may be used in preferred polymeric reaction It can colour few.From this viewpoint, the oligomeric fluorenes A1 preferably as raw material monomer is coloured few as far as possible.Due to tone and concentration into Ratio, thus can be to be measured under various concentration and be standardized as value obtained from 10 mass % concentration.Herein, it is low The tone (APHA values) of polyfluorene A1 can be measured：According to JIS-K0071-1 (1998), by Kishida Chemical societies system (1000 degree) dilutions of color standard liquid are made, made dilution and oligomeric fluorenes A1 are encased in the colorimetric cylinder of internal diameter 20mm simultaneously It is compared, thus measures the tone.

5% weightless temperatures of the oligomeric fluorenes A1 of the present invention in thermogravimetric measure is preferably 230 DEG C or more, is more preferably 250 DEG C or more.Further it is particularly preferably 270 DEG C or more.Fluorenes is the structure very rich in electronics, the substituent group being bonded in fluorenes ring Reactivity it is high, easily generate thermal decomposition.If it can be produced in polymerization using the low monomer of heat decomposition temperature in the polymerization Heat is decomposed, polymerization may be coloured less than desired molecular weight or obtained polymer, thus preferably as The heat decomposition temperature of the oligomeric fluorenes A1 of raw material monomer is also high.

<1.7 have the manufacturing method of the oligomeric fluorenes A1 of 1 reactive functional groups>

It is not particularly limited for the manufacturing method of the oligomeric fluorenes A1 of the present invention, for example, following methods：In alkali In the presence of make oligomeric fluorenes represented by following formula (3) and the olefine reaction with electron-withdrawing group represented by following formula (4), So as to manufacture the oligomeric fluorenes A1 represented by following formula (1).

[changing 90]

In formula, R³It is 1~4 to be each independently Direct Bonding or the carbon number with or without substituent group Alkylidene.

X is ester group, amide groups, carboxyl, cyano or nitro.

N represents 1~5 integer value.

In above-mentioned formula (3) and (4), as R³~R⁹、R^a~R^c, it is preferable to use R is used as in above-mentioned formula (1) by X and n³ ~R⁹、R^a~R^c, X and the situation illustrated in n.

<1.7.1 there is the alkene of electron-withdrawing group>

In addition, as the alkene with electron-withdrawing group represented by above-mentioned formula (4), can enumerate methyl acrylate, Ethyl acrylate, phenyl acrylate, allyl acrylate, glycidyl acrylate, 2-Hydroxy ethyl acrylate, acrylic acid The esters of acrylic acid such as 4- hydroxybutyls, 1,4 cyclohexane dimethanol mono acrylic ester；Methyl methacrylate, methacrylic acid second Ester, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, methacrylic acid -2- hydroxy methacrylates Wait methyl acrylic esters；The alpha-substituted unsaturation esters such as 2- ethyl methyl acrylates, 2- phenylacrylic acid methyl esters；Cinnamic acid first The β such as ester, ethyl cinnamate, M Cr, butenoic acid ethyl-substitution unsaturation esters；Beta-nitrostyrene equiconjugate nitro Olefines；The 'alpha ', ' bela '-unsaturated nitriles class such as acrylonitrile；The alpha, beta-unsaturated aldehydes class such as methacrylaldehyde, methacrolein, crotonaldehyde.Wherein, it is excellent Choosing can be introduced directly into the esters of unsaturated carboxylic acids represented by the following general formula (4-1) of reactive functional groups.

[changing 91]

(in formula, R^cWith the R in formula (4)^cIt is identical, R⁹Represent the organic substituent that carbon number is 1~10.).Herein, make For R⁹Carbon number be 1~10 organic substituent it is preferable to use be 1~10 as the carbon number in " ester group " Group illustrated in organic substituent.

In the unsaturated carboxylic acid represented by general formula (4-1), more preferably esters of acrylic acid, methyl acrylic ester or α- The unsaturated esters of substitution, from reaction speed and reaction selectivity aspect, further preferred R^cFor hydrogen atom or methyl Esters of acrylic acid or methyl acrylic ester.R⁹During smaller, industrial at low cost and distillation is refined easily, reactivity is also high, because And particularly preferably methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate or Person's phenyl methacrylate.

On the other hand, the esters of unsaturated carboxylic acids represented by formula (4-1) is 2-Hydroxy ethyl acrylate, acrylic acid -4- hydroxyls In the case that butyl ester, 1,4-CHDM mono acrylic ester etc. have the esters of hydroxy alkyl, it can be obtained by a step The raw material of polyestercarbonate, polyester, thus particularly preferably.

The two or more alkene with electron-withdrawing group can also be used, but from the aspect of refined simplicity, it is excellent Choosing uses a kind of alkene with electron-withdrawing group.

It is not particularly limited for the dosage of the alkene with electron-withdrawing group, from selectively obtaining single addition body From the aspect of, be preferably more than 0.1 equivalent, more preferably more than 0.3 equivalent, it is more than further preferably 0.5 equivalent, it is especially excellent Elect as more than 0.7 equivalent, and below preferably 2.0 equivalents, more preferably below 1.8 equivalents, further preferably 1.5 equivalents Below, it is particularly preferably below 1.2 equivalents.

<1.7.2 alkali>

In R³For methylene situation in addition in the case of, have formula (3) represented by oligomeric fluorenes reactivity There is larger difference.Therefore, it is divided into R³It is recorded for the situation and situation in addition of methylene.

In R³In the case of methylene, the oligomeric fluorenes represented by formula (3) is easily divided in the presence of a base in a solvent Solution reaction.Therefore, decomposition reaction etc. can be inhibited in the case where being reacted using 2 coating systems of organic layer and water layer The reason for side reaction, it is preferable to use water-soluble inorganic bases.Wherein from the aspect of cost, reactivity, preferred as alkali Hydroxide, further particularly preferably sodium hydroxide or potassium hydroxide.

In addition, the concentration on aqueous solution, in the case where using particularly preferred sodium hydrate aqueous solution, if due to dense Spend low, reaction speed can significantly reduce, thus particularly preferably using be usually more than 5wt/wt%, be preferably 10wt/wt% with Upper, more preferably more than 25wt/wt% aqueous solution.

In R³In the case of beyond methylene, can also it be reacted even with 2 coating systems of organic layer and water layer, but In the case where the organic base being dissolved in organic layer is used to be reacted, since reaction carries out rapidly and it is preferable to use organic Alkali.Wherein preferably there is the alkali alcoholate of fully alkalescence, the low sodium methoxide of more preferable industrial cost or second in the reaction Sodium alkoxide.Alkali alcoholate herein can use the substance of powdery, can also use the liquids such as alcoholic solution.It and can be with Alkali metal is made to react to prepare with alcohol.

In R³In the case of for methylene, on the dosage of alkali, compared with the oligomeric fluorenes represented by starting materials of formulae (3), thereon Limit is not particularly limited, but when the dosage of alkali is excessive, the refined load after stirring or reaction may increase, thus use In the case of the sodium hydrate aqueous solution of more than 25wt/wt% as particularly preferred alkali, it is represented to be commonly angled relative to formula (3) Oligomeric fluorenes for below 20 times of volumes, be preferably below 10 times of volumes, below further preferably 5 times of volumes.In alkali When measuring very few, reaction speed significantly reduces, thus alkali is usually 0.2 times of volume compared with the oligomeric fluorenes represented by starting materials of formulae (3) It is more than amount.More than preferably 0.5 times of volume, more than more preferably 1 times of volume.

In R³In the case of beyond methylene, on the dosage of alkali, compared with the oligomeric fluorenes represented by starting materials of formulae (3), Its upper limit is not particularly limited, but when the dosage of alkali is excessive, the refined load after stirring or reaction may increase, thus In the case of sodium methoxide or sodium ethoxide used as particularly preferred alkali, it is 5 to be commonly angled relative to the oligomeric fluorenes represented by formula (3) It is times mole following, be preferably less than 2 times moles, be more preferably less than 1 times mole, be particularly preferably less than 0.5 times mole. When alkali number is very few, reaction speed significantly reduces, thus alkali is usually compared with the oligomeric fluorenes represented by starting materials of formulae (3) 0.005 times mole or more.Preferably 0.01 times mole or more, more preferably 0.05 times mole or more, particularly preferably 0.1 times is rubbed More than you.

<1.7.3 phase transfer catalyst>

In the case where being reacted using 2 coating systems of organic layer and water layer, in order to improve reaction speed, it is preferable to use Phase transfer catalyst.

As phase transfer catalyst, can enumerate tetramethyl ammonium chloride, tetrabutylammonium bromide, methyl tricapryl ammonium chloride, Three decyl ammonium chloride of methyl, benzyltrimethylammonium chloride, tri-n-octyl methyl ammonium chloride, tetrabutylammonium iodide, acetyl group trimethyl The halide of the quaternary ammonium salts such as ammonium bromide, benzyltriethylammoinium chloride (not including fluorine)；N, N- dimethyl pyrrolidine chloride, N- Ethyl-N-methyl pyrrolidines iodide, N- butyl-N- crassitudes bromide, N- Benzyl-N-methyl pyrrolidines chlorine The halide of the seasons pyrrolidinium such as compound, N- ethyl-N-methyl pyrrolidines bromides (not including fluorine)；N- butyl-N- first The seasons morpholine such as base morpholine bromide, N- butyl-N-methylmorpholine iodide, N- pi-allyls-N-methylmorpholine bromide The halide of salt (not including fluorine)；N- methyl-N-benzyls piperidinium chloride, N- methyl-N-benzyls piperidinium bromide, N, The seasons such as N- lupetidines iodide, N- methyl-N ethyl Piperidineacetic acids salt, N- methyl-N ethyl piperidines iodide The halide of piperidinium salt (not including fluorine)；Crown ether-like etc..It is preferred that quaternary ammonium salt, further preferred benzyltrimethylammonium chloride or Person's benzyltriethylammoinium chloride.They can be used alone, and can also share two or more.

The dosage of phase transfer catalyst compared with the oligomeric fluorenes represented by starting materials of formulae (3) it is excessive when, have ester hydrolysis or The tendency that the side reactions such as michael reaction significantly carry out step by step, and from cost aspect, it is commonly angled relative to formula (3) institute table The oligomeric fluorenes shown is also less than 5 times moles, is preferably less than 2 times moles, further preferably less than 1 times mole.Phase transfer is urged When the dosage of agent is very few, there is the significantly reduced tendency of reaction speed, thus the dosage of phase transfer catalyst is low compared with raw material Polyfluorene is usually 0.01 times mole or more.Preferably 0.1 times mole or more, more preferably 0.5 times mole or more.

<1.7.4 solvent>

It is preferable to use solvent progress for the reaction of the alkene with electron-withdrawing group represented by above-mentioned formula (4).

In R³In the case of for methylene, by using the solvent being separated with water, it is known that having being capable of suppressed FCM (3) tendency of the side reactions such as the decomposition reaction of oligomeric fluorenes represented by.Further, starting materials of formulae can preferably be dissolved using (3) in the case of the solvent of the oligomeric fluorenes represented by, from carrying out good tendency aspect with reaction, it is preferable to use originals The solubility of oligomeric fluorenes represented by material formula (3) is the solvent of more than 0.5 mass %, is 1.0 matter more preferably using the solubility Measure more than %, particularly preferably using the solvent that the solubility is more than 1.5 mass %.In particular, it is preferred that halogen system aliphatic Hydrocarbon, halogen system aromatic hydrocarbon, aromatic hydrocarbon or ether series solvent, particularly preferred dichloromethane, chlorobenzene, chloroform, 1,2- dichloros Benzene, tetrahydrofuran, 1,4- dioxane or methylcyclopentyl ether.

On the other hand, in R³In the case of for the group beyond methylene, it is known that have represented by organic base and formula (3) The dissolubility of oligomeric fluorenes brings reaction speed the tendency of larger impact, and in order to ensure the dissolubility, it is preferable to use with certain The solvent of dielectric constant more than value.As the solvent that can preferably dissolve organic base and the oligomeric fluorenes represented by formula (3), preferably Heteroaromatic, alkyl nitrile series solvent, acid amides series solvent, sulfoxide series solvent, particularly preferred pyridine, acetonitrile, N, N- dimethyl methyls Amide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), sulfolane.

Above-mentioned solvent can be used alone, and two or more may be used in combination.

On the dosage of solvent, the upper limit is not particularly limited, if the generation in view of the purpose thing in each reactor is imitated Rate, then usually using reaching 20 times of volumes of oligomeric fluorenes represented by starting materials of formulae (3), be preferably 15 times of volumes, further The amount of preferably 10 times volumes.On the other hand, if the dosage of solvent is very few, the dissolubility of reagent is deteriorated, stirs change hardly possible, together The carry out of Shi Fanying is slow, thus is used as lower limit, usually used 1 times of volume for reaching the oligomeric fluorenes represented by starting materials of formulae (3), The amount of preferably 2 times of volumes, further preferably 4 times of volumes.

<1.7.5 reaction formation>

Batch-type reaction, the form that circulation type reacts or they are composed may be employed in the form of reaction, to its form It is not particularly limited.

It, will when reacting and starting in putting into reaction reagent in the input method in reactor in the case of batch-type Alkene with electron-withdrawing group is by the case of disposably adding and being fed intake, due to the alkene with electron-withdrawing group Hydrocarbon exists with high concentration, thus the polymerisation of side reaction easily carries out.So as to preferably low represented by addition starting materials of formulae (3) A small amount of gradually addition has the alkene of electron-withdrawing group every time after polyfluorene, phase transfer catalyst, solvent and alkali.

<1.7.6 reaction condition>

If temperature is too low, it cannot get sufficient reaction speed, if temperature on the contrary is excessively high, with electron-withdrawing group Alkene has the tendency for easily carrying out polymerisation, thus temperature treatment is particularly important.Therefore, as reaction temperature, tool It says, usually within the range having a lower limit of 0 DEG C, preferably 10 DEG C, more preferably 15 DEG C is implemented body.On the other hand, usually it is in the upper limit 40 DEG C, preferably 30 DEG C, more preferably 20 DEG C are implemented.

On the General reactions time, usual lower limit for 2 it is small when, be preferably 4 it is small when, further preferably 6 it is small when, the upper limit does not have Be particularly limited to, be usually 30 it is small when, be preferably 20 it is small when, further preferably 10 it is small when.

<1.7.7 the separation and purification of purpose thing>

After termination of the reaction, following methods, which can be used, is precipitated the oligomeric fluorenes A1 represented by the above-mentioned formula of purpose thing (1), so as to The separation of the oligomeric fluorenes A1 represented by the above-mentioned formula of purpose thing (1) is carried out, the method is by filtering byproduct metal halogenation Object and remaining inorganic base is removed from reaction solution after progress solvent concentration method or adding purpose object it is bad molten The method of agent；Etc..

In addition, after termination of the reaction, acid water and the above-mentioned formula of dissolvable purpose thing (1) institute can also be added into reaction solution The solvent of the oligomeric fluorenes A1 represented extracts.The purpose thing gone out using solvent extraction can be by the side that is concentrated to solvent Method or the method for addition poor solvent etc. are separated.

As the solvent that can be used in extraction, as long as can dissolve the oligomeric fluorenes A1 represented by the above-mentioned formula of purpose thing (1) , it is not particularly limited, but is adapted in use to the halogens such as the aromatic hydrocarbon compounds such as toluene, dimethylbenzene, dichloromethane, chloroform system It is one kind or two or more in solvent etc..

It, can be with polyester or polyester carbonic acid in the case that X is ester group in the oligomeric fluorenes A1 represented by formula (1) obtained herein The form of the precursor of ester starting monomer uses, but can also be used after refine.As method for refining, may be employed common Method for refining, such as recrystallization or reprecipitation method, Hydrolysis kinetics, column chromatography, there is no restriction.Oligomeric fluorenes A1 can additionally be dissolved In appropriate solvent, handled using activated carbon.The solvent that can be used at this time and the solvent phase that can be used during extraction Together.

It, can be directly with polyester or polyester in the case that X is carboxyl in the oligomeric fluorenes A1 represented by formula (1) obtained herein The form of the precursor of carbonate source monomer uses.In addition the oligomeric fluorenes that X is ester group can be converted by esterification.

It, can be by using hydrogen in the case that X is nitro or cyano in the oligomeric fluorenes A1 represented by formula (1) obtained herein The hydrogenation or manufactured using the hydride reduction that the reducing agents such as lithium aluminium hydride carry out with ammonia that the methods of palladium carbon under atmosphere carries out The oligomeric fluorenes of base.In addition, in the case where X is cyano, No. 3280169 specifications of U.S. Patent No. and U.S. Patent No. can be passed through The method migration of No. 3324084 specifications etc. is into the oligomeric fluorenes that X is ester group.

<2 have the Oligofluorenylene compounds A2 of 2 different reactive functional groups>

The oligomeric fluorenes (hereinafter sometimes called " oligomeric fluorenes A2 ") with 2 different reactive functional groups of the present invention It is the carbon atom of 9 comprising the fluorenes unit a of 2 or more with or without substituent group each other by with or without taking The alkylidene of Dai Ji, the arlydene with or without substituent group or the sub- aralkyl with or without substituent group are with chain Shape is bonded the oligomeric fluorenes of the oligomeric fluorene structural units a formed, which is characterized in that,

There is following formula on the carbon atom of 9 of the fluorenes unit a of any one end of the oligomeric fluorene structural units a (A) reactive functional groups represented by have and reactivity official on the carbon atom of 9 of the fluorenes unit a of another end Different arbitrary reactive functional groups can be rolled into a ball.

[changing 92]

As the alkylidene of bonding fluorenes unit a, arlydene and sub- aralkyl, preferably may be employed respectively<1.1 alkylene Base, arlydene, sub- aralkyl>In illustrated group.

Similarly, the substituent group that can have as fluorenes unit a, preferably may be employed<1.2 fluorenes unit a can have Substituent group>In illustrated group.

Similarly, as the R in formula (A)^a~R^cAnd X, it preferably may be employed respectively<1.3 reactive functional groups>Middle institute The group of illustration.

<2.1 arbitrary reactive functional groups>

As described above, the present invention oligomeric fluorenes A2 on the carbon atom of 9 of the fluorenes unit a of any one end have it is upper The reactive functional groups represented by formula (A) are stated, are had and the reaction on the carbon atom of 9 of the fluorenes unit a of another end The different arbitrary reactive functional groups of property functional group.

It is not particularly limited on above-mentioned arbitrary reactive functional groups, the regulation of formula (A) can be unsatisfactory for, and also may be used To meet the regulation of formula (A) but different from another reactive functional groups.

In this way, there are 2 different reactive functional groups by 1 oligomeric fluorenes, it can be easily to resin so as to have Assign the tendency of the specific physical property from two kinds of reactive functional groups.

The concrete structure of above-mentioned arbitrary reactive functional groups is enumerated below, but is not limited to these, can enumerate hydroxyl Methyl, 2- hydroxyethyls, 3- hydroxypropyls, hydroxybutyl, 2,2- dimethyl -3- hydroxypropyls, 2- methoxy -2- methyl Propylidene, 4- hydroxy phenyls, 4- hydroxy-3-methyls phenyl, 4- (2- hydroxyl-oxethyls) phenyl, (4- (hydroxymethyl) hexamethylene- 1- yls) hydroxyls such as methyl；Methoxycarbonyl, ethoxy carbonyl, phenyloxycarbonyl, ethoxy carbonyl methyl, 2- (ethyoxyl carbonyls Base) ethyl, 2- (methoxycarbonyl) ethyl, 2- (phenyloxycarbonyl) ethyl, 2- methyl -2- (ethoxy carbonyl) ethyl, 2- first The ester groups such as base -2- (methoxycarbonyl) ethyl, 2- methyl -2- (phenyloxycarbonyl) ethyl, 2- (methoxycarbonyl) propyl；2- hydroxyls Base oxethyl carbonyl, 2- (2- hydroxyl-oxethyls) carbonylethyl, 2- methyl -2- (2- hydroxyl-oxethyls) carbonylethyl, 2- (2- hydroxyls Base oxethyl) carbonyl propyl, 2- (4- hydroxybutoxies) carbonylethyl, 2- methyl -2- (4- hydroxybutoxies) carbonylethyl, 2- [[4- (hydroxymethyl) hexamethylene -1- bases] methoxyl group] carbonylethyl, 2- methyl -2- [[4- (hydroxymethyl) hexamethylene -1- bases] Methoxyl group] the hydroxyls ester group such as carbonylethyl；The carboxyls such as carboxyl, carboxymethyl group, 2- carboxy ethyls, 2- methyl -2- carboxy ethyls；Ammonia The amino such as ylmethyl, 2- amino-ethyls, 3- aminopropyls；Acryloyloxymethyl, methacryloxymethyl, 2- (propylene Acyloxy) ethyl, 2- (methacryloxy) ethyl, 3- (acryloxy) propyl, 3- (methacryloxy) propyl Wait acryloyl groups；Epoxy groups such as 2,3- glycidyl, 2,3- glycidyl oxy methyls, 2- (2,3- glycidoxies) ethyl etc..

It should be noted that the oligomeric fluorenes A2 of the present invention can be will have the oligomeric fluorenes of divalent as the poly- of repetitive unit The raw material for closing object is used, and reactive functional groups are preferably only at 2, for manufacturing the polymerizing condition of various resin combinations Under, in the substituent group that plays a role as polymerisation reactivity group is preferably not included in.

Among these, on the preferred compositions of the reactive functional groups represented by formula (A) and another reactive functional groups, Since polyester can be manufactured by a kind of Oligofluorenylene compounds, can enumerate：Formula (A) is ester group, another reactive functional groups is The combination of hydroxyl；The combination that formula (A) is carboxyl, another reactive functional groups is hydroxyl；And formula (A) is ester group, another Reactive functional groups are the combination of hydroxyl ester group.In addition, ester group, hydroxyl, carboxyl and hydroxyl ester group and previous paragraphs in this section Ester group, hydroxyl, carboxyl and the hydroxyl ester group meaning for falling the concrete structure as reactive functional groups of middle illustration are identical.

<2.2 concrete structure>

As the oligomeric fluorenes A2 of the present invention, the substance represented by specifically it is preferable to use the following general formula (2).

[changing 93]

In formula (2), R³It is 1~4 to be each independently Direct Bonding or the carbon number with or without substituent group Alkylidene.

Or for selected from by be 1~10 with or without the carbon number of substituent group alkylidene, with or without Arlydene that the carbon number of substituent group is 4~10 and with or without substituent group carbon number be 6~10 sub- aralkyl Base composition group in the group of 2 or more by oxygen atom, with or without substituent group sulphur atom, with or without The group that the nitrogen-atoms or carbonyl of substituent group are formed by connecting.

X is ester group, amide groups, carboxyl, cyano or nitro.

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

N represents 1~5 integer value.

In above-mentioned formula (2), as R³It is preferable to use as the R in above-mentioned formula (1)³Illustrated group.

In addition, as R⁴~R⁹It is preferable to use as the R in above-mentioned formula (1)⁴~R⁹Illustrated group.

In addition, as R^a~R^cIt is preferable to use as the R in above-mentioned formula (A) with X^a~R^cWith the group illustrated in X.

As R¹⁰, aftermentioned<The oligomeric fluorenes of 4.1 divalents>In it is preferable to use as substituents alpha¹And α²It is illustrated Group.

" ester group, the amide groups " that " ester group, amide groups " in A can be preferably used as the X in above-mentioned formula (A) is illustrated Group.

In addition, the concrete structure of " amino " is not particularly limited in A, for example,：(i) there are 2 on nitrogen-atoms The primary amino radical of hydrogen atom；(ii) there is the secondary amino group of hydrogen atom and carbon number for 1~10 organic substituent on nitrogen-atoms； (iii) there is the tertiary amino for the organic substituent that 2 carbon numbers are 1~10 independently on nitrogen-atoms.As carbon atom The organic substituent that number is 1~10 is 1~10 it is preferable to use the carbon number in " ester group " of the X as above-mentioned formula (A) Organic substituent illustrated in group.

Among these, by using a kind of oligomeric fluorenes A2 of the present invention, polyester, polyamide can be manufactured, thus A is preferably Hydroxyl or amino, due to easy to manufacture, thus more preferably hydroxyl.

<2.3 have the concrete example of the oligomeric fluorenes A2 of 2 different reactive functional groups>

The concrete example of oligomeric fluorenes A2 as the present invention can enumerate the structure shown in following [F] group.

[changing 94]

[changing 95]

<2.4 have the physical property of the oligomeric fluorenes A2 of 2 different reactive functional groups>

With it is above-mentioned<1.6 have the physical property of the oligomeric fluorenes A1 of 1 reactive functional groups>Item in situation about illustrating it is identical.

<2.5 have the manufacturing method of the oligomeric fluorenes A2 of 2 different reactive functional groups>

It is not particularly limited for the manufacturing method of the oligomeric fluorenes A2 of the present invention, for example, following methods：Make It states the oligomeric fluorenes represented by formula (1) to react with the compound with electrophilicity, manufactures the oligomeric fluorenes A2 represented by above-mentioned formula (2).

[changing 96]

Hereinafter, by above-mentioned formula (2) represented by oligomeric fluorenes A2 manufacturing method according to the compound with electrophilicity kind Class is divided into autofrettage A, autofrettage B, autofrettage C, autofrettage D and is recorded.

<2.5.1 autofrettage A：The manufacturing method of addition based on formaldehydes>

With hydroxymethyl as the oligomeric fluorenes represented by the following formula (2a) of reactive functional groups can in the presence of a base, It is manufactured according to the reaction represented by autofrettage A by the oligomeric fluorenes A1 represented by following formula (1) and formaldehydes.

[changing 97]

In formula (2a), R³~R⁹、R^a~R^c, X and n it is identical with above-mentioned formula (1).

<2.5.1.1 formaldehydes>

The formaldehydes used in autofrettage A do not limit especially as long as that can supply the substance of formaldehyde into reaction system It is fixed, paraformaldehyde, trioxane that gaseous formaldehyde, formalin, oxymethylene polymerization form etc. can be enumerated.These it In, during using paraformaldehyde, industrial cost it is low and due to for it is powdered thus it is operational easily, can accurate weighing, it is thus special Not not preferably.

On the dosage of formaldehydes, compared with the oligomeric fluorenes A1 of raw material, the upper limit is not particularly limited, if but dosage it is excessive, Then there is the increased tendency of refined load after reaction, thus be commonly angled relative to oligomeric fluorenes A1 and be less than 10 times moles, be preferably 5 It is times mole following, be more preferably less than 3 times moles.On lower limit, rub due to being calculated as 1 times compared with raw material with theoretical amount You, thus lower limit is usually 1 times mole or more.In order to accelerate reaction progress, not retained material or intermediate, thus formaldehydes phase It is slightly excessively used for the oligomeric fluorenes A1 of raw material and does not also have any problems.The preferable amount of formaldehydes is oligomeric compared with raw material at this time Fluorenes A1 is 1.1 times moles or more, further preferably 1.2 times moles or more.

<2.5.1.2 alkali>

As alkali, the alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide are used；Calcium hydroxide, hydroxide The hydroxide of the alkaline-earth metal such as barium；The carbonate of the alkali metal such as sodium carbonate, sodium acid carbonate, potassium carbonate；Magnesium carbonate, calcium carbonate etc. The carbonate of alkaline-earth metal；The alkali metal salt of the phosphoric acid such as sodium phosphate, dibastic sodium phosphate, potassium phosphate；N-BuLi, tert-butyl lithium etc. have Machine lithium salts；The alkali alcoholates such as sodium methoxide, sodium ethoxide, potassium tert-butoxide；The hydrogenated alkali metals salt such as sodium hydride, hydrofining；Three second The tertiary amines such as amine, diazabicyclo endecatylene；Quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide etc..They It can be used alone, can also share two or more.

Among them, preferably there is the alkali alcoholate of fully alkalescence in the reaction, more preferable industrial cost is low Sodium methoxide or sodium ethoxide.Alkali alcoholate herein can use the substance of powdery, can also use the liquid objects such as alcoholic solution Matter.And alkali metal can be made to react to prepare with alcohol.

The dosage of alkali does not have the special upper limit, when dosage is excessive, has the increased tendency of refined load after reaction, thus Being less than 1 times mole, preferably less than 0.5 times mole, further preferably less than 0.2 times mole compared with oligomeric fluorenes A1 is It is good.On the other hand, when the dosage of alkali is very few, reaction carries out slowly, thus as lower limit, being commonly angled relative to the oligomeric fluorenes A1 of raw material is 0.01 times mole or more, preferably 0.05 times mole or more.

<2.5.1.3 solvent>

It is preferable to use solvent progress by autofrettage A.

Specifically, workable solvent can be enumerated：Acetonitrile, propionitrile as alkyl nitrile series solvent etc.；As ketone system Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) of solvent etc.；As the methyl acetate of ester series solvent, ethyl acetate, acetic acid third Ester, phenylacetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, 3- methoxy methyl propionates, 3- ethoxy-propionic acids The ring-type esters such as the esters of the straight-chains such as methyl esters, methyl lactate, ethyl lactate, gamma-butyrolacton, caprolactone, ethylene glycol monomethyl Ether acetic acid ester, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol -1- methyl ether acetates, the third two Ether-ethers classes such as alcohol -1- monoethyl ether acetates etc.；As the diethyl ether of ether series solvent, tetrahydrofuran, 1,4- dioxane, methyl ring Amyl ether, t-butyl methyl ether etc.；As the 1,2- dichloroethanes of halogen-based solvent, dichloromethane, chloroform, tetra- chloroethenes of 1,1,2,2- Alkane etc.；Chlorobenzene, 1,2- dichloro-benzenes as halogen system aromatic hydrocarbon etc.；N,N-dimethylformamide as acid amides series solvent, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone etc.；Dimethyl sulfoxide (DMSO), sulfolane as sulfoxide series solvent etc.；As ring The monocyclic aliphatic hydrocarbons such as pentamethylene, hexamethylene, cycloheptane, the cyclooctane of formula aliphatic hydrocarbon；For the methyl ring penta of its derivative Alkane, ethyl cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2- dimethyl cyclohexanes, 1,3- dimethyl cyclohexanes, 1,4- bis- Hexahydrotoluene, isopropyl cyclohexane, n-propyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl butylcyclohexane, 1,2,4- trimethyl-cyclohexanes, 1,3,5- trimethyl-cyclohexanes etc.；The polycycles aliphatic hydrocarbon such as decahydronaphthalenes；Pentane, just oneself The non-ring type aliphatic hydrocarbon such as alkane, normal heptane, normal octane, isooctane, n -nonane, n-decane, n-dodecane, n-tetradecane；As Toluene, paraxylene, ortho-xylene, meta-xylene of aromatic hydrocarbon etc.；As the methanol of alcohol series solvent, ethyl alcohol, isopropanol, just Butanol, the tert-butyl alcohol, hexanol, octanol, cyclohexanol etc..

Wherein, for the dissolubility height of the anion generated by oligomeric fluorenes A1, the original that there is reaction to carry out good tendency The acid amides series solvent of cause, preferably polar solvent or sulfoxide series solvent, particularly preferred n,N-Dimethylformamide.

These solvents can be used alone, and two or more may be used in combination.On the dosage of solvent, the upper limit does not have There is special limitation, if in view of the formation efficiency of the purpose thing in each reactor, it is usually used to reach the oligomeric fluorenes A1 of raw material 10 times of volumes, be preferably 7 times of volumes, further preferably 4 times of volumes amount.On the other hand, if the dosage of solvent It is very few, then change hardly possible is stirred, while the progress with reaction is slowly inclined to, thus as lower limit, it is low usually using raw material is reached 1 times of volume of polyfluorene A1 is preferably 2 times of volumes, the amount of further preferably 3 times of volumes.

<2.5.1.4 reaction formation>

When carrying out autofrettage A, the form of reaction may be employed batch-type reaction, circulation type reaction or they combine and Into form, its form is not particularly limited.

In reaction reagent being put into the input method in reactor for batch-type, react start when by alkali In the case of being fed intake by disposably adding, since known decomposition reaction easily carries out, thus preferably raw material is being added in The method for adding alkali after oligomeric fluorenes A1, formaldehydes and solvent on a small quantity several times, every time.

<2.5.1.5 reaction condition>

If the temperature of autofrettage A is too low, cannot get sufficient reaction speed, if otherwise temperature it is excessively high, understand have into The tendency of row decomposition reaction preferably carries out temperature treatment.Therefore, in the n,N-Dimethylformamide used as optimum solvent and In the case of sodium ethoxide as optimal alkali, usually within the range having a lower limit of -50 DEG C, the upper limit implemented for 30 DEG C.Specifically, in R³ In the case of for methylene, it is preferably 20 DEG C, is implemented under conditions of more preferably 10 DEG C in the upper limit of reaction temperature.It is another Aspect is implemented under conditions of lower limit is preferably -20 DEG C, is more preferably 0 DEG C or more.In R³In the case of for ethylidene, It is preferably 25 DEG C, implements under conditions of more preferably 20 DEG C in the upper limit of reaction temperature.On the other hand, lower limit be preferably 0 DEG C, Implemented under conditions of more preferably 10 DEG C or more.

<2.5.1.6 the separation and purification of purpose thing>

After termination of the reaction, reaction solution can be added in the acid waters such as dilute hydrochloric acid or adds the acid waters such as dilute hydrochloric acid It is added in reaction solution, the oligomeric fluorenes represented by purpose thing formula (2a) is precipitated, thus separated.

In addition, after termination of the reaction, the solvent of the oligomeric fluorenes represented by dissolvable purpose thing formula (2a) can also be added with water It is added in reaction solution, extracts.The purpose thing gone out using solvent extraction can by by the method for solvent concentration or addition not Method of good solvent etc. is separated.

Oligomeric fluorenes represented by obtained formula (2a) can be directly used in as polymer raw material in polymerization, can also carried out It is polymerize after refined.As method for refining, may be employed common method for refining, such as recrystallization or reprecipitation method, Hydrolysis kinetics, Column chromatography etc., there is no restriction.

Fecund gives birth to problem in the polymerization for the presence of metal ingredient, can make the 1st race of long period type periodic table and the 2nd race Content ratio of the metal in monomer is below 500 mass ppm, is more preferably below 200 mass ppm, is more preferably 50 Below quality ppm, particularly preferably below 10 mass ppm.In order to remove metal ingredient, liquid separation operation is typically highly effective , but only it is dissolved in n,N-Dimethylformamide or tetrahydrofuran is contour since the oligomeric fluorenes represented by purpose thing formula (2a) has Tendency in polar solvent, thus the liquid separation operation carried out using 2 coating systems is mostly extremely difficult.On the other hand, for anti- Precipitate after should stopping, even if the hot common refinement treatments such as washing that suspend washed, carried out using arbitrary solvent, It is difficult to fully remove the mixed metal ingredient of institute, possible remaining has the metal ingredient of hundreds of quality ppm orders of magnitude in precipitate. As for removing the good method for refining of metal ingredient, the reaction precipitate containing impurity is dissolved in N, N- dimethyl formyls The method that is precipitated it is added in water after in the higher solvent of the dissolubilities such as amine, tetrahydrofuran as easy and effective nothing Machine salt remove method and it is preferred that.

<2.5.2 autofrettage B：The manufacturing method of addition reaction based on the alkene with electron-withdrawing group>

Oligomeric fluorenes represented by following formula (2b) can be in the presence of a base, according to the reaction represented by autofrettage B by following Oligomeric fluorenes A1 and the alkene (4-2) with electron withdrawing group different from above-mentioned formula (4) represented by formula (1) are manufactured.

[changing 98]

In formula (2b), R³~R⁹、R^a~R^c, X and n it is identical with above-mentioned formula (1).In addition, R^a2~R^c2It is each independently hydrogen original Son, with or without substituent group carbon number be 1~10 alkyl, with or without the carbon number of substituent group be 4 ~10 aryl is 6~10 aralkyl with or without the carbon number of substituent group, and Xa is ester group, amide groups, carboxylic Base, cyano or nitro.Wherein, R^a~R^cWith X and R^a2~R^c2In Xa, at least arbitrary 1 is different.

As R^a2~R^c2And Xa, it preferably may be employed as the R in formula (A)^a~R^cWith the group illustrated in X, R^a~R^cWith X and R^a2~R^c2With in Xa, it is necessary to make at least arbitrary 1 it is different.Particularly, from easily to resin imparting from differential responses It sets out in terms of the specific physical property of property functional group, X is different from Xa in preferred formula (2b).

Oligomeric fluorenes represented by formula (2b) can be made according to the method for the oligomeric fluorenes A1 represented by the above-mentioned formula (1) of manufacture It makes.At this point it is possible to be separated, refined after oligomeric fluorenes A1 is manufactured, manufactured afterwards；It can also be represented in formula (3) Oligomeric fluorenes and formula (4) represented by the olefine reaction with electron-withdrawing group after, then having represented by formula (4-2) The alkene of electron-withdrawing group is reacted.

<2.5.3 autofrettage C：The system of oligomeric fluorenes represented by the formula (2c) of alkylation, hydrolysis based on oligomeric fluorenes A1 Make method)>

Oligomeric fluorenes represented by following formula (2c) can be manufactured by following methods, and the method is：It is low by passing through The alkylated reaction of alkylating agent represented by polyfluorene A1 and formula (8) synthesizes the leaving group that has represented by formula (2c-1) The process (process (ia)) of oligomeric fluorenes and the method for next hydrolysis (process (iia))；Alternatively, it is also possible to pass through Following methods are manufactured, and the method is：It is anti-by the alkylation by oligomeric fluorenes A1 and the alkylating agent represented by formula (9) The process of the oligomeric fluorenes with blocking group represented by formula (2c-2) (process (ib)) and next hydrolysis should be synthesized React the method for (process (iib))；Etc..

[changing 99]

In formula, R³~R⁹、R^a~R^c, X and n it is identical with above-mentioned formula (1).R¹⁰With the R of above-mentioned formula (2)¹⁰It is identical.

In addition, Xb and Xc represents leaving group.As the example of leaving group, can enumerate halogen atom (not including fluorine), Mesyl or p-toluenesulfonyl etc..

T represents blocking group.As the example of blocking group, methoxy, 2- methoxy ethoxy first can be enumerated Base, THP trtrahydropyranyl, tert-butoxycarbonyl, benzyloxycarbonyl, trimethyl silyl or t-butyldimethylsilyl Deng.

The alkylated reaction of fluorenes class is widely known by the people, for example, there have report to propose double (bromine hexyl) fluorenes of 9,9-, 9,9- to be double Double (alkylhalide group) fluorenes (J.Org.Chem., 2010,75,2714.) of the 9,9- such as (iodine hexyl) fluorenes.It, can according to these technological thoughts The oligomeric fluorenes with leaving group is synthesized using oligomeric fluorenes A as raw material.In addition, the hydrolysis on halogen, it is known to many cases report It accuses (Bull.Korean Chem.Soc., 2008,29.2491.), thus can be oligomeric represented by the route synthesizes formula (2c) Fluorenes.

As the alkylating agent used in process (ia), can enumerate：Diiodomethane, 1,2- ethylidene periodides, 1,3- diiodo-s Propane, bis- iodobutanes of 1,4-, bis- iodopentanes of 1,5-, bis- iodohexanes of 1,6-, methylene bromide, glycol dibromide, 1,3- dibromos third Alkane, 1,4- dibromobutanes, pentamethylene bromide, 1,6- dibromo-hexanes, dichloromethane, 1,2- dichloroethanes, 1,3- dichloropropanes, The alkyl dihalide of the straight-chains such as the bromo- 3- chloropropanes of 1,4- dichloroetane, 1,5- dichloropentane, 1,6- dichloro hexanes, 1- is (no Including fluorine atom)；2,2- dimethyl -1,3- dichloropropanes etc. include the alkyl dihalide of branch (not including fluorine atom)；1, The aralkyl dihalide (not including fluorine atom) such as double (bromomethyl) benzene of 4-, double (bromomethyl) benzene of 1,3-；Glycol dinitrate sulfonic acid The disulfonate of the glycol such as ester, glycol dinitrate benzene sulfonate, propylene glycol bis-mesylate, tetramethylene glycol bis-mesylate Deng.

As the alkylating agent used in process (ib), chloro- 2, the 2- diformazans of 3- bromopropyl alcohols, 2- bromopropyl alcohols, 3- can be enumerated Protectives of halogenated alkyls alcohol such as base -1- propyl alcohol etc..

<2.5.4. autofrettage D：Autofrettage based on the oligomeric fluorenes represented by the alkylated formula (2d) of oligomeric fluorenes A1)>

Oligomeric fluorenes represented by formula (2d) can pass through the alkylation of the alkylating agent represented by oligomeric fluorenes A1 and formula (10) It reacts to manufacture.

[changing 100]

In formula (10), Xb and R¹⁰It is identical with above-mentioned formula (8).R²¹With R⁹It is identical.

In formula (2d), R³~R⁹、R^a~R^c, X and n it is identical with above-mentioned formula (1).

R¹⁰For the formula (2d) beyond Direct Bonding oligomeric fluorenes can by the presence of a base, according to<2.5.3 autofrettage C> The middle method identical as the method recorded in process (ia) or (iib) is to the alkylating agent represented by oligomeric fluorenes A1 and formula (10) Reaction is alkylated to manufacture.

As the alkylating agent used in autofrettage D, can enumerate methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, Solid acid n-butyl chloroacete, chloroacetic acid tert-butyl ester, methyl bromoacetate, bromoacetate, bromo-acetic acid tert-butyl, iodoacetic acid methyl esters, iodine second Acetoacetic ester, the iodoacetic acid tert-butyl ester, methyl chloropropionate, chloropropionate, the chloropropionic acid tert-butyl ester, methyl bromide c, ethyl bromide, The halogenated alkanes acid alkyl esters such as the bromo-propionic acid tert-butyl ester, iodopropionic acid methyl esters, iodopropionic acid ethyl ester, the iodopropionic acid tert-butyl ester；4- chloromethylbenzenes Methyl formate, 4- bromomethyl-benzoic acid methyl esters, 4- chloromethyl benzoic acids ethyl ester, 4- bromomethyl-benzoic acid ethyl esters, 3- chloromethylbenzenes Halogenated alkyls benzoic acid alkyl base ester such as methyl formate, 3- bromomethyl-benzoic acid methyl esters etc..

<3 oligomeric fluorenes compositions>

The oligomeric fluorenes composition of the present invention includes oligomeric fluorenes A1 (Oligofluorenylene compounds with 1 reactive functional groups) And/or they (are referred to as by oligomeric fluorenes A2 (Oligofluorenylene compounds with 2 different reactive functional groups) sometimes below " oligomeric fluorenes A ") and with the oligomeric fluorenes A have different chemical structures aftermentioned oligomeric fluorenes B.Particularly, from the poly- of control resin The aspect of sum velocity or molecular weight etc. is set out, and preferably comprises oligomeric fluorenes A1, on the other hand, from easily obtain resulting from 2 kinds with The aspect of the resin characteristics of upper reactive functional groups etc. is set out, and preferably comprises oligomeric fluorenes A2.

<3.1 oligomeric fluorenes B>

The carbon atoms of 9 of the above-mentioned oligomeric fluorenes B comprising the fluorenes unit b of 2 or more with or without substituent group is each other By with or without substituent group alkylidene, with or without the arlydene of substituent group or with or without taking The sub- aralkyl of Dai Ji with chain bonding form oligomeric fluorene structural units (hereinafter referred to oligomeric fluorene structural units b),

[changing 101]

In formula (B), R^d~R^fIt is each independently hydrogen atom, the carbon number with or without substituent group is 1~10 The aryl or the carbon atom with or without substituent group that alkyl, the carbon number with or without substituent group are 4~10 Count the aralkyl for 6~10, X¹For ester group, amide groups, carboxyl, cyano or nitro.* it is the carbon original with 9 of fluorenes unit b The associative key that son combines.

As the alkylidene of bonding fluorenes unit b, arlydene and sub- aralkyl, preferably may be employed respectively<1.1 alkylene Base, arlydene, sub- aralkyl>In illustrated group.In addition, the group of bonding fluorenes unit b is bonded fluorenes unit a with oligomeric fluorenes Group can be the same or different.It is preferably identical from the aspect that can be manufactured simultaneously.

Similarly, as the R in formula (B)^d~R^fAnd X¹, preferably may be employed respectively<1.3 reactive functional groups>Middle work For R^a~R^cWith the group illustrated in X.In addition, the R in formula (B)^d~R^fAnd X¹With the R of the formula (A) in oligomeric fluorenes^a~R^cIt can with X With it is identical can not also be same.It is preferably identical from the aspect that can be manufactured simultaneously.

As the oligomeric fluorenes B of the present invention, the substance represented by specifically it is preferable to use the following general formula (7).

[changing 102]

In formula (7), R¹³It is each independently Direct Bonding, the Asia that the carbon number with or without substituent group is 1~4 Alkyl,

R¹⁴~R¹⁹Be each independently hydrogen atom, with or without substituent group carbon number be 1~10 alkyl, Aryl that carbon number with or without substituent group is 4~10 with or without the carbon number of substituent group is 1~10 Acyl group, with or without substituent group carbon number be 1~10 acyloxy, the carbon atom with or without substituent group Aryloxy group that alkoxies of the number for 1~10, the carbon number with or without substituent group are 1~10, with or without taking Vinyl, the carbon with or without substituent group that the amino of Dai Ji, the carbon number with or without substituent group are 1~10 Atomicity be 1~10 acetenyl, the sulphur atom with substituent group, the silicon atom with substituent group, halogen atom, nitro or Cyano.Wherein, in R¹⁴~R¹⁹In, adjacent at least two group can be mutually bonded to form ring.

R^d~R^fIt is each independently hydrogen atom, the alkyl that the carbon number with or without substituent group is 1~10, tool Have or aryl that the carbon number without substituent group is 4~10 or the carbon number with or without substituent group be 6~ 10 aralkyl,

X¹For ester group, amide groups, carboxyl, cyano or nitro.

N represents 1~5 integer value.

As the R in formula (7)¹³, preferably may be employed as the R in formula (1)³Illustrated group.Similarly, as formula (7) R in¹⁴~R¹⁹, preferably may be employed as the R in formula (1)⁴~R⁹Illustrated group.In addition, as in formula (7) R^d~R^f, preferably may be employed as the R in formula (1)^a~R^cIllustrated group.In addition, as the X in formula (7)¹, preferably may be used With the group illustrated in the X that is employed as in formula (1).As the n in formula (7), preferably may be employed as the n institutes in formula (1) The group of illustration.

The concrete example of oligomeric fluorenes B as the present invention can enumerate the structure shown in following [G] group.

[changing 103]

[changing 104]

[changing 105]

<3.4 content>

It on the content of the above-mentioned oligomeric fluorenes A in the oligomeric fluorenes composition of the present invention, is not particularly limited, polymerize from control It sets out in terms of the molecular weight of object, is preferably more than 0.1 mass %, more preferably more than 0.5 mass %, is still more preferably More than 1 mass %, and preferably below 60 mass %, more preferably below 50 mass %, still more preferably be 40 matter Measure below %.

It on the content of the above-mentioned oligomeric fluorenes B in the oligomeric fluorenes composition of the present invention, is not particularly limited, polymerize from improving It sets out in terms of the degree of polymerization of object, is preferably more than 5 mass %, more preferably more than 10 mass %, is still more preferably 15 More than quality %.Additionally, it is preferred that it is below 60 mass %, more preferably below 50 mass %, is still more preferably 40 matter Measure below %.

In addition, the content ratio of the oligomeric fluorenes A and oligomeric fluorenes B contained by oligomeric fluorenes composition, are not particularly limited, The molar ratio of contained oligomeric fluorenes A and oligomeric fluorenes B are (oligomeric from the molecular weight aspect of control polymer, composition The molal quantity of the molal quantity of fluorenes A/oligomeric fluorenes B) it is preferably more than 0.001, is more preferably more than 0.005, further preferably More than 0.01, and from improve polymer degree of polymerization aspect, be preferably less than 0.05, more preferably less than 0.03, Further preferably less than 0.02.

In oligomeric fluorenes composition contained oligomeric fluorenes A, the molal quantity of oligomeric fluorenes B can also for example utilize calibration curve by The area % of HPLC analyses estimates.

<4 resin combinations>

Resin combination can be manufactured using the oligomeric fluorenes of the present invention.

In the case where using oligomeric fluorenes A as oligomeric fluorenes, for example, can obtain being had shown in following formula (5) by end Structure the resin combination that is formed of polymer or resin combination containing the polymer.

[changing 106]

In formula (5), R³It is each independently Direct Bonding, the Asia that the carbon number with or without substituent group is 1~4 Alkyl,

X is ester group, amide groups, carboxyl, cyano or nitro.

N represents 1~5 integer value.

* the associative key to be combined with linking group.

As the R in formula (5)³~R⁹、R^a~R^cAnd n, the R being employed as in formula (1) can be suitble to³~R⁹、R^a~R^cAnd n Illustrated situation.

The polymer of the resin combination of the present invention preferably has the oligomeric fluorenes of divalent as repetitive unit.

In this case, the resin combination of the present invention is except containing polymerization of the oligomeric fluorenes as repetitive unit with divalent Beyond object, aftermentioned other polymer can also be contained, can additionally contain additive etc..

On method of the oligomeric fluorenes for obtaining that there is divalent as the polymer of repetitive unit, it is not particularly limited, such as In the case of using Oligofluorenylene compounds A2 as oligomeric fluorenes, it can obtain having from the two or more of reactive functional groups Linking group and polymer of the oligomeric fluorenes as repetitive unit with divalent.Also, it by using oligomeric fluorenes B, can also obtain To polymer of the oligomeric fluorenes as repetitive unit with divalent.

The oligomeric fluorenes of divalent includes the fluorenes unit of 2 or more with or without substituent group, and 9 of the fluorenes unit Carbon atom each other by the alkylidene with or without substituent group, arlydene or tool with or without substituent group Have or the sub- aralkyl without substituent group is bonded with chain.

As fluorenes unit it is preferable to use illustrated in the fluorenes unit a as oligomeric fluorenes A fluorenes unit, as oligomeric fluorenes B Fluorenes unit b illustrated in fluorenes unit.

Similarly, as the alkylidene of bonding fluorenes unit, it is preferable to use the bonding fluorenes unit a's as oligomeric fluorenes A Group illustrated in alkylidene, the group illustrated in as the alkylidene of the bonding fluorenes unit b of oligomeric fluorenes B.

In addition, as Asia of the arlydene it is preferable to use the bonding fluorenes unit a as oligomeric fluorenes A for being bonded fluorenes unit Group illustrated in aryl, the group illustrated in as the arlydene of the bonding fluorenes unit b of oligomeric fluorenes B.

In addition, as the sub- aralkyl of bonding fluorenes unit, it is preferable to use the bonding fluorenes unit a's as oligomeric fluorenes A Group illustrated in sub- aralkyl, the group illustrated in as the sub- aralkyl of the bonding fluorenes unit b of oligomeric fluorenes B.

The oligomeric fluorenes of above-mentioned divalent or：In the fluorenes unit of 2 or more, at 9 of the fluorenes unit positioned at two ends Carbon atom on be bonded with substituents alpha respectively¹And α², make the substituents alpha¹And α²For divalent group.In this case, α¹And α²It can With it is identical can not also be same.In addition, substituents alpha¹And α²In include Direct Bonding, i.e. the carbon of 9 that can also make fluorenes unit is former Son is divalent group.

As substituents alpha¹And α²It is not particularly limited, Direct Bonding, the carbon original with or without substituent group can be enumerated Alkylidene that subnumber is 1~10, with or without substituent group carbon number be 4~10 arlydene or have or not Carbon number with substituent group is 6~10 sub- aralkyl；Or selected from by the carbon number with or without substituent group Alkylidene for 1~10, with or without substituent group carbon number be 4~10 arlydene and with or without substitution The carbon number of base be 6~10 sub- aralkyl form group in the group of 2 or more by oxygen atom, with or without The group that the sulphur atom of substituent group, nitrogen-atoms or carbonyl with or without substituent group are formed by connecting.

Enumerate below " be selected from by be 1~10 with or without the carbon number of substituent group alkylidene, have or do not have The Asia virtue that arlydene that the carbon number of substituted base is 4~10 and carbon number with or without substituent group are 6~10 The group of 2 or more in the group of alkyl composition by oxygen atom, with or without substituent group sulphur atom, have or do not have The concrete structure of the group that the nitrogen-atoms or carbonyl of substituted base are formed by connecting ", but these are not limited to, it can enumerate following Divalent group shown in [H] group.

[changing 107]

[H]

Among these, preferably can keep the transparency of resin combination and assign while stability flexibility, The group that the group of 2 or more in alkylidene, arlydene or sub- aralkyl is formed by connecting by oxygen atom, more preferably may be used The alkylidene shown in following [I] group of the glass transition temperature of resin combination is improved while flexibility is assigned and passes through oxygen The group that atom is formed by connecting.

[changing 108]

[I]

Among these, in substituents alpha¹And α²In at least one be Direct Bonding or substituents alpha¹And α²In at least 1 In the case that a carbon number is more than 2, since fluorenes ring (fluorenes unit) is generally perpendicularly orientated compared with main chain, even if thus The ratio of the oligomeric fluorenes of divalent in resin combination is few, it may have easily shows the tendency of inverse wave length dispersiveness.The latter's In the case of, from same aspect, preferably make α¹And α²The carbon number of the two is more than 2.On the other hand, substituent group is made α¹And α²In the case that the carbon number of the two is 1 (that is, with or without the methylene of substituent group), fluorenes ring (fluorenes unit) phase It is not generally perpendicularly to be orientated for main chain, but is significantly obliquely orientated, so even changes resin combination in wide scope In divalent oligomeric fluorenes ratio, it may have be easily formed in the tendency of the small flat dispersiveness of difference of phase difference in wide band.

It may further be preferable that due to not having an aromatic rings and with the low photoelasticity system that can be realized required by optical film Several tendency, Direct Bondings, methylene, ethylidene, n-propylene, positive butylidene, methylmethylene, 1- methyl ethylidene, Alicyclic ring shown in 2- methyl ethylidene, 2,2- dimethylpropylidenes, 2- methoxy -2- methyl propylenes or following [J] group Formula alkylidene.

[changing 109]

[J]

(the position of substitution of 2 associative keys in each ring structure shown in above-mentioned [J] group is arbitrary, and 2 associative keys can To be substituted on same carbon.)

It is still more preferably Direct Bonding, methylene, ethylidene, n-propylene, positive butylidene, methylmethylene, 1- Methyl ethylidene, 2- methyl ethylidene or 2,2- dimethylpropylidenes.Particularly preferably methylene, ethylidene or positive Asia third Base.

On the other hand, for the purpose of the reliability under the mechanical strength of the obtained film of improvement, high temperature, it is preferably able to carry The glass transition temperature of high resin composition, carbon number be 4~10 arlydene or selected from by with or without Alkylidene that the carbon number of substituent group is 1~10 and with or without substituent group carbon number be 4~10 arlydene The group that 2 or more groups in the group of composition are formed by connecting by oxygen atom, more preferably Isosorbide-5-Nitrae-phenylene, 1,5- Asias naphthalene The divalent group shown in base, 2,6- naphthylenes or following [H2] groups.

[changing 110]

[H2]

In addition, in the case of applied to the phase difference film with inverse wave length dispersiveness, substituents alpha is suitably selected¹And α²It is Important.For example, due to low with unexpected inverse wave length dispersiveness as 1 group by the carbon number represented of methylene Tendency, thus α¹And α²Preferably Direct Bonding or its at least any one be carbon number be more than 2 group.

It is further preferred that it can be realized low photoelastic coefficient, straight required by optical film due to not having aromatic rings Connect bonding, ethylidene, n-propylene, positive butylidene, methylmethylene, 1- methyl ethylidene, 2- methyl ethylidene, 2,2- diformazans The ester ring type alkylidene shown in base propylidene, 2- methoxy -2- methyl propylenes or above-mentioned [J] group；Or it can increase The glass transition temperature of high resin composition, 1,4- phenylenes, selected from by the carbon number with or without substituent group 2 in the group of arlydene that alkylidene for 1~10 and the carbon number with or without substituent group are 4~10 composition with On the group that is formed by connecting by oxygen atom of group.

Most preferably ethylidene or n-propylene.Due to inclining when chain length is longer with what glass transition temperature reduced To, thus preferably shorter chain-like groups, such as the group that preferred carbon number is less than 3.Further, due to molecular structure Reduce, it is thus possible to improve the concentration (fluorenes ratio) of the fluorenes ring in repetitive unit, show institute's phase well so as to efficiency The optics physical property of prestige.

In this way, the resin combination of the present invention passes through by having the carbon atom of 9 of the fluorenes unit b of 2 or more to lead to each other The polymer for crossing the repetitive unit that specific carbon-carbon bond is formed by connecting is formed or containing the polymer, can be more so as to have Effectively obtain the tendency of the optical characteristics from fluorenes ring.

As the oligomeric fluorenes of above-mentioned divalent, the substance represented by specifically it is preferable to use the following general formula (11).

[changing 111]

In formula (11), R¹~R³It is each independently Direct Bonding or the carbon number with or without substituent group is 1~4 alkylidene.

N represents 1~5 integer value.

As the R in above-mentioned formula (11)¹And R², substituents alpha can be preferably used as respectively¹And α²Illustrated group.

In addition, as the R in above-mentioned formula (11)³~R⁹And n, the R that can be preferably used as respectively in above-mentioned formula (1)³~ R⁹With the situation illustrated in n.

<4.2 polymer>

Contained polymer has the oligomeric fluorenes of divalent as repetitive unit in the resin combination of the present invention.It for example, can The polymer being formed by connecting with the oligomeric fluorenes for enumerating divalent each other by arbitrary linking group.In addition, the polymer or The copolymer of arbitrary repetitive unit beyond oligomeric fluorenes with divalent.

<4.3 linking group>

With above-mentioned《Invention 2》's<3.4 linking group>Item in the linking group that illustrates it is identical.

<4.4 copolymer>

Oligomeric fluorenes with divalent as repetitive unit polymer or further include arbitrary divalent organic group Copolymer of group's (oligomeric fluorenes for not including divalent wherein) as repetitive unit.In this case, repetitive unit preferably passes through each other Above-mentioned linking group is connected.

In the copolymer, as the arbitrary divalent organic group that can be shared with the oligomeric fluorenes of divalent, and above-mentioned《Invention 2》's<3.5 copolymer>Item in the group that illustrates it is identical.

<4.5 copolymerization compositions>

With above-mentioned《Invention 2》's<3.7 copolymerization compositions>Item in illustrate copolymerization composition it is identical.

With above-mentioned《Invention 2》's<The composition of 3.9 resin combinations>Item in the composition that illustrates it is identical.

《Invention 4》

Hereinafter, to the present invention 4 oligomeric fluorenes diester and used the oligomeric fluorenes diester resin combination manufacturer Method is described in detail.

It should be noted that (general formula) formula (1) recorded below, (1a), (1b), (1a-I), (1a-II), (10e), (I) ~(V), (IIa), (IIb), (VI-1) are used to illustrate each structure in the present invention 4.

<1 oligomeric fluorenes diester A>

The oligomeric fluorenes diester (hereinafter sometimes called " oligomeric fluorenes diester A ") of the present invention is included with or without substitution The fluorenes unit of 2 or more of base, the carbon atom of 9 of the fluorenes unit are bonded or directly with one another by with or without taking The alkylidene of Dai Ji, the arlydene with or without substituent group or the sub- aralkyl with or without substituent group are with chain Shape is bonded, and the content ratio of metal is below 500 mass ppm.

<1.1 concrete structure>

As the oligomeric fluorenes diester of the present invention, the substance represented by specifically it is preferable to use the following general formula (1).

[changing 112]

In formula, R¹~R³It is 1~4 to be each independently Direct Bonding or the carbon number with or without substituent group Alkylidene.

R¹⁰It is the organic substituent that carbon number is 1~10.

N represents 1~5 integer value.

In above-mentioned formula (1), as R¹And R², can be preferably used in respectively above-mentioned《Invention 1》R¹And R²The group In illustrated group.

Similarly, as R³It is preferable to use above-mentioned《Invention 1》R³The group in illustrated group.

As R⁴~R⁹It is preferable to use above-mentioned《Invention 1》R⁴~R⁹The group in illustrated group.

In addition, as R¹⁰It is preferable to use above-mentioned《Invention 2》's<1.3 ester group>It is middle to be used as organic substituent institute example The group shown.

Due to that can reduce the thermal stability of oligomeric fluorenes diester A, cause coloring, thus the content of above-mentioned metal is preferably 400 Below quality ppm, more preferably below 200 mass ppm, further preferably 100 mass ppm are preferably 50 further below Below quality ppm, particularly preferably below 10ppm, it is most preferably below 5 mass ppm.

The species of above-mentioned metal is not particularly limited, due to the gold used when oligomeric fluorenes diester is manufactured as catalyst Belong to it is possible that being mixed into, thus be thought of as selected from the 1st race of long period type periodic table, the 2nd race, the 12nd race, the 14th race and transition metal At least one of metal.Specifically, as the 1st race's metal, lithium, sodium, potassium, caesium can be enumerated, it, can as group II metal To enumerate magnesium, calcium, barium, as the 12nd race's metal, zinc, cadmium can be enumerated, as the 13rd race's metal, aluminium can be enumerated, as 14 race's metals, can enumerate tin, lead, as transition metal, can enumerate iron, copper, titanium, zirconium, manganese, cobalt, vanadium.The present invention's is oligomeric Catalyst remaining when fluorenes diester is due to manufacture etc., usually contains metal.

In the oligomeric fluorenes diester of the present invention, sodium, the potassium isometric preiodic type cycle brought by following processes may be contained The metal of 2nd races such as metal, the calcium of 1 races of Biao, the process carry out hydroxyl first for formaldehydes is made to have an effect in the presence of a base The process of base.Additionally, it is possible to the isometric preiodic types of transition metal, sodium, potassium such as titanium, copper, the iron brought by following processes can be contained The metal of 14th races such as metal, the tin of the 12nd race such as metal, zinc, the cadmiums of the 2nd race such as the 1st race of periodic table, magnesium, calcium, the process are The process that diaryl carbonates esters is made to have an effect and carry out transesterification in the presence of catalyst for ester exchange reaction.

It is preferably transition metal, more preferably from the aspect of the reactivity of catalyst for ester exchange reaction among these Titanium or zirconium, further preferably titanium.

The measuring method of content as metal, for example, ICP-QMS methods.

As make amount of metal be above range method, for example, common method for refining, for example recrystallize, sink again Filter operations, the column chromatographys such as shallow lake method, Hydrolysis kinetics, filter filtering etc..In addition, utilizing the low of the ester-interchange method manufacture present invention In the case of polyfluorene diester A, the carboxylic acid composition of the moisture in reduction raw material or impurity is critically important in advance.

The manufacturing method of oligomeric fluorenes on the present invention is not particularly limited, such as can be by the manufacture that is shown in following formula The methods of method A or autofrettage B, is manufactured.

[changing 113]

Herein, in each structural formula, R¹~R³It is each independently Direct Bonding or with or without substituent group Carbon number is 1~4 alkylidene.

N represents 1~5 integer value.

R¹⁰It is the organic substituent that carbon number is 1~10.

<1.3.1 autofrettage A>

Autofrettage A is following methods：Using fluorenes class (I) as raw material, 9- hydroxymethyl fluorenes classes (IV) are converted to, are passed through afterwards Dehydration synthesis alkene body (V), makes alkene body (V) react with fluorenyl anion, manufactures R³For the oligomeric fluorenes chemical combination of methylene Object (II).It should be noted that unsubstituted 9- hydroxymethyls fluorenes can be bought as reagent.It also can oligomeric fluorenes that thus place obtains Compound (II) imports ester group oligomeric fluorenes diester (1) is made according to aftermentioned process (ii).

It is such as low it has been known that there is 9- hydroxymethyl fluorenes to be converted into after 9- methylene -9H- fluorenes synthesizing by anionic polymerisation The method (J.Am.Chem.Soc., 123,2001,9182-9183.) of the mixture of polyfluorene.These methods are may be referred to, are manufactured Oligofluorenylene compounds (II).

<1.3.2 autofrettage B>

Autofrettage B is following methods：By carrying out the cross-linking reaction (process (i)) of raw material fluorenes class (I) come synthesis of oligonucleotides fluorenes Compound (II) manufactures oligomeric fluorenes diester (1) thereafter by ester group (process (ii)) is imported.

[changing 114]

In the above formulas, R¹~R¹⁰With the R in formula (1)¹~R¹⁰Meaning is identical.

Autofrettage B is divided into the autofrettage of process (i) Oligofluorenylene compounds (II) and the oligomeric fluorenes diester of process (ii) below (1) autofrettage is recorded.

<1.3.3 process (i)：The manufacturing method of Oligofluorenylene compounds (II)>

[changing 115]

In the above formulas, R³~R⁹With the R in n and above-mentioned formula (1)³~R⁹Meaning is identical.

The manufacturing method of the Oligofluorenylene compounds (II) in process (i) is divided into n and R below³Situation recorded.

<1.3.3.1n=1, R³For the situation of Direct Bonding：9,9’：The manufacturing method of 9 ', 9 "-three difluorenes>

9, there are many synthetic method of 9 '-difluorene is known, can be synthesized by Fluorenone or 9- bromine fluorenes (J.Chem.Res., 2004,760；Tetrahedron Lett.,2007,48,6669.).It should be noted that 9,9 '-difluorene can be used as reagent to purchase Enter.

<1.3.3.2n=2, R³For the situation of Direct Bonding：9,9’：The manufacturing method of 9 ', 9 "-three difluorenes>

<1.3.3.3 process (ia)：R³For the manufacturing method of the situation of methylene>

Have methylene-crosslinked Oligofluorenylene compounds can be by fluorenes class (I) and formaldehydes represented by the following general formula (IIa) Represented reaction is manufactured according to the following formula in the presence of a base.

[changing 116]

In the above formulas, R⁴~R⁹With the R in n and above-mentioned formula (1)⁴~R⁹It is identical with n meanings.

<1.3.3.3.1 formaldehydes>

(definition of theoretical amount)

Manufacture as the Oligofluorenylene compounds (IIa) of target in the case of, formaldehydes compared with raw material fluorenes class (I) reason Stoichiometric (molar ratio) is represented by n/ (n+1).

(the reasons why being preferably more than theoretical amount)

In the case of using more than the formaldehydes of theoretical amount compared with fluorenes class (I), have can generate with as the low of target Polyfluorene compound (IIa) is further crosslinked the tendency of the Oligofluorenylene compounds formed compared to fluorenes.Due to the fluorenes of Oligofluorenylene compounds Number of rings, which more increases dissolubility, can more reduce, thus there are the oligomeric fluorenes chemical combination that 4 or more fluorenes ring crosslinkings form in purpose thing In the case of object, it is known that there is the increased tendency of refined load.Therefore it is usually preferred to the dosage of formaldehydes is goal theory amount Less than n/ (n+1) times moles.

In addition, if the dosage of formaldehydes is significantly less than theoretical amount n/ (n+1), with the Oligofluorenylene compounds as target (IIa) Oligofluorenylene compounds few compared to the number of crosslinks of fluorenes ring have residual for main product or raw material fluorenes class (I) unreacted, It will be appreciated that the tendency being greatly reduced with yield.

Optimum amount on formaldehydes as a result, specifically, in the case of n=1, compared with fluorenes class (I) usually 0.1 times mole or more, preferably 0.3 times mole or more, further preferably 0.38 times mole or more, and usually 0.5 times Below mole, be preferably less than 0.46 times mole, be more preferably less than 0.42 times mole.

In addition, in the case of n=2, it is usually 0.5 times mole or more, is preferably 0.55 times mole or more, is further excellent Elect 0.6 times mole or more as, and usually less than 0.66 times mole, be preferably less than 0.65 times mole, be more preferably Less than 0.63 times mole.It follows that according to the dosage of formaldehydes, the structure of main product and the ratio of product have very big change Change, it, can be to obtain the Oligofluorenylene compounds of target n numbers in high yield by being used under conditions of formaldehydes dosage is limited (IIa)。

<1.3.3.3.2 alkali>

In the case of being reacted using homogeneous system, among them, preferably there is the alkali of fully alkalescence in the reaction The alkoxide of metal, more preferable industrial cost low sodium methoxide and sodium ethoxide.Alkali alcoholate herein can use powdery Substance can also use the liquids such as alcoholic solution.And alkali metal can be made to react to prepare with alcohol.

On the other hand, in the case of being reacted using two coating systems, among them, preferably have in the reaction abundant The aqueous solution of the alkali metal hydroxide of alkalescence, the low sodium hydroxide of more preferable industrial cost, the aqueous solution of potassium hydroxide.

In addition, the concentration on aqueous solution, in the case where using particularly preferred sodium hydrate aqueous solution, when concentration is low Reaction speed significantly reduces, thus particularly preferably use is usually more than 10wt/wt%, is preferably more than 25wt/wt%, is more excellent Elect the aqueous solution of more than 40wt/wt% as.

In the case of being reacted using homogeneous system, the dosage of alkali has no the special upper limit compared with raw material fluorenes class (I), but If dosage is excessive, the refined load increase after stirring or reaction, thus usually less than 10 times moles of fluorenes class (I), preferably For less than 5 times moles, further preferably less than 1 times mole.On the other hand, if the dosage of alkali is very few, react into the retardation of walking It is slow, thus as lower limit, be commonly angled relative to raw material fluorenes class (I) for more than 0.01 times mole, preferably 0.1 times mole or more, into One step is preferably 0.2 times mole or more.

On the other hand, in the case of being reacted using two coating systems, the dosage of alkali has no spy compared with raw material fluorenes class (I) The other upper limit, if but dosage it is excessive, the refined load increase after stirring or reaction, thus usually 10 times moles of fluorenes class (I) Below, it is preferably less than 5 times moles, further preferably less than 2 times moles.On the other hand, if the dosage of alkali is very few, react Carry out it is slow, thus as lower limit, be commonly angled relative to raw material fluorenes class (I) as more than 0.1 times mole, preferably 0.3 times mole Above, it is more preferably 0.4 times mole or more.

<1.3.3.3.3 solvent>

It is preferable to use solvent progress for process (ia).As the concrete example for the solvent that can be used, can enumerate：As alkyl Acetonitrile, propionitrile of nitrile series solvent etc.；As the diethyl ether of ether series solvent, tetrahydrofuran, 1,4- dioxane, methylcyclopentyl Ether, t-butyl methyl ether etc.；As the 1,2- dichloroethanes of halogen-based solvent, dichloromethane, chloroform, 1,1,2,2- tetrachloroethanes Deng；Chlorobenzene, 1,2- dichloro-benzenes as halogen system aromatic hydrocarbon etc.；N,N-dimethylformamide, N as acid amides series solvent, N- dimethyl acetamides, N-Methyl pyrrolidone etc.；Dimethyl sulfoxide (DMSO), sulfolane as sulfoxide series solvent etc.；As ring type The monocyclic aliphatic hydrocarbons such as pentamethylene, hexamethylene, cycloheptane, the cyclooctane of aliphatic hydrocarbon, be its derivative methyl cyclopentane, Ethyl cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2- dimethyl cyclohexanes, 1,3- dimethyl cyclohexanes, 1,4- dimethyl Hexamethylene, isopropyl cyclohexane, n-propyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl butylcyclohexane, 1,2, The polycycles aliphatic hydrocarbons such as 4- trimethyl-cyclohexanes, 1,3,5- trimethyl-cyclohexanes etc., decahydronaphthalenes；Pentane, n-hexane, just The non-ring type aliphatic hydrocarbon such as heptane, normal octane, isooctane, n -nonane, n-decane, n-dodecane, n-tetradecane；As aromatic series Toluene, paraxylene, ortho-xylene, meta-xylene of hydrocarbon etc.；As the methanol of alcohol series solvent, ethyl alcohol, isopropanol, n-butanol, The tert-butyl alcohol, hexanol, octanol, cyclohexanol etc..

In the reaction of homogeneous system, since the dissolubility of the anion generated by fluorenes class (I) is high, it is good that there is reaction to carry out Good tendency, thus the preferably acid amides series solvent of polar solvent or sulfoxide series solvent.Wherein, N, N- bis- are particularly preferably Methylformamide.This is because, dissolubility of the Oligofluorenylene compounds (IIa) in n,N-Dimethylformamide is low, in purpose thing It is precipitated rapidly after generation, inhibits the progress of the reaction more than it, there is the tendency that the selectivity of purpose thing increases.

In the reaction of two coating systems, 2 layers are formed with alkaline aqueous solution, by the dissolubility of the anion of fluorenes class (I) generation There is height reaction to carry out good tendency, thus the preferably ether series solvent or halogen-based solvent of polar solvent.It is wherein special It You Xuanwei not tetrahydrofuran.This is because, dissolubility of the Oligofluorenylene compounds (IIa) in tetrahydrofuran is low, given birth in purpose thing Into rear rapid precipitation, inhibit the progress of the reaction more than it, there is the tendency that the selectivity of purpose thing increases.

These solvents can be used alone, and two or more may be used in combination.

On the dosage of solvent, usually using reach 10 times of volumes of raw material fluorenes class (I), be preferably 7 times of volumes, into One step is preferably the amount of 4 times of volumes.On the other hand, if the dosage of solvent is very few, stir become difficult and meanwhile have reaction into It goes and is slowly inclined to, thus be used as lower limit, usually used 1 times of volume for reaching raw material fluorenes class (I), preferably 2 times of volumes, The amount of further preferably 3 times volumes.

<1.3.3.3.4 reaction formation>

<1.3.3.3.5 reaction condition>

For process (ia), in order to inhibit the life for the compound that fluorenes ring crosslinking forms compared with Oligofluorenylene compounds (IIa) Into preferably being reacted at low temperature as far as possible.On the other hand, if temperature is too low, sufficient reaction speed may be cannot get.

Therefore, as specific reaction temperature, usually it is 40 DEG C, is preferably 30 DEG C, more preferably 20 DEG C of temperature in the upper limit Under implemented.On the other hand, within the range having a lower limit of -50 DEG C, be preferably -20 DEG C, more preferably 0 DEG C implemented.

On the General reactions time in process (ia), usual lower limit is 30 minutes, is preferably 60 minutes, further preferably For 2 it is small when, the upper limit is not particularly limited, but usually 20 it is small when, be preferably 10 it is small when, further preferably 5 it is small when.

<1.3.3.3.6 the separation and purification of purpose thing>

After termination of the reaction, reaction solution can be added in the acid waters such as dilute hydrochloric acid or adds the acid waters such as dilute hydrochloric acid It is added in reaction solution, purpose thing Oligofluorenylene compounds (IIa) is precipitated, thus separated.

In addition, after termination of the reaction, the solvent of dissolvable purpose thing Oligofluorenylene compounds (IIa) can be also added to water In reaction solution, extract.The purpose thing gone out using solvent extraction can be by bad molten by the method for solvent concentration or addition Method of agent etc. is separated.But since Oligofluorenylene compounds (IIa) have dissolubility in a solvent very at room temperature Low tendency, thus the method that it is precipitated generally preferably is contacted with acid water.

Obtained Oligofluorenylene compounds (IIa) can also use directly as the raw material of process (ii), can also carry out essence For in process (ii) after system.As method for refining, common method for refining, such as recrystallization, reprecipitation method, extraction essence may be employed System, column chromatography etc., there is no restriction.

<1.3.3.4 process (ib)：R³For the manufacturing method of the situation beyond Direct Bonding>

Oligofluorenylene compounds represented by the following general formula (IIb) can be using fluorenes class (I) as raw material, in alkylating agent (VIIIa) and in the presence of alkali manufactured according to the reaction represented by following formula (ib).

[changing 117]

Oligofluorenylene compounds in above-mentioned formula are represented with structural formula (IIb).

In above-mentioned formula, R³、R⁴~R⁹With the R in n and above-mentioned formula (1)³、R⁴~R⁹It is identical with n meanings.X represents leaving group. As the example of leaving group, halogen atom (not including fluorine) or mesyl or p-toluenesulfonyl etc. can be enumerated.

In the autofrettage of Oligofluorenylene compounds (IIb), using n-BuLi as alkali, the anion of fluorenes class (I) is being generated Afterwards, the method for itself and alkylating agent (VIIIa) coupling is made to be widely known by the people, it is known to R³For the situation or R of ethylidene³For Asia Propyl etc. autofrettage (Organometallics, 2008,27,3924；J.Molec.Cat.A：Chem.,2004,214, 187.).In addition, in addition to alkylidene also have using xylylene carry out it is crosslinked report example (J.Am.Chem.Soc., 2007,129,8458.).But using these using n-BuLi method carry out industry manufacture when, secure context, into Present aspect has the tendency of extremely difficult.

As the alkylating agent used in process (ib), can enumerate：Diiodomethane, 1,2- ethylidene periodides, 1,3- diiodo-s Propane, bis- iodobutanes of 1,4-, bis- iodopentanes of 1,5-, bis- iodohexanes of 1,6-, methylene bromide, glycol dibromide, 1,3- dibromos third Alkane, 1,4- dibromobutanes, pentamethylene bromide, 1,6- dibromo-hexanes, dichloromethane, 1,2- dichloroethanes, 1,3- dichloropropanes, The alkyl dihalide of the straight-chains such as the bromo- 3- chloropropanes of 1,4- dichloroetane, 1,5- dichloropentane, 1,6- dichloro hexanes, 1- is (no Including fluorine atom)；2,2- dimethyl -1,3- dichloropropanes etc. include the alkyl dihalide of branch (not including fluorine atom)；1, The aralkyl dihalide (not including fluorine atom) such as double (bromomethyl) benzene of 4-, double (bromomethyl) benzene of 1,3-；Glycol dinitrate sulfonic acid The disulfonate of the glycol such as ester, glycol dinitrate benzene sulfonate, propylene glycol bis-mesylate, tetramethylene glycol bis-mesylate Deng.

<1.3.4 the manufacturing method of oligomeric fluorenes diester (1)>

In the following, the manufacturing method of the oligomeric fluorenes diester (1) in the process (ii) represented by following formula is pressed into R¹And R²Species point It is not recorded.

[changing 118]

In the above formulas, R¹~R⁹With the R in n and above-mentioned formula (1)¹~R⁹It is identical with n meanings.R_i、R_iiAnd R_iiiRepresent hydrogen Alkyl that atom, the carbon number with or without substituent group are 1~10, the carbon number with or without substituent group are 4~10 aryl or with or without substituent group carbon number be 6~10 aralkyl.

<1.3.4.1 process (iia)：In general formula (1), the autofrettage based on Michael (Michael) addition>

Oligomeric fluorenes diester represented by the following general formula (1a) can be in the presence of a base according to represented by following processes (iia) By Oligofluorenylene compounds (II) and α, beta-unsaturated esters (VI) are manufactured for reaction.

[changing 119]

In above-mentioned formula, R³~R¹⁰With the R in n and above-mentioned formula (1)³~R¹⁰It is identical with n meanings.R_i、R_iiAnd R_iiiIt is each independent Ground represents alkyl, the carbon with or without substituent group that hydrogen atom, the carbon number with or without substituent group are 1~10 Aryl that atomicity is 4~10 or with or without substituent group carbon number be 6~10 aralkyl.

<1.3.4.1.1 α, beta-unsaturated esters>

As alpha, beta-unsaturated esters (VI), methyl acrylate, ethyl acrylate, phenyl acrylate, acrylic acid can be enumerated Allyl ester, glycidyl acrylate, 2-Hydroxy ethyl acrylate, acrylic acid -4- hydroxybutyls, 1,4 cyclohexane dimethanol The esters of acrylic acid such as mono acrylic ester, methyl methacrylate, ethyl methacrylate, phenyl methacrylate, metering system Methyl acrylic esters, the 2- ethyls third such as allyl propionate, glycidyl methacrylate, methacrylic acid -2- hydroxy methacrylates The alpha-substituted unsaturation esters such as e pioic acid methyl ester, 2- phenylacrylic acid methyl esters, methyl cinnamate, ethyl cinnamate, M Cr, The β such as butenoic acid ethyl-substitution unsaturation esters.Wherein, it is preferably able to be introduced directly into the following general formula of polymerisation reactivity group (VI-1) esters of unsaturated carboxylic acids represented by

[changing 120]

(in formula, R¹⁰Represent the organic substituent that carbon number is 1~10, R_iiiRepresent hydrogen atom, with or without taking Alkyl that the carbon number of Dai Ji is 1~10, with or without substituent group carbon number be 4~10 aryl or tool Have or aralkyl that carbon number without substituent group is 6~10.), esters of acrylic acid, the methyl being more preferably included in Esters of acrylic acid or alpha-substituted unsaturation esters, from reaction speed and reaction selectivity aspect, further preferred R_iiiFor The esters of acrylic acid or methyl acrylic ester of hydrogen atom or methyl.Due to R¹⁰For smaller group when, industrial cost it is low and Distillation is refined easily, reactivity is also high, thus still more preferably methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, phenyl acrylate or phenyl methacrylate.Among these, due to being difficult to be hydrolyzed, being difficult to give birth to Into by-product carboxylic acid, thus particularly preferably ethyl acrylate, ethyl methacrylate.

On the other hand, the organic substituent on ester group, be 2-Hydroxy ethyl acrylate, acrylic acid -4- hydroxybutyls, In the case that 1,4-CHDM mono acrylic ester etc. has the esters of hydroxy alkyl, can polyester carbon be obtained by a step The raw material of acid esters, polyester, thus particularly preferably.

The polymerization activities of alpha, beta-unsaturated esters (VI) is high, thus in the presence of with high concentration, have easily due to light, heat, The outside stimulus such as soda acid and the tendency polymerizeing.At this point, it is highly exothermic due to being accompanied by, thus may can be very dangerous. Therefore, from security aspect, the dosage of alpha, beta-unsaturated esters (VI) is preferred with being less excessively used.It is commonly angled relative to original Expect Oligofluorenylene compounds (II) for less than 10 times moles, preferably less than 5 times moles, further preferably less than 3 times moles.It closes In lower limit, due to being calculated as 2 times moles compared with raw material with theoretical amount, thus lower limit is usually 2 times moles or more.It is anti-in order to accelerate It should carry out, retained material or intermediate, the dosage of alpha, beta-unsaturated esters (VI) are not compared with raw material Oligofluorenylene compounds (II) 2.2 times moles or more, further preferably 2.5 times moles or more.

<1.3.4.1.2 alkali>

In R³For methylene situation in addition in the case of, have Oligofluorenylene compounds (II) reactivity have compared with The tendency of big difference.Therefore, it is divided into R³It is recorded for the situation and situation in addition of methylene.

In R³In the case of methylene, Oligofluorenylene compounds (II) easily carry out decomposing in a solvent anti-in the presence of a base It should.Therefore, it is secondary anti-for decomposition reaction etc. can be inhibited in the case where being reacted using 2 coating systems of organic layer and water layer The reason for answering, it is preferable to use water-soluble inorganic bases.Wherein from the aspect of cost, reactivity, the hydrogen-oxygen of preferred as alkali The aqueous solution of compound, the particularly aqueous solution of the aqueous solution of more preferable sodium hydroxide or potassium hydroxide.

In addition, the concentration on aqueous solution, in the case where using particularly preferred sodium hydrate aqueous solution, if concentration is low Then reaction speed can significantly reduce, thus use is usually more than 10wt/wt%, is preferably more than 30wt/wt%, more preferably The aqueous solution of more than 40wt/wt%.

In R³In the case of for methylene, on the dosage of alkali, compared with raw material Oligofluorenylene compounds (II), the upper limit does not have Have special limitation, but when the dosage of alkali is excessive, the refined load after stirring or reaction may increase, thus used as In the case of the sodium hydrate aqueous solution of more than the 40wt/wt% of particularly preferred alkali, oligomeric fluorenes (II) is commonly angled relative to as 10 Below times volume, be preferably below 5 times of volumes, below further preferably 2 times of volumes.When alkali number is very few, reaction Speed significantly reduces, thus alkali is usually more than 0.1 times of volume compared with raw material Oligofluorenylene compounds (II).Preferably 0.2 More than times volume, more than more preferably 0.5 times of volume.

In R³In the case of beyond methylene, on the dosage of alkali, compared with raw material Oligofluorenylene compounds (II), thereon Limit is not particularly limited, but when the dosage of alkali is excessive, the refined load after stirring or reaction may increase, thus use In the case of sodium methoxide or sodium ethoxide as particularly preferred alkali, Oligofluorenylene compounds (II) are commonly angled relative to as 5 times moles Below, it is preferably less than 2 times moles, further preferably less than 1 times mole, particularly preferably less than 0.5 times mole.In alkali number When very few, reaction speed significantly reduces, thus alkali is usually 0.005 times mole or more compared with the oligomeric fluorenes of raw material (II).It is excellent Elect 0.01 times mole or more, more preferably 0.05 times mole or more, particularly preferably 0.1 times mole or more as.

<1.3.4.1.3 phase transfer catalyst>

As phase transfer catalyst, can enumerate tetramethyl ammonium chloride, tetrabutylammonium bromide, methyl tricapryl ammonium chloride, Three decyl ammonium chloride of methyl, benzyltrimethylammonium chloride, tri-n-octyl methyl ammonium chloride, tetrabutylammonium iodide, acetyl group trimethyl The halide of the quaternary ammonium salts such as ammonium bromide, benzyltriethylammoinium chloride (not including fluorine)；N, N- dimethyl pyrrolidine chloride, N- Ethyl-N-methyl pyrrolidines iodide, N- butyl-N- crassitudes bromide, N- Benzyl-N-methyl pyrrolidines chlorine The halide of the seasons pyrrolidinium such as compound, N- ethyl-N-methyl pyrrolidines bromides (not including fluorine)；N- butyl-N- first The seasons morpholine such as base morpholine bromide, N- butyl-N-methylmorpholine iodide, N- pi-allyls-N-methylmorpholine bromide The halide of salt (not including fluorine)；N- methyl-N-benzyls piperidinium chloride, N- methyl-N-benzyls piperidinium bromide, N, The seasons such as N- lupetidines iodide, N- methyl-N ethyl Piperidineacetic acids salt, N- methyl-N ethyl piperidines iodide The halide of piperidinium salt (not including fluorine)；Crown ether-like etc..It is preferred that quaternary ammonium salt, further preferred tetrabutylammonium bromide, benzyl three Ammonio methacrylate or benzyltriethylammoinium chloride.

The dosage of phase transfer catalyst compared with raw material Oligofluorenylene compounds (II) it is excessive when, there is ester hydrolysis or step by step The tendency that the side reactions such as michael reaction significantly carry out, and from cost aspect, it is commonly angled relative to Oligofluorenylene compounds (II) also it is less than 5 times moles, is preferably less than 2 times moles, further preferably less than 1 times mole.Phase transfer catalyst When dosage is very few, there is the significantly reduced tendency of reaction speed, thus the dosage of phase transfer catalyst is compared with the oligomeric fluorenes of raw material It is usually 0.01 times mole or more to close object (II).Preferably 0.1 times mole or more, more preferably 0.5 times mole or more.

<1.3.4.1.4 solvent>

It is preferable to use solvent progress for process (iia).

In R³In the case of for methylene, by using the solvent being separated with water, it is known that having can inhibit low The tendency of the side reactions such as the decomposition reaction of polyfluorene compound (II).Further, the oligomeric fluorenes of raw material can preferably be dissolved using In the case of the solvent of compound (II), for the reason for carrying out good tendency is reacted, it is preferable to use the oligomeric fluorenes of raw material The solubility of compound (II) is the solvent of more than 0.5 mass %, is more than 1.0 mass % more preferably using the solubility, special It is preferable to use the solvents that the solubility is more than 1.5 mass %.In particular, it is preferred that halogen system aliphatic hydrocarbon, halogen system virtue Fragrant race's hydrocarbon, aromatic hydrocarbon or ether series solvent, particularly preferred dichloromethane, chlorobenzene, chloroform, 1,2- dichloro-benzenes, tetrahydrofuran, 1,4- dioxane or methylcyclopentyl ether.

These solvents can be used alone, and two or more may be used in combination.

On the dosage of solvent, the upper limit is not particularly limited, if the generation in view of the purpose thing in each reactor is imitated Rate, then usually using reach raw material Oligofluorenylene compounds (II) 20 times of volumes, be preferably 15 times of volumes, further preferably For the amount of 10 times of volumes.On the other hand, if the dosage of solvent is very few, the dissolubility of reagent is deteriorated, stirs change hardly possible, while anti- The carry out answered is slow, thus as lower limit, usually used 1 times of volume for reaching raw material Oligofluorenylene compounds (II) is preferably 2 The amount of times volume, further preferably 4 times of volumes.

In R³In the case of beyond methylene, it is known that there is the dissolubility of organic base and Oligofluorenylene compounds (II) to anti- Speed band is answered to carry out the tendency of larger impact, in order to ensure the dissolubility, it is preferable to use with dielectric constant more than certain value Solvent.As the solvent that can preferably dissolve organic base and Oligofluorenylene compounds (II), optimization aromatic heterocycle, alkyl nitrile are molten Agent, acid amides series solvent, sulfoxide series solvent, particularly preferred pyridine, acetonitrile, n,N-Dimethylformamide, n,N-dimethylacetamide, Dimethyl sulfoxide (DMSO), sulfolane.

These solvents can be used alone, and two or more may be used in combination.

On the dosage of solvent, the upper limit is not particularly limited, if the generation in view of the purpose thing in each reactor is imitated Rate, then usually using reach the oligomeric fluorenes of raw material (II) 20 times of volumes, be preferably 15 times of volumes, further preferably 10 times The amount of volume.On the other hand, if the dosage of solvent is very few, the dissolubility of reagent is deteriorated, stirs change hardly possible, while has reaction Progress be slowly inclined to, thus as lower limit, usually using reaching 1 times of volume of the oligomeric fluorenes of raw material (II), be preferably 2 times The amount of volume, further preferably 4 times of volumes.

<1.3.4.1.5 reaction formation>

<1.3.4.1.6 reaction condition>

Process (iia) if in temperature it is too low, cannot get sufficient reaction speed, if otherwise temperature is excessively high, with α, The polymerisation of beta-unsaturated esters (VI) easily carries out, by hydrolyzing the oligomeric fluorenes represented by easily generation the following general formula (1a-I) The tendency of monoesters monocarboxylic acid and the oligomeric fluorenes dicarboxylic acids represented by (1a-II), thus preferably carry out temperature treatment.Therefore, as Reaction temperature, specifically, usually within the range having a lower limit of 0 DEG C, preferably 10 DEG C, more preferably 15 DEG C is implemented.On the other hand, lead to Often it is 40 DEG C, preferably 30 DEG C, more preferably 20 DEG C in the upper limit to be implemented.

[changing 121]

In above-mentioned formula, n, R³~R¹⁰、R_i、R_iiAnd R_iiiWith n, R in above-mentioned formula (1a)³~R¹⁰、R_i、R_iiAnd R_iiiMeaning phase Together.

On the General reactions time in process (iia), when usual lower limit is 30 minutes, preferably 1 is small, further preferably For 2 it is small when, if the reaction time is long, the oligomeric fluorenes diester (1a) that generates is likely to occur hydrolysis and generates carboxylic acid, thus usually For 10 it is small when, be preferably 5 it is small when, further preferably 2 it is small when.

<1.3.4.1.7 the separation and purification of purpose thing>

After termination of the reaction, following methods, which can be used, is precipitated the oligomeric fluorenes diester (1a) of purpose thing, so as to carry out purpose thing The separation of oligomeric fluorenes diester (1a), the method are by filtering byproduct metal halide and the inorganic base of remaining from anti- The method for answering the poor solvent of the method that solvent concentration is carried out after being removed in liquid or adding purpose object；Etc..

In addition, after termination of the reaction, acid water and the oligomeric fluorenes diester of dissolvable purpose thing can also be added into reaction solution The solvent of (1a) extracts.The purpose thing gone out using solvent extraction can pass through the method concentrated to solvent or addition Method of poor solvent etc. is separated.

As the solvent that can be used in extraction, as long as can dissolve the oligomeric fluorenes diester (1a) of purpose thing, without spy It does not limit, but is adapted in use to 1 in halogen-based solvents such as the aromatic hydrocarbon compounds such as toluene, dimethylbenzene, dichloromethane, chloroform etc. Kind or two or more.

The oligomeric fluorenes diester (1a) obtained herein can directly make by polyester or in the form of polyestercarbonate starting monomer With or can also be used etc. in the form of the precursor of polycarbonate starting material monomer, but can also carry out it is refined after make With.Particularly, the carboxylic acid compositions such as oligomeric fluorenes monoesters monocarboxylic acid (1a-I) and oligomeric fluorenes dicarboxylic acids (1a-II) are being contained as impurity In the case of, in the manufacture of oligomeric fluorene diaryl ester (2), the catalyst poison as catalyst for ester exchange reaction can be not only caused, Tenor contained by oligomeric fluorene diaryl ester (2) can also increase, it is known that it is related with the reduction of thermal stability, therefore preferably into Row purification operations.As method for refining, common method for refining, such as recrystallization, reprecipitation method, Hydrolysis kinetics, column color may be employed Spectrum etc., there is no restriction.In Hydrolysis kinetics, by using alkalescence aqueous solution, so as to by carboxylic acid composition with the shape of carboxylate Formula is removed and gone in water layer, thus preferably.More preferably using sodium acid carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide etc. The aqueous solution of inorganic base is still more preferably difficult to happen the water-soluble of the weak base such as the sodium acid carbonate, sodium carbonate, potassium carbonate of hydrolysis Liquid.In addition, also oligomeric fluorenes diester (1a) can be dissolved in appropriate solvent, handled using activated carbon.It can make at this time Solvent is identical with the solvent that can be used during extraction.

The oligomeric fluorenes diester (1a) obtained herein can be directly as polyester or polyestercarbonate starting monomer or conduct The precursor of polycarbonate starting material monomer uses etc..

<1.3.4.2 process (iib)：Manufacturing method based on alkylated reaction>

Oligomeric fluorenes diester (1b) can be by by Oligofluorenylene compounds (II) and alkylating agent (VIIIb) and (VIIIc) The method of alkylated reaction manufactured.

[changing 122]

In above-mentioned formula, R¹~R¹⁰With the R in n and above-mentioned formula (1)¹~R¹⁰It is identical with n meanings.X represents leaving group.As The example of leaving group can enumerate halogen atom (not including fluorine), mesyl or p-toluenesulfonyl etc..

The alkylated reaction of fluorenes class is widely known by the people, for example, there have report to propose double (bromine hexyl) fluorenes of 9,9-, 9,9- to be double Double (alkylhalide group) fluorenes (J.Org.Chem., 2010,75,2714.) of the 9,9- such as (iodine hexyl) fluorenes.It, can according to these technological thoughts Carry out synthesis of oligonucleotides fluorenes diester (1b) using Oligofluorenylene compounds (II) as raw material.

As the alkylating agent used in process (iib), methyl chloroacetate, methyl bromoacetate, iodoacetic acid first can be enumerated Ester, ethyl chloroacetate, bromoacetate, ethyl iodoacetate, propyl chloroacetate, Solid acid n-butyl chloroacete, chloroacetic acid tert-butyl ester, bromine second Tert-butyl acrylate, the iodoacetic acid tert-butyl ester, methyl chloropropionate, methyl bromide c, iodopropionic acid methyl esters, chloropropionate, the tertiary fourth of chloropropionic acid Ester, the bromo-propionic acid tert-butyl ester, ethyl bromide, iodopropionic acid ethyl ester, chlorobutanoate, bromo butyric acid methyl ester, iodine methyl butyrate, chloro-butyric acid The halogenated alkanes acid alkyl esters such as ethyl ester, neoprene acid ethyl ester, iodine ethyl butyrate, the iodopropionic acid tert-butyl ester；Phenyl chloroacetate, bromoacetic acid benzene The halogenated-chain acids aryl esters such as ester, iodoacetic acid phenyl ester；4- chloromethyl benzoic acids methyl esters, 4- bromomethyl-benzoic acid methyl esters, 4- chloromethanes The alkyl halides such as yl benzoic acid ethyl ester, 4- bromomethyl-benzoic acid ethyl esters, 3- chloromethyl benzoic acids methyl esters, 3- bromomethyl-benzoic acid methyl esters Yl benzoic acid Arrcostab etc..

It should be noted that after the reaction terminating of process (iib), preferably the oligomeric fluorenes diester of purpose thing (1b) is divided From refined.As the method that separation and purification is made, preferably may be employed<1.3.4.1.7 the separation and purification of purpose thing>In The method of record.

<1.3.4.3 manufacturing method (two virtue of oligomeric fluorenes based on ester exchange reaction of the oligomeric fluorene diaryl ester of general formula (2) The autofrettage of base ester compound (2))>

Oligomeric fluorene diaryl ester compounds (2) can be by passing through oligomeric fluorenes diester compound (1) and diaryl carbonate The method of the ester exchange reaction process (process (iic)) of class (11a) is manufactured.

[changing 123]

In above-mentioned formula, R¹~R¹⁰With the R in n and above-mentioned formula (1)¹~R¹⁰It is identical with n meanings.Ar¹Expression has or does not have The carbon number of substituted base is 4~10 aryl.

<1.3.4.3.1 manufacturing method (the oligomeric fluorenes two based on ester exchange reaction of the oligomeric fluorene diaryl ester of general formula (2) The autofrettage of aryl ester compound (2))>

Ar¹For be 4~10 with or without the carbon number of substituent group aryl oligomeric fluorene diaryl ester compounds (2) can in the presence of ester exchange catalyst according to the reaction represented by process (iic) by oligomeric fluorenes diester compound (1), two virtue Base carbonates (11a) are manufactured.

<1.3.4.3.1.1 oligomeric fluorenes diester compound (1)>

When the content of the carboxylic acid of oligomeric fluorenes diester compound (1) is more, carboxylic acid becomes the catalyst of catalyst for ester exchange reaction Poison has the tendency for needing largely to use catalyst for ester exchange reaction.Therefore, if the content of carboxylic acid is more, with oligomeric fluorenes two The increased tendency of tenor contained by aryl ester compound (2).From the metal reduced contained by oligomeric fluorene diaryl ester (2) It sets out in terms of amount, the content of the carboxylic acid in oligomeric fluorenes diester compound (1) is preferably below 5 mass %, is more preferably 3 matter It measures below %, further preferably below 2 mass %, be still more preferably below 1 mass %.In addition, carboxylic acid content is fewer The more preferred, if wanting to make it for 0 mass %, impurity, which is mixed into etc., in order to prevent is possible to that effect is raised or produced with significant cost Rate reduces.The content for maintaining productivity and accessible carboxylic acid is usually more than 0.1 mass %.

As the carboxylic acid contained by oligomeric fluorenes diester compound (1), for example, oligomeric fluorenes monoesters monocarboxylic acid, oligomeric Fluorenes dicarboxylic acids.

The molal quantity of oligomeric fluorenes monoesters monocarboxylic acid, oligomeric fluorenes dicarboxylic acids contained by oligomeric fluorenes diester compound (1) is for example The area % that can be analyzed using calibration curve by HPLC is estimated.

<1.3.4.3.1.2 diaryl carbonate esters>

Diaryl carbonate esters as reaction reagent can enumerate diphenyl carbonate, carboxylol ester, double (chlorobenzenes Base) carbonic ester, m-cresyl, carbonic acid dinaphthyl ester, double (biphenyl) esters of carbonic acid etc..Wherein preferred low cost and can industry obtain The diphenyl carbonate obtained.

These diaryl carbonates can be used alone, and can also be used in mixed way two or more.

On the dosage of diaryl carbonate esters, the special upper limit is had no compared with the oligomeric fluorenes diester (1) of raw material, if but dosage Excessively, then there is the increased tendency of refined load after reaction, thus usually less than 20 times moles of oligomeric fluorenes diester, preferably For less than 10 times moles, further preferably less than 5 times moles.

On the other hand, if the dosage of arylcarbonic acid esters is very few, the oligomeric fluorenes diester (1) of raw material or as intermediate as Oligomeric fluorenes list aryl ester (10e) shown in lower might have residual, thus as lower limit, be commonly angled relative to the oligomeric fluorenes diester of raw material (1) it is 1 times mole or more, is preferably 1.5 times moles or more, further preferably 2 times moles or more.

[changing 124]

<1.3.4.3.1.3 catalyst for ester exchange reaction>

As catalyst for ester exchange reaction, can enumerate：It is four titanium butoxides, four isobutoxy titaniums, titanium tetramethoxide, four different Titanium propanolate, purity titanium tetraethoxide, four (2- ethyl hexyl oxies) titaniums, four (stearic oxygroup) titaniums, four phenoxide titaniums, titanium acetylacetone (IV), the titanium compounds such as double (acetylacetone,2,4-pentanedione) titaniums (IV) of diisopropoxy；Lithium carbonate, dibutylamino lithium, acetylacetone,2,4-pentanedione lithium, benzene The alkali metal compounds such as oxygroup sodium, phenoxy group potassium；The cadmium compounds such as acetylacetone,2,4-pentanedione cadmium, cadmium carbonate；Acetylacetone,2,4-pentanedione zirconium, zirconocene etc. Zirconium compounds；Vulcanized lead, lead hydroxide, plumbite, zincate, ceruse, lead acetate, tetrabutyl lead, tetraphernl-lead, triphenyl The lead compounds such as lead, dimethoxy lead, two phenoxy group lead；Copper acetate, bis-acetylacetonate copper, copper oleate, cupric dibutyldithiocarbamate, dimethoxy The copper compounds such as copper, copper chloride；The iron such as iron hydroxide, ferric carbonate, triacetoxyl group iron, trimethoxy iron, triple phenoxyl iron Close object；The zinc compounds such as bis-acetylacetonate zinc, diacetoxy zinc, dimethoxy zinc, diethoxy zinc, two phenoxy group zinc；Two Normal-butyl tin oxide, diphenyl tin oxide, di-n-octyl tin oxide, dimethoxy di-n-butyl tin, two propylene of di-n-butyl tin Acid esters, di-n-butyl tin dimethylacrylate, di-n-butyl tin dilaurate, tetramethoxy tin, four phenoxy group tin, four fourths The organo-tin compounds such as base -1,3- diacetoxy distannoxanes；The aluminium such as aluminium acetate, aluminum methoxide, aluminum ethoxide, phenoxy group aluminium Compound；The vfanadium compound such as vanadium dichloride, vanadium trichloride, vanadium tetrachloride, vanadic sulfate；Phenoxy group tetraphenylphosphonium Deng phosphonium salts etc.. They can be used alone, and can also share two or more.

On the dosage of catalyst for ester exchange reaction, the special upper limit is had no compared with the oligomeric fluorenes diester (1) of raw material, if but with Amount is excessive, then the refined load increase after reacting, thus usually 20 moles of below % of fluorenes, be preferably 10 moles of below %, Further preferably 5 moles of below %.

On the other hand, when the dosage of catalyst for ester exchange reaction is very few, the reaction time may be long, thus under conduct Limit is commonly angled relative to the oligomeric fluorenes diester of raw material as 0.1 mole of more than %, preferably 0.5 mole of more than %, further preferably 1 Mole more than %.

<1.3.4.3.1.4 solvent>

Reaction dissolvent can be used in process (iic), but preferably without using reaction dissolvent, merely with the oligomeric fluorenes two of raw material Ester (1), diaryl carbonate esters and catalyst for ester exchange reaction are reacted.But in the oligomeric fluorenes diester (1) of raw material, two Arylcarbonic acid esters room temperature is solid, is difficult in the case of stirring, and can also use reaction dissolvent.Using the feelings of reaction dissolvent Under condition, as long as can suitably to dissolve and/or disperse the oligomeric fluorenes diester (1) of above-mentioned raw materials, diaryl carbonate esters and ester The solvent of exchange reaction catalyst, species are arbitrary.

Specifically, the solvent that can be used can be enumerated：Acetonitrile, propionitrile as alkyl nitrile series solvent etc.；As ketone Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) of series solvent etc.；As the diethyl ether of ether series solvent, tetrahydrofuran, 1,4- dioxies Six rings, methylcyclopentyl ether, t-butyl methyl ether etc.；As the 1,2- dichloroethanes of halogen-based solvent, dichloromethane, chloroform, 1, 1,2,2- tetrachloroethanes etc.；Chlorobenzene, 1,2- dichloro-benzenes as halogen system aromatic hydrocarbon etc.；As the N of acid amides series solvent, N- bis- Methylformamide, DMAC N,N' dimethyl acetamide etc.；Dimethyl sulfoxide (DMSO), sulfolane as sulfoxide series solvent etc.；As ring type fat The monocyclic aliphatic hydrocarbons such as pentamethylene, hexamethylene, cycloheptane, the cyclooctane of fat race hydrocarbon；Methyl cyclopentane, second for its derivative Cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2- dimethyl cyclohexanes, 1,3- dimethyl cyclohexanes, 1,4- diformazan basic rings Hexane, isopropyl cyclohexane, n-propyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl butylcyclohexane, 1,2,4- Trimethyl-cyclohexane, 1,3,5- trimethyl-cyclohexanes etc.；The polycycles aliphatic hydrocarbon such as decahydronaphthalenes；Pentane, n-hexane, positive heptan The non-ring type aliphatic hydrocarbon such as alkane, normal octane, isooctane, n -nonane, n-decane, n-dodecane, n-tetradecane；As aromatic hydrocarbon Toluene, paraxylene, ortho-xylene, meta-xylene, 1,3,5- trimethylbenzenes, 1,2,4- trimethylbenzenes, 1,2,3,4- tetrahydrochysenes Naphthalene etc.；Pyridine as heteroaromatic etc..

Since the reaction preferably carries out at a high temperature of usually 100 DEG C or more, thus in above-mentioned solvent, preferred boiling point Chlorobenzene, 1,2- dichloro-benzenes, trichloro-benzenes, toluene, paraxylene, ortho-xylene, meta-xylene for 100 DEG C or more of solvent, 1, 3,5- trimethylbenzenes, 1,2,4- trimethylbenzenes, 1,2,3,4- naphthanes, decahydronaphthalenes, N,N-dimethylformamide, N, N- diformazans Yl acetamide, dimethyl sulfoxide (DMSO) or sulfolane, for can suitably dissolve the oligomeric fluorenes diester (10b) of raw material, boiling point 130 DEG C or more, can carry out the reason for reaction under higher temperature, particularly preferred 1,2- dichloro-benzenes, dimethylbenzene, 1,3,5- trimethyls Benzene, 1,2,4- trimethylbenzenes or 1,2,3,4- naphthanes, decahydronaphthalenes.

These solvents can be used alone, and two or more may be used in combination.

On the dosage of solvent, the upper limit is not particularly limited, if the generation in view of the purpose thing in each reactor is imitated Rate, then usually using reach the oligomeric fluorenes diester (1) of raw material 15 times of volumes, be preferably 10 times of volumes, further preferably 5 The amount of times volume.On the other hand, if the dosage of solvent is very few, the dissolubility of reagent is deteriorated, stirs change hardly possible, simultaneous reactions It carries out slowly, thus as lower limit, reaches 1 times of volume usually using the densimeter with the oligomeric fluorenes diester (1) of raw material, is preferably The amount of 2 times of volumes, further preferably 4 times of volumes.

<1.3.4.3.1.5 reaction formation>

<1.3.4.3.1.6 reaction condition>

<1.3.4.3.1.7 the separation and purification of purpose thing>

After termination of the reaction, poor solvent can be added into reaction solution, the oligomeric fluorene diaryl ester (2) of purpose thing is precipitated, Thus separated.

In addition, after termination of the reaction, the solvent of the oligomeric fluorene diaryl ester (2) of dissolvable purpose thing can be also added to water In reaction solution, extract.The purpose thing gone out using solvent extraction can be by using the side of poor solubility caused by temperature difference Method separates the solvent method concentrated or the method for adding poor solvent etc..

Obtained oligomeric fluorene diaryl ester (2) also can be as polycarbonate starting material or polyester containing polyestercarbonate Raw material is directly used in polymerization.As method for refining, common method for refining, such as recrystallization, reprecipitation method, extraction essence may be employed System, column chromatography etc., there is no restriction.

Using recrystallization, reprecipitation method when method for refining carry out refined, as good solvent, specifically workable solvent can be with Enumerate the acetonitrile as alkyl nitrile series solvent, propionitrile etc.；Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) as ketone series solvent Deng；As the diethyl ether of ether series solvent, tetrahydrofuran, 1,4- dioxane, methylcyclopentyl ether, t-butyl methyl ether etc.；As The 1,2- dichloroethanes of halogen-based solvent, dichloromethane, chloroform, 1,1,2,2- tetrachloroethanes etc.；As halogen system aromatic hydrocarbon Chlorobenzene, 1,2- dichloro-benzenes etc.；N,N-dimethylformamide, DMAC N,N' dimethyl acetamide as acid amides series solvent etc.；As Dimethyl sulfoxide (DMSO), sulfolane of sulfoxide series solvent etc.；As the toluene of aromatic hydrocarbon, paraxylene, ortho-xylene, diformazan Benzene, 1,3,5- trimethylbenzenes, 1,2,4- trimethylbenzenes, 1,2,3,4- naphthanes etc.；Pyridine as heteroaromatic etc..

Oligomeric fluorene diaryl ester (2) is big for the poor solubility of temperature, thus preferably boiling point is that 100 DEG C or more of methyl is different Butyl ketone, 1,4- dioxane, methylcyclopentyl ether, t-butyl methyl ether, 1,1,2,2- tetrachloroethanes, chlorobenzene, 1,2- dichloro-benzenes, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), sulfolane, toluene, paraxylene, ortho-xylene, Dimethylbenzene, 1,3,5- trimethylbenzenes, 1,2,4- trimethylbenzenes, 1,2,3,4- naphthanes, pyridine.Among these, more preferably in ester Also stablize at high temperature in the presence of exchange catalysts, for the toluene of the small aromatic hydrocarbon of non-halogen, carrying capacity of environment, to diformazan Benzene, ortho-xylene, meta-xylene, 1,3,5- trimethylbenzenes, 1,2,4- trimethylbenzenes.

These good solvents can be used alone, and two or more may be used in combination.

On the dosage of solvent, the upper limit is not particularly limited, if the refined effect in view of the purpose thing in each reactor Rate, then usually using 15 times of quality, further preferably preferably 10 times of quality, the 5 times of matter for reaching oligomeric fluorene diaryl ester (2) The amount of amount.On the other hand, if the dosage of solvent is very few, the dissolubility of reagent is deteriorated, stirs change hardly possible, and simultaneous reactions delay Slowly, thus as lower limit, reach 0.3 times of quality usually using the densimeter with oligomeric fluorene diaryl ester (2), be preferably 0.5 times The amount of quality, further preferably 1 times of quality.

, when method for refining carry out refined, the poor solubility of temperature generation can be being utilized, only using recrystallization, reprecipitation method Crystallization is carried out using good solvent, but in order to improve the rate of recovery, it is preferable to use poor solvents.Tool as workable poor solvent Body example can enumerate the monocyclic aliphatic hydrocarbons such as the pentamethylene as ring type aliphatic hydrocarbon, hexamethylene, cycloheptane, cyclooctane；For Methyl cyclopentane, ethyl cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2- dimethyl cyclohexanes, the 1,3- bis- of its derivative Hexahydrotoluene, 1,4- dimethyl cyclohexanes, isopropyl cyclohexane, n-propyl hexamethylene, t-butylcyclohexane, normal-butyl hexamethylene Alkane, isobutyl butylcyclohexane, 1,2,4- trimethyl-cyclohexanes, 1,3,5- trimethyl-cyclohexanes etc.；The polycycles such as decahydronaphthalenes fat Race's hydrocarbon；Pentane, n-hexane, normal heptane, normal octane, isooctane, n -nonane, n-decane, n-dodecane, n-tetradecane etc. are acyclic Formula aliphatic hydrocarbon；As the methanol of alcohol series solvent, ethyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, hexanol, octanol, cyclohexanol etc..

Since highly polar impurity can be removed, thus, as the preferred methanol of poor solvent, ethyl alcohol, isopropanol, positive fourth The alcohol series solvents such as alcohol, the tert-butyl alcohol, hexanol, octanol, cyclohexanol, the short methanol of more preferable carbochain, ethyl alcohol.

There is the crystal polymorphism for stablizing shape and metastable setting in oligomeric fluorene diaryl ester (2).Using good solvent, pass through The poor solubility that temperature generates is crisp with the crystallization that metastable setting is precipitated come when being precipitated crystallization, has when mutually becoming stablizing shape The tendency of micronizing.The crystallization of micronizing as resin raw material industrially in use, poor fluidity, it is possible to cause and feed intake It is bad.On the other hand, will be used as the toluene of good solvent, paraxylene, ortho-xylene, meta-xylene, 1,3,5- trimethylbenzenes, The aromatic hydrocarbons such as 1,2,4- trimethylbenzenes, 1,2,3,4- naphthanes and the methanol as poor solvent, ethyl alcohol, isopropanol, positive fourth Alcohol, the tert-butyl alcohol, hexanol, octanol, cyclohexanol are when alcohol series solvents are combined, due to from the crystallization that can initially obtain stablizing shape, It is not micronized, thus preferably.

When will be used as the aromatic hydrocarbon of good solvent and be combined as the alcohol series solvent of poor solvent, if alcohol series solvent Addition temperature it is low, then alcohol series solvent addition before metastable setting crystallization be precipitated, have the increased tendency of its ratio.Therefore, The addition temperature of alcohol series solvent is usually 20 DEG C or more, is preferably 30 DEG C or more, more preferably 40 DEG C or more, is particularly preferably 50 DEG C or more.

In the crystallization of the metastable setting of oligomeric fluorene diaryl ester (2), if utilizing powder x-ray diffraction measurement device (XRD) analyzed, 2 θ=5.6 °, 8.5 °, 11.0 °, 12.5 °, 12.9 °, 14.9 °, 16.3 °, 19.1 ° (θ=± 0.2 °) Observe characteristic peak.Since the crystallization of metastable setting is crisp, easily causes phase transfer, thus by persistently being stirred in crystallization And be micronized, cause from the discharge in reactor is bad or filterability is deteriorated.In addition, the crystallization of metastable setting is to impact Also it is weak, it feeds intake caused by being reduced in order to avoid powder fluidity bad, the peak of these incidence angles is free of in preferably crystallizing.

If the amount of good solvent used is very few in the crystallization of oligomeric fluorene diaryl ester (2), it is difficult to dissolve oligomeric two virtue of fluorenes Base ester (2), purification efficiency also reduces, thus the lower limit of the amount of good solvent is usually 0.3 times compared with oligomeric fluorene diaryl ester (2) The amount of quality, the amount for being preferably the amount of 0.5 times of quality, being more preferably 0.7 times of quality are still more preferably 0.9 times of quality Amount.In addition, if the amount of good solvent is excessive, loss of the oligomeric fluorene diaryl ester (2) in filtrate increases, and yield rate reduces, because And the upper limit of the amount of good solvent is compared with the amount that oligomeric fluorene diaryl ester (2) is usually 5 times of quality, preferably 4 times of quality Amount, the more preferably amount of 3 times of quality are still more preferably the amount of 2 times of quality.

If the amount of poor solvent used is very few in the crystallization of oligomeric fluorene diaryl ester (2), oligomeric fluorene diaryl ester (2) Loss in filtrate increases, and yield rate reduces, thus, the lower limit of the amount of poor solvent is compared with oligomeric fluorene diaryl ester (2) Usually the amount of 2 times of quality, be preferably 3 times of quality amount, more preferably 3.5 times of quality amount, still more preferably be 4 times of matter The amount of amount.In addition, if the amount of poor solvent is excessive, purification efficiency also reduces, and kettle efficiency reduces, and productivity reduces, because And the upper limit of the amount of poor solvent is compared with the amount that oligomeric fluorene diaryl ester (2) is usually 10 times of quality, preferably 9 times of quality Amount, more preferably the amount of 8 times of quality, be still more preferably the amount of 7 times of quality.

In order to from the crystallization for initially obtaining stablizing shape, if disposably adding in substantial amounts of poor solvent, solubility drastically under Drop, crystallization was once precipitated, therefore crystal size is difficult to increase.For oligomeric fluorene diaryl ester (2), if specific good molten Specific poor solvent is added in agent on a small quantity, then the tendency risen with solubility.It will be specific bad by using the property Solvent is added separately or intermittently supplies specific poor solvent, has the tendency that can further increase crystal size.Make For specific good solvent, preferably toluene, paraxylene, ortho-xylene, meta-xylene, 1,3,5- trimethylbenzenes, 1,2,4- front threes The aromatic hydrocarbons such as base benzene, 1,2,3,4- naphthanes, more preferable industrial cost is low, the toluene that is readily available, paraxylene, adjacent diformazan Benzene, meta-xylene.As specific poor solvent, preferably methanol, ethyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, hexanol, octanol, The alcohol series solvents such as cyclohexanol, more preferable industrial cost is low, the isopropanol, methanol, the ethyl alcohol that are readily available.Particularly preferable as specific Good solvent ortho-xylene, as specific poor solvent methanol combination.

Specific poor solvent is divided into 2 times in the case of being added, if the specific poor solvent initially added Ratio is excessively high, then poor solvent influence enhancing, do not observe solubility raising effect, thus usually 40 mass % with Under, be preferably below 30 mass %, more preferably below 20 mass %.On the other hand, if that initially adds is specific bad molten The ratio of agent is too low, then does not observe poor solvent additive effect, thus usually more than 5 mass %, preferably 10 mass % Above, more than 15 mass % are more preferably.

Specific poor solvent is divided into 2 times in the case of being added, it is necessary to by specific good solvent and specifically The combination of poor solvent adjusts optimal addition temperature, in the case of particularly preferred ortho-xylene and methanol, if methanol Addition temperature it is low, then before methanol is added metastable setting crystallization be precipitated, have the increased tendency of its ratio.Therefore, initially The addition temperature of the methanol of addition is usually 45 DEG C or more, is preferably 50 DEG C or more, more preferably 55 DEG C or more, is further excellent Elect 60 DEG C or more as.The lower limit of the temperature of the methanol then added is usually 0 DEG C or more, is preferably 5 DEG C or more, is more preferably 10 DEG C or more.On the other hand, the upper limit of the temperature of the methanol then added is usually less than 42 DEG C, is preferably less than 40 DEG C, is more excellent Elect less than 38 DEG C as.

The grain diameter of oligomeric fluorene diaryl ester (2) is significantly changed according to the difference of crystallization condition.If the grain size of particle It is too small, then the blocking of filter cloth easily occurs in the filter progress of crystallization, filtration time is elongated or liquid holdup raises, and has The tendency that the purity of oligomeric fluorene diaryl ester (2) reduces.In addition, in use, powder fluidity is deteriorated, have as resin raw material May cause feed intake it is bad.Therefore, the lower limit of the average grain diameter of the particle of oligomeric fluorene diaryl ester (2) be usually 50 μm or more, Preferably 70 μm or more, more preferably more than 90 μm, still more preferably for 130 μm or more, be particularly preferably 170 μm or more. If the average grain diameter of the particle of oligomeric fluorene diaryl ester (2) is excessive, as resin raw material in use, it is possible that block filtering Device.Therefore, the upper limit of the average grain diameter of the particle of oligomeric fluorene diaryl ester (2) is usually below 2cm, is preferably below 1cm, more Preferably below 0.5cm, still more preferably it is below 0.3cm.

The grain diameter of oligomeric fluorene diaryl ester (2) is significantly changed according to crystallization condition.If the grain size of particle is too small, The blocking of filter cloth easily occurs in the filter progress of crystallization, filtration time is elongated or liquid holdup raises, and has oligomeric fluorenes two The tendency that the purity of aryl ester (2) reduces.In addition, as resin raw material in use, powder fluidity be deteriorated, it is possible to cause It feeds intake bad.Therefore, the accumulation % that the grain size of the particle of oligomeric fluorene diaryl ester (2) is 50 μm or more is usually 50 μm or more and is More than 50%, it is preferably more than 60%, be more preferably more than 70%, is still more preferably more than 80%, particularly preferably More than 90%.

The grain size for the agglutinator that primary crystallization or the primary crystallization aggegation obtained by crystallization forms is according to reactor or stirs It mixes the various conditions such as the shape, mixing speed, the material of reactor of paddle and changes.If in general becoming large-sized, shearing force Increase, thus it is easily pulverized, and grain size has the tendency to become smaller.But by according to above-mentioned crystallization condition, such as even with 1m³Above reactor can also obtain the oligomeric fluorene diaryl ester (2) of preferable particle size.

It is operated by the way that crystallization is repeated, the content of metal can be reduced.At this point, recrystallization temperature is lower, then purpose is oligomeric The yield of fluorene diaryl ester (2) more improves, but the tendency that the purification efficiency with metal reduces.

In the case where particularly preferred catalyst for ester exchange reaction Ti compounds are used as catalyst, oligomeric fluorenes two The removing of Ti in aryl ester (2) is difficult, and the remaining of Ti becomes problem sometimes.In this case, preferably after termination of the reaction Reaction solution or the oligomeric fluorene diaryl ester (2) separated once is dissolved into again in the solution formed in above-mentioned solvent Water is added, makes Ti its inactivations, is changing into insoluble titanium residue, removes titanium residue in filter progress afterwards.At this point, It in the case of adding water in reaction solution after reaction terminating, carries out that refined titanium level of residue is more, filter progress is caused big negative Lotus, thus the tendency being deteriorated with filterability.It is therefore preferable that poor solvent is added in reaction terminating liquid for the time being, it will be most of Ti compounds remove, be afterwards redissolved the oligomeric fluorene diaryl ester (2) after separation, after being inactivated with water, carry out to filterer Sequence.

The grain size of titanium residue is very small, if aperture greatly if can not remove titanium residue completely, it is possible to be mixed into product.Cause This, the aperture of the filter material used in filter progress is usually less than 10 μm, is preferably less than 5 μm, more preferably less than 1 μm.Separately On the one hand, if the aperture of filter material is too small, the rate of filtration reduces, it is possible to cause the delay of activity time.Therefore, as filtering The aperture of the filter material used in process is usually 0.01 μm or more, is preferably 0.05 μm or more, more preferably 0.1 μm or more.Separately Outside, when the filtering surface of the filter material used in filter progress is plane, titanium residue is piled up in filtering surface, makes its blocking, therefore in order to Shorten filtration time, it is necessary to the filter area of excess.On the other hand, if the shape of the filter material used in filter progress is filter bag It is such closing bottom surface cylindrical shape, then titanium residue can be piled up in bottom surface, can also filter, therefore can reduce stifled from side The danger of plug, therefore it is preferred that.In addition, the material on the filter material used in filter progress, from it is at low cost, be industrially readily available Aspect is set out, and is preferably polypropylene system, cotton and polyester system, from the high aspect of heat resistance, be preferably polyester system, cotton and Teflon system, more preferably at low cost, the heat resistance also filter material of high cotton and polyester.As filter progress, can enumerate Suction filtration, centrifugal filtration, pressure filtration.Wherein, pressure filtration is preferred when the rate of filtration is fast.In order to improve the rate of filtration, pressurize The pressure of filtering is usually more than 0.11MPa, is preferably more than 0.15Mpa, more preferably more than 0.20MPa.Pressure filtration Upper limit value additionally depends on equipment, in order to avoid causing big load to equipment, be usually below 5.0MPa, be preferably 3.0MPa with Under, more preferably below 1.0MPa.

Filtration adjuvant can be used in filter progress.As filtration adjuvant, diatomite, cellulose powder, sulphur can be enumerated Sour magnesium, sodium sulphate, silica gel, activated alumina, activated carbon, atlapulgite, perlite, glass fibre, bead etc..

Among these, preferably filter area is big, adsorbs the few diatomite of caused loss, cellulose powder, perlite.

<2 oligomeric fluorenes diester B>

The oligomeric fluorenes diester (hereinafter sometimes called " oligomeric fluorenes diester B ") of the present invention is included with or without substitution The fluorenes unit of 2 or more of base,

The content ratio of carboxylic acid is below 5 mass %.

As alkylidene, arlydene, sub- aralkyl, preferably may be employed<1.1 alkylidenes, arlydene, sub- aralkyl> In illustrated group.

Similarly, as fluorenes unit, preferably may be employed<The substituent group that 1.2 fluorenes units can have>In it is illustrated Fluorenes unit.

The present invention oligomeric fluorenes diester B can be：It is bonded respectively on the carbon atom of 9 of the fluorenes unit of two ends Substituted base α¹And α², in the substituents alpha¹And α²On be bonded with ester group.In this case, α¹And α²Can it is identical can not also Together.In addition, substituents alpha¹And α²In include Direct Bonding, i.e. can have ester group with Direct Bonding on the carbon atom of 9 of fluorenes unit.

As ester group, preferably may be employed above-mentioned《Invention 2》's<1.3 ester group>In illustrated ester group.Particularly, by In with the raised tendency of patience for hydrolysis, thus the preferably alkyl of straight-chain, more preferably methyl or ethyl.

As substituents alpha¹And α², preferably may be employed above-mentioned《Invention 2》's<1.4 substituents alpha¹And α²>In it is illustrated Group.

In addition, as the concrete structure of oligomeric fluorenes diester B, it is preferable to use the structures shown in above-mentioned general formula (1).Separately Outside, as concrete example, the structure shown in above-mentioned [H] group can be enumerated.

As described above, in the oligomeric fluorenes diester of the present invention, the content ratio of carboxylic acid is below 10 mass %.Make by doing so The content of carboxylic acid is prescribed limit, using the oligomeric fluorenes diester as raw material and in the case of manufacturing diaryl ester, with can be with Amount of metal contained by the diaryl ester is reduced to the tendency of prescribed limit.

From reducing the amount of metal aspect contained by diaryl ester, the content of above-mentioned carboxylic acid be preferably 8 mass % with Under, more preferably below 5 mass %, further preferably below 4 mass %, still more preferably for below 3 mass %, especially Preferably below 2 mass %, it is most preferably below 1 mass %.In addition, carboxylic acid content is more few the more preferred, if wanting it is made to be 0 matter % is measured, impurity, which is mixed into etc., in order to prevent is possible to reduce with the rise of significant cost or production efficiency.Maintain productivity and can The content of the carboxylic acid reached is usually more than 0.1 mass %.

It is by hydrolyzing by-product when oligomeric fluorenes diester manufactures to think above-mentioned carboxylic acid.Species on above-mentioned carboxylic acid does not have It is particularly limited to, for example, any one ester group (in oligomeric fluorenes diester, is substituted by carboxylic acid by oligomeric fluorenes monoesters monocarboxylic acid Substance), oligomeric fluorenes dicarboxylic acids (in oligomeric fluorenes diester, 2 ester groups are substituted by the substance of carboxylic acid).

As the measuring method of carboxylic acid content, for example, being quantified using high performance liquid chromatography to separated carboxylic acid Method.

As carboxylic acid amount is made to be the method for above range, for example, common method for refining, for example utilizing buck Filter operations, the column chromatographys such as water washing operations, recrystallization, reprecipitation method, Hydrolysis kinetics, filter filtering etc..In addition, utilizing two In the case of the oligomeric fluorenes diester B of the reaction manufacture present invention of coating systems, pass through the low temperature of reaction temperature, the contracting in reaction time It is short to wait inhibition hydrolysis critically important.

In addition, other physics values of the oligomeric fluorenes diester B of the present invention are not particularly limited, preferably satisfy above-mentioned《Invention 3》 's<1.6 have the physical property of the oligomeric fluorenes A1 of 1 reactive functional groups>Item in illustrated physics value.

The manufacturing method of oligomeric fluorenes B on the present invention is not particularly limited, for example, can utilize with<1.3.4 oligomeric fluorenes The manufacturing method of diester (1)>Described in the identical method of method manufactured.

Embodiment

The present invention is described in more detail below by embodiment and comparative example, but as long as without departing from its main points, the present invention is simultaneously From the restriction of following embodiment.

《Embodiment 1-1~1-6, comparative example 1-1~1-17》

The quality evaluation and the evaluating characteristics of resin and hyaline membrane of the oligomeric fluorenes monomer of the present invention carry out as follows. It should be noted that evaluating characteristics are not limited to the following method, those skilled in the art can suitably select.

(1) aluminium in fluorenes system monomer, sodium content

The following aluminium measured in the monomer (hereinafter sometimes called fluorenes system monomer) comprising fluorenes ring, sodium content.Analysis is tried After sample carries out wet type resolution process, aluminium content is carried out using ICP-AES (HORIBA Jobin Yvon societies manufacture ULTIMA 2C) With quantifying for sodium content.In addition, on sodium content, according to the difference of analysis sample, also share and utilized atom light absorption method The analysis that (VARIAN SpectrAA-220P) is carried out.

(2) chlorinity in fluorenes system monomer

The following chlorinity measured in fluorenes system monomer.The burner AQF- manufactured using Mitsubishi chemical Co., Ltd 2100M makes analysis sample burn, and the gas of generation is made to be absorbed into pure water.Thereafter, the pure water for absorbing gas is imported into Japan The ion chromatography DX-500 of Dionex Co., Ltd. manufacture, has carried out quantifying for chlorinity.

(3) heat decomposition temperature of fluorenes system monomer

The glass transition temperature of fluorenes system monomer uses the differential thermogravimetric same time-division that SII Nanotechnology societies manufacture Analysis apparatus TG-DTA6300 is measured.About 4mg fluorenes system monomer is put into the aluminium dish of society manufacture and is sealed, Under the nitrogen stream of 200mL/ minutes, 600 DEG C are warming up to by room temperature (20~30 DEG C) for 10 DEG C/min with heating rate.According to gained Sample weight is reduced the temperature of 5wt% as 5wt% weightless temperatures by the TG data (Thermogravimetric Data) arrived.For containing solvent Monomer, with measure start when weight compared with reduce by¹After the weight of solvent of H-NMR estimations, weight change will not occur The initial stage weight is reduced the temperature of 5wt% as 5wt% weightless temperatures by weight at the time of change as initial stage weight.In addition, According to obtained TG data (Thermogravimetric Data), the reduction of weight is being not confirmed and is observing the peak of precipitous endothermic peak Push up the fusing point as sample.

(4) the very big wavelength of absorption in the UV, visible light region (UV-Vis) of fluorenes system monomer

UV, visible light region (the UV-Vis of fluorenes system monomer：280~800nm) the very big wavelength of absorption use (strain) Shimadzu system Make manufactured ultravioletvisible absorption spectrophotometer UV-1650PC to be measured.On solution is measured, made using tetrahydrofuran For solvent, accurately prepared according to using the concentration that fluorenes ring is counted as 10 μM.Cell uses the quartz cell of 1cm square, in temperature It is measured in the environment of 23 ± 5 DEG C of degree.The absorption spectrum of solution is measured in the range of 280nm~800nm, will be absorbed Maximum as absorbing very big wavelength (λ_max)。

(5) reduced viscosity of resin

Above-mentioned resin is dissolved in dichloromethane, prepares the resin solution that concentration is 0.6g/dL.Use gloomy friendly physics and chemistry Industrial society manufactures Ubbelohde viscosity tube, is measured for 20.0 DEG C ± 0.1 DEG C in temperature, determine solvent by time t₀And solution Pass through time t.Use obtained t₀With the value of t, relative viscosity η is obtained by following formula (I)s_rel, and then obtained by use Relative viscosity η_rel, specific viscosity η is obtained by following formula (ii)_sp。

η_rel=t/t₀···(I)

η_sp=(η-η₀)/η₀=η_rel-1···(ii)

Thereafter, by obtained specific viscosity η_spDivided by concentration c (g/dL), reduced viscosity η is obtained_sp/c.The value is higher, point Son amount is bigger.

(6) melt viscosity of resin

By granular resin 90 DEG C vacuum drying 5 it is small when more than.Using dry particle, Toyo Seiki strain formula meeting is utilized The capillary rheometer of society's manufacture is measured.Measuring temperature be 240 DEG C, shear velocity is 9.12~1824sec^-1Between measure Melt viscosity uses 91.2sec^-1When melt viscosity value.It should be noted that hole has used mode diameter as φ 1mm, length For the hole of 10mm.

(7) glass transition temperature (Tg) of resin

The glass transition temperature of above-mentioned resin uses the differential scanning calorimetry (DSC) that SII Nanotechnology societies manufacture DSC6220 is measured.About 10mg resins are put into the aluminium dish of society manufacture and are sealed, in the nitrogen of 50mL/ minutes It flows down, 250 DEG C is warming up to by 30 DEG C for 20 DEG C/min with heating rate.After temperature is kept for 3 minutes, with 20 DEG C/min of speed It is cooled to 30 DEG C.It is kept for 3 minutes at 30 DEG C, is warming up to 200 DEG C again with 20 DEG C/min of speed.According in the 2nd heating Extrapolation glass transition initial temperature is obtained in obtained DSC data, which is by low temperature side The slope of curve of baseline to the straight line that high temperature side extends and the stepped changing unit in glass transition reaches maximum The temperature for the intersection point that the drawn tangent line of point intersects, using the extrapolation glass transition initial temperature as glass transition temperature. When the glass transition temperature is 125 DEG C or more, excellent heat resistance is evaluated as.

(8) shaping of film

Unstretching film is made up of following two methods.

In aftermentioned embodiment 1-1 and comparative example 1-1~1-12, compression molding is carried out in the following order, is made Unstretching film.For 90 DEG C be dried in vacuo 5 it is small when more than about 4g resin particles, use long 14cm, width 14cm, thickness The spacer of 0.1mm in the laying polyimide film up and down of sample, preheats 3 minutes for 200 DEG C~230 DEG C, in pressure in temperature It pressurizes under conditions of 40MPa after five minutes, takes out and cooled down together with spacer, make membrane.In this method, it can not make The thickness and precision of film is less than 5%.It should be noted that in this specification, thickness and precision is calculated by following formula.That is, on thickness Spend precision, measure the thickness of each position of film, show mobility scale maximum or the difference of minimum value and setting value compared with putting down The ratio of average.

Thickness and precision [%]=| the maximum of thickness or minimum value-setting value |/average value × 100

In addition, in aftermentioned embodiment 1-2~1-6 and comparative example 1-13~1-17, made by extrusion by melting Long unstretching film.Extrusion by melting carries out as follows.For 90 DEG C be dried in vacuo 5 it is small when more than resin particle, profit Single screw extrusion machine (screw diameter 25mm, the barrel design temperature manufactured with い The ず Hua Gong Machine Co., Ltd.：220 DEG C~240 DEG C), from T moulds (wide 200mm, design temperature：200~240 DEG C) it squeezes out.For the film of extrusion, while (setting is warm with chill roll Degree：120~150 DEG C) it cools down while with coiling machine it is made to produce long unstretching film for web-like.In addition, in the above-mentioned methods, Distance of die lip width or the temperature of chill roll, T moulds and chill roll by adjusting T moulds etc. can realize less than 5% film Thickness and precision.

(9) measure of refractive index

The rectangle of long 40mm, width 8mm are cut by the unstretching film above by pressure sintering or extrusion by melting making Test film, as measure sample.Using the interference light filter of 589nm (D lines), the multi-wavelength manufactured by (strain) Atago Abbe index meters DR-M4/1550 determines refractive index n_D.Single bromonaphthalene is used to be carried out as interface liquid at 20 DEG C in measure It measures.

(10) measure of total light transmittance

The unstretching film of about 100 μm of film thickness has been made by above-mentioned extrusion by melting, has utilized Japanese electric color industry strain formula The nephelometer COH400 of commercial firm's manufacture determines total light transmittance.

(11) photoelastic coefficient

Use the double refraction detection device that will include He-Ne lasers, polarizer, compensating plate, analyzer, photodetector The device being composed with oscillating mode determination of viscoelasticity device (Rheology societies manufacture DVE-3) is measured.(detailed content is joined According to Japanese Rheology association will Vol.19, p93-97 (1991).)

The sample of wide 5mm, long 20mm are cut by the unstretching film made by any of the above-described kind of method, is fixed on viscoelastic Property measurement device, at room temperature storage modulus E ' is measured with frequency 96Hz at 25 DEG C.Meanwhile the laser of injection is made to pass sequentially through partially Shake element, sample, compensating plate, analyzer, and is picked up using photodetector (photodiode), is passed to locking amplification Device is obtained compared with its amplitude and the phase difference strained for the waveform of angular frequency or 2 ω, and strain optical coefficient is obtained O’.At this point, adjustment polarizer and analyzer direction, make them orthogonal, and make they respectively with the prolonging direction of sample into The angle of π/4.Photoelastic coefficient C is obtained using storage modulus E ' and strain optical coefficient O ' by following formula.

C=O '/E '

When the photoelastic coefficient is less than 20, photoelasticity excellent is evaluated as.

(12) elasticity modulus

The rectangular test film of wide 5mm, long 50mm are cut by the film obtained by the above method, determines energy storage mould Measure (E ') and loss modulus (E ").In measure, using the rheometer RSA-III of TA Instruments societies manufacture, with stretching die Temperature is warming up to respectively by distance 20mm, 3 DEG C/min of heating rate, frequency 1Hz, the condition of strain 0.1% from 0 DEG C between formula, collet It more than the glass transition temperature of sample, is measured until sample is used up and stopped.Storage modulus in the present invention uses 30 DEG C of storage modulus.

(13) water absorption rate

The unstretching film that thickness is 100 μm~300 μm, cut growth 100mm, width are produced by any of the above-described kind of method The square of 100mm, produces sample.Using the sample, " water absorption rate of plastics and boiling according to described in JIS K 7209 Moisture content test method " determines water absorption rate.

(14) toughness (crooked test) of film

The unstretching film that thickness is 100 μm~200 μm is produced by any of the above-described kind of method, length is gone out by the film production The rectangular test film of 40mm, width 10mm.40mm is opened at the interval on vice or so composition surface, the both ends of test film are consolidated It is scheduled in composition surface.Then the interval for making left and right composition surface with the speed below 2 mm/seconds reduces, and is expressed into always not making film In the case of outside the composition surface of vice, the film reduced overall of approximate U-shaped will be bent in the composition surface.Near composition surface Between completely it is closely sealed until test film be cleaved into bending section 2 (or 3 or more fragmentation) situation be used as " having crackle ", even if will The situation that complete closely sealed test film does not also split and bends between composition surface is used as " flawless ".Implement 5 for same kind of film It is secondary repeat test, will wherein more than 4 times for " having crackle " situation conduct " ×：Less than 3 times are " to have by generation brittle break " The situation of crackle " is used as " zero：Brittle break does not occur ", by there is a situation where brittle break is evaluated as excellent tenacity.

(15) stretching of film

According to the production method of above-mentioned unstretching film, phase difference film is produced by following two methods.

For the unstretching film made by pressure sintering, stretched using following methods.It is cut by unstretching film The diaphragm of wide 50mm, long 125mm use the batch-type two-way stretch device (two-way stretch device that Island industry society manufactures BIX-277-AL), with the draft temperature of+15 DEG C of glass transition temperature of resin, the tensile speed of 300%/minute and 1.5 times Stretching ratio carry out the free end simple tension of above-mentioned diaphragm, obtain stretched film.

For the unstretching film made by extrusion by melting, with the tensile speed of 300%/minute, 2 times of stretching times Rate, the draft temperature of+10 DEG C of glass transition temperature of resin are stretched, and stretched film have been obtained if unbroken, with every Secondary 1 DEG C of mode reduces draft temperature, until carrying out into stretching film fracture.Using the temperature being broken once before Draft temperature under the stretched film that obtains, carried out aftermentioned evaluation.

(16) phase difference of stretched film, wavelength dispersion, birefringence

The central portion of the stretched film obtained by the above method is cut into wide 4cm, long 4cm, machine is measured using prince The measuring difference of phases device KOBRA-WPR of Co., Ltd.'s manufacture is measuring wavelength 450,500,550,590,630nm measure phases Difference measures wavelength dispersibility.Wavelength dispersibility is used in the ratio between the phase difference R450 and R550 of 450nm and 550nm measure (R450/ R550) represent.When R450/R550 is more than 1, wavelength dispersion is just, during less than 1, disperses for inverse wave length.As 1/4 wavelength In the case of plate use, the ideal value of R450/R550 is 0.818 (450/550=0.818).

By the value as obtained from 1 subtracts the value of R450/R550 divided by the molar ratio of fluorenes system monomer, obtained value is made During the expression power disperseed for inverse wave length, if the value is more than 0.01, it is excellent to evaluate the expression power that inverse wave length is disperseed.

It should be noted that the value of the B (R450/R550) as of the invention 1 formula (1)~(3), using in following evaluations The value of the wavelength dispersion of middle measure, the evaluation have used the stretched film obtained by the unstretching film made by above-mentioned pressure sintering.

In addition, using the phase difference R550 of 550nm and the thickness of stretched film, birefringence n is obtained by following formula.

Birefringence=R550 [nm]/(film thickness [mm] × 10⁶)

Birefringent value is bigger, represents that the degree of orientation of polymer is higher.In addition, birefringent value is bigger, can more reduce For obtaining the thickness of the film of desired phase difference value.

In above-mentioned various evaluations, there is no during the project for being evaluated as difference, the balancing good of various characteristics is evaluated as.

In the following, the synthetic method of the monomer used in manufacture of resin is illustrated.

The synthesis of [synthesis example 1] double (fluorenes -9- bases) methane (compound 1)

[changing 125]

Fluorenes (120g, 722mmol), n,N-Dimethylformamide (480ml) are packed into 1L four-hole boiling flasks, nitrogen is carried out and puts Postcooling is changed to less than 5 DEG C.Add in sodium ethoxide (24.6g, 361mmol), several times, every time a small amount of addition paraformaldehyde (8.7g, 289mmol), temperature is made to be no more than 10 DEG C, and is stirred.2 it is small when after, be added dropwise 1N hydrochloric acid (440ml), stop reaction.To institute Obtained aaerosol solution is filtered, and is eluted using deionized water (240ml).Thereafter, obtained thick product point is made It is scattered in deionized water (240ml), when stirring 1 is small.After being filtered to the suspension, carried out using deionized water (120ml) Elution.After obtained thick product is made to be distributed in toluene (480ml), item is being heated to reflux using Dean-Stark apparatus It is dehydrated under part.Recover to room temperature (20 DEG C), filtered, is dried under reduced pressure at 80 DEG C until reaching constant, so as to obtain Double (fluorenes -9- bases) methane (compound 1) 84.0g (yields as white solid：84.5%th, HPLC purity：94.0%).Chemical combination Object 1¹Chemical shift in H-NMR spectrum is as follows.

¹H-NMR(400MHz,CDCl₃) 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)

The synthesis of [synthesis example 2] double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (compound 2)

[changing 126]

Double (fluorenes -9- bases) methane (compound 1,80g, 232.3mmol), N- obtained above are packed into 1L three-necked flasks Benzyl-N, N, N- triethyl ammonium chloride (10.6g, 46.5mmol), dichloromethane (400ml) use water-bath after carrying out nitrogen displacement It controls as 15 DEG C~20 DEG C, after adding in 50% sodium hydrate aqueous solution (64ml), the color change of solution is into light red.Thereafter, Ethyl acrylate (50.5ml, 465mmol) was added dropwise with 5 minutes.1 it is small when after further add in ethyl acrylate (25.3ml, 232mmol), while being carried out with HPLC following responses, while when stirring 9 is small.Single addition body, which is confirmed, using HPLC reaches 5% It after below, is cooled down with ice bath, controls temperature that 3N hydrochloric acid (293ml) is added dropwise, be quenched.It is straight that profit washes with water organic layer It after being in neutrality to fluidity, is dried, filtered using anhydrous magnesium sulfate, vacuum distillation removes solvent.Make obtained thick generation Object is dispersed in methanol (400ml), be heated to reflux within 30 minutes, so as to carry out heat suspension washing.Thereafter recover to room temperature (20 DEG C), after suction filtration, it is dried under reduced pressure at 80 DEG C until reaching constant, so as to obtain double [9- (2- ethyoxyl carbonyls as white solid Base ethyl) fluorenes -9- bases] methane (compound 2) 96.1g (yields：75.9%th, HPLC purity：96.0%).Compound 2¹H- Chemical shift in NMR spectra is as follows.

¹H-NMR(400MHz,CDCl₃) 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)

In addition, the 5wt% weightless temperatures (under nitrogen atmosphere) of compound 2 are 295 DEG C, fusing point is 141 DEG C.

The synthesis of [synthesis example 3] double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 3)

[changing 127]

Double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (chemical combination obtained above are packed into 1L four-hole boiling flasks Object 2,50.0g, 91.80mmol), diphenyl carbonate (98.3g, 459mmol), original four-isopropyl titanate (1.3mL, 4.59mmol), vacuum degree is adjusted to 3kPa, 145 DEG C~150 DEG C of temperature ranges by-product is distilled off while into Row 6 stirs when small.90 DEG C are cooled to, after confirming reaction terminating by HPLC, toluene (100ml) is added in, is cooled to 50 DEG C.Xiang Qi Middle addition methanol (250ml), after being cooled to 5 DEG C, is filtered.Obtained white solid is made to be dispersed in toluene (100ml), It is heated to reflux 30 minutes.After being cooled to 50 DEG C, methanol (200ml) is added in.After being cooled to room temperature (20 DEG C), filtered, 100 It DEG C is dried under reduced pressure until reaching constant, so as to obtain double [9- (the 2- phenyloxycarbonyls ethyl) fluorenes -9- bases] as white solid Methane (compound 3) 50g (yields：85%th, HPLC purity：98.1%).Compound 3¹Chemical shift in H-NMR spectrum is such as Under.

¹H-NMR(400MHz,CDCl₃) 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).

In addition, the 5wt% weightless temperatures (under nitrogen atmosphere) of compound 3 are 336 DEG C, fusing point is 176 DEG C.

The synthesis of double (fluorenes -9- bases) ethane (compound 4) of [synthesis example 4] 1,2-

[changing 128]

Fluorenes (2.0g, 12mmol), tetrahydrofuran (35ml) are packed into 100ml four-hole boiling flasks, after carrying out nitrogen displacement, Less than -50 DEG C are cooled in ethyl alcohol-the dry ice bath.Several times, every time a small amount of addition 1.6mol/L n-BuLis (7.8ml, Temperature 12.5mmol) is made to be no more than -40 DEG C, and is stirred.Thereafter, 10 DEG C, when progress 1 is small after stirring are warming up to, adds in 1, 2- Bromofumes (0.55ml, 6.4ml) stir when further progress 2 is small.Thereafter, 1N hydrochloric acid (0.5ml) is added dropwise, to generation Aaerosol solution is filtered, and after washing, is dried under reduced pressure at 80 DEG C to constant is reached, so as to obtain 1,2- pairs as white solid (fluorenes -9- bases) ethane (compound 4) 0.63g (yields：29.2%th, HPLC purity：98.0%).In addition, vacuum distillation removes filter The solvent of liquid adds in ethyl alcohol (25ml), be stirred within 30 minutes.Suspension is filtered, is dried under reduced pressure at 80 DEG C straight To constant is reached, so as to obtain as double (fluorenes -9- bases) ethane (compound 4) 0.44g (yields of 1,2- of white solid： 20.5%th, HPLC purity：84.0%).If obtained white solid is merged, for 1.07g (yields：49.7%).Chemical combination Object 4¹Chemical shift in H-NMR spectrum is as follows.

¹H-NMR(400MHz,CDCl₃) 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)

The synthesis of double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] ethane (compound 5) of [synthesis example 5] 1,2-

[changing 129]

Be packed into 1L four-hole boiling flasks double (fluorenes -9- bases) ethane (compound 4,85g, 237mmol) of 1,2- obtained above, Tetrahydrofuran (725ml), n,N-Dimethylformamide (85ml), carry out nitrogen displacement after add in sodium ethoxide (3.23g, 47.5mmol), room temperature (20 DEG C) is warming up to, stir within 30 minutes.Using 2.5 it is small when be added dropwise ethyl acrylate (59.3ml, 545mmol).After confirming raw material disappearance by HPLC, 0.1N hydrochloric acid (55ml) is added dropwise into reaction solution, stops reaction.Decompression After tetrahydrofuran is distilled off, toluene (425ml) is added in, using pure water cleaning organic layer until fluidity is in neutrality, Zhi Houli It is dried, is filtered with anhydrous magnesium sulfate, vacuum distillation removes solvent.Obtained thick product is made to be dispersed in methanol In (400ml), be heated to reflux 1 it is small when come carry out heat suspend washing.Thereafter recover to room temperature (20 DEG C), after suction filtration, subtract at 80 DEG C Press dry dry until reaching constant, it is double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] as 1,2- of white solid so as to obtain Ethane (compound 5) 101g (yields：76.1%th, HPLC purity：98.6%).Compound 5¹Chemical potential in H-NMR spectrum It moves as follows.

¹H-NMR(400MHz,CDCl₃) 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)

In addition, the 5wt% weightless temperatures (under nitrogen atmosphere) of compound 5 are 306 DEG C, fusing point is 150 DEG C.

The synthesis of double [9- (the 2- phenyloxycarbonyls ethyl) fluorenes -9- bases] ethane (compound 6) of [synthesis example 6] 1,2-

[changing 130]

Double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- of the 1,2- obtained by the above method are packed into 1L four-hole boiling flasks Base] ethane (compound 5,100.0g, 179mmol), diphenyl carbonate (115g, 537mmol), original four-isopropyl titanate (2.62ml, 8.95mmol) after carrying out nitrogen displacement, is warming up to 135 DEG C, progress 24 is stirred when small.On the way, small by 12 When at the time of, by 20 it is small when at the time of, additional diphenyl carbonate (38.3g, 179mmol) by several times.It is confirmed instead by HPLC After should terminating, add in toluene (400ml), be heated to reflux 1 it is small when.After being cooled to room temperature (20 DEG C), filtered.Make obtained White solid is dispersed in toluene (300ml), be heated to reflux 1 it is small when.It after being cooled to room temperature (20 DEG C), is filtered, at 80 DEG C It is dried under reduced pressure until reaching constant, so as to obtain as double [9- (the 2- phenyloxycarbonyls ethyl) fluorenes -9- of 1,2- of white solid Base] ethane (compound 6) 82g (yields：70.0%th, HPLC purity：98.0%).Compound 6¹Chemistry in H-NMR spectrum Displacement is as follows.

¹H-NMR(400MHz,CDCl₃) 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)

In addition, the 5wt% weightless temperatures (under nitrogen atmosphere) of compound 6 are 337 DEG C, fusing point is 232 DEG C.

The synthesis of [synthesis example 7] double [9- (3- hydroxypropyls)-fluorenes -9- bases] methane (compound 7)

[changing 131]

Double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] first obtained in synthesis example 2 are fitted into 500ml four-hole boiling flasks After carrying out nitrogen displacement, less than 5 DEG C are cooled to using ice bath for alkane (compound 2,50g, 91.8mmol), toluene (250ml), Be added dropwise while being maintained at less than 10 DEG C double (2- methoxy ethoxies) sodium aluminum hydrides 65wt% toluene solutions (82.7ml, 275mmol), stirred when progress 1 is small.After confirming raw material disappearance by HPLC, ethyl acetate (9.9ml) is added dropwise, carries out 30 points After clock stirring, 3.1N sodium hydrate aqueous solutions are further added dropwise, progress 2 is stirred when small.Obtained aaerosol solution is taken out Filter, is eluted using deionized water (100ml).Thereafter, obtained thick product is made to be dispersed in deionized water (150ml) In, stir within 30 minutes.It is eluted after suction filtration, until fluidity is in neutrality, is eluted using toluene (50ml).Make gained To thick product be dispersed in tetrahydrofuran (150ml), by heating dissolved.Tetrahydrofuran solution recovers to room temperature After (20 DEG C), by short silica gel Filter column (50g), eluted using tetrahydrofuran (350ml), using evaporator to obtained molten Liquid carries out vacuum distillation and removes solvent.Obtained thick product is made to be dispersed in toluene (250ml), heat back within 30 minutes Stream, so as to carry out heat suspension washing.Recover to room temperature (20 DEG C) to be filtered, be dried under reduced pressure at 80 DEG C afterwards until reaching permanent Amount, so as to obtain double [9- (3- hydroxypropyls)-fluorenes -9- bases] methane (compound 7) 35.5g (yields as white solid： 83.9%th, HPLC purity：99.8%).Sodium content, aluminium content in solid are respectively less than 1ppm.Compound 7¹In H-NMR spectrum Chemical shift it is as follows.

¹H-NMR(400MHz,CDCl₃) 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)

In addition, the 5wt% weightless temperatures (under nitrogen atmosphere) of compound 7 are 301 DEG C, fusing point is 214 DEG C.

The synthesis of double [9- (the 3- hydroxypropyls)-fluorenes -9- bases] ethane (compound 8) of [synthesis example 8] 1,2-

[changing 132]

It is double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] that the 1,2- obtained in synthesis example 5 is fitted into 1L four-hole boiling flasks Ethane (compound 5,100g, 179mmol), tetrahydrofuran (500ml), carry out nitrogen displacement after, using ice bath be cooled to 5 DEG C with Under, less than 15 DEG C are maintained at while the 65wt% toluene solutions of double (2- methoxy ethoxies) sodium aluminum hydrides are added dropwise (161ml, 537mmol), progress 1 are stirred when small.After confirming raw material disappearance by HPLC, ethyl acetate (32ml) is added dropwise, into After row stirring in 45 minutes, 3.1N sodium hydrate aqueous solutions (257ml) are further added dropwise, progress 1 is stirred when small.Vacuum distillation removes After tetrahydrofuran, obtained aaerosol solution is filtered, is eluted using deionized water (100ml).Thereafter, gained is made To thick product be dissolved in ethyl acetate (700ml), utilize deionized water (100ml) clean 3 times.Organic layer is utilized into sulphur After sour magnesium drying, by short silica gel Filter column (50g), eluted using tetrahydrofuran (800ml), using evaporator to obtained Solution carries out vacuum distillation and removes solvent.Obtained thick product is made to be dispersed in toluene (400ml), is heated to reflux 30 points Thus clock washs to carry out heat suspension.Recover to room temperature (20 DEG C) to be filtered, be dried under reduced pressure at 100 DEG C afterwards until reaching To constant, so as to obtain as double [9- (3- hydroxypropyls)-fluorenes -9- bases] ethane (compound 8) 75.6g of 1,2- of white solid (yield：89.0%th, HPLC purity：98.7%).Sodium content in solid is 2ppm, aluminium content is less than 2ppm.Compound 8¹Chemical shift in H-NMR spectrum is as follows.

¹H-NMR(400MHz,DMSO-d₆) δ 7.81 (d, J=7.3Hz, 4H), 7.35 (t, J=7.3Hz, 4H), 7.29 (t, J=7.3H z, 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).

In addition, the 5wt% weightless temperatures (under nitrogen atmosphere) of compound 8 are 312 DEG C, fusing point is 253 DEG C.

The synthesis of [synthesis example 9] double (9- hydroxymethyl fluorenes -9- bases) methane (compound 9)

[changing 133]

Be fitted into 500mL four-hole boiling flasks obtained in synthesis example 1 double (fluorenes -9- bases) methane (compound 1,100g, 290mmol), n,N-Dimethylformamide (400ml) after carrying out nitrogen displacement, adds in paraformaldehyde (18.3g, 610mmol). After being cooled to less than 5 DEG C, sodium ethoxide (0.698g, 13mmol) is added in, being stirred makes temperature be no more than 10 DEG C.1.5 it is small when after, Addition 1N hydrochloric acid (32ml) makes temperature be no more than 25 DEG C, stops reaction.Water (300ml) is further added in, is stirred, to gained To aaerosol solution filtered, eluted using deionized water (100ml).Obtained thick product is made to be dispersed in tetrahydrochysene After in furans (400ml), it is heated to reflux when progress 1 is small.Recover to room temperature (20 DEG C), be dried under reduced pressure after suction filtration at 80 DEG C until Reach constant, obtain white solid 108g (yields：91%th, HPLC purity：99.1%).Sodium in obtained white solid contains It measures as 620ppm.Thereafter white solid is made to be dispersed in toluene (800ml) and water (200ml) mixed liquor, progress 1 is heated back when small Stream after filtering, drying, is measured the sodium content in obtained solid, result 390ppm.Further make obtained White solid is dispersed in n,N-Dimethylformamide (500ml), after uniform solution is made in heating, is cooled to less than 40 DEG C, It is slowly added drop-wise in the hydrochloric acid (1500ml) of 0.03N.Obtained aaerosol solution is filtered, it is made to be dispersed in deionization In water (200ml), progress 1 is stirred when small.After being filtered to the suspension, eluted using deionized water (100ml).Make After obtained product is dispersed in toluene (800ml), lower carry out azeotropic dehydration is being heated to reflux.Recover to room temperature (20 DEG C), after suction filtration, be dried under reduced pressure at 100 DEG C until reach constant, so as to obtain as white solid it is double (9- hydroxymethyls fluorenes- 9- yls) methane (compound 9) 104g (yield 87%, HPLC purity：99.8%).The content of sodium, chlorine in solid is respectively smaller than 10ppm.Compound 9¹Chemical shift in H-NMR spectrum is as follows.

¹H-NMR(400MHz,DMSO-d₆) δ 7.12 (d, J=7.3Hz, 4H), 7.01-6.93 (m, 8H), 6.77 (dt, J1 =7.3H z, J2=1.0Hz, 4H), 4.97 (t, J=4.6Hz, 2H), 3.31 (s, 2H), 3.23 (d, J=4.3Hz, 4H)

In addition, the UV-Vis spectrum (solvents of compound 9：THF the very big wavelength X of absorption in)_maxBe present in 263nm, 292nm and 304nm.And the 5wt% weightless temperatures (under nitrogen atmosphere) of compound 9 are 289 DEG C, and fusing point is 226 DEG C.

The synthesis of double (the 9- hydroxymethyl fluorenes -9- bases) ethane (compound 10) of [synthesis example 10] 1,2-

[changing 134]

Be fitted into 1L four-hole boiling flasks double (fluorenes -9- bases) ethane of the 1,2- that is obtained in synthesis example 4 (compound 4,100g, 278.9mmol), paraformaldehyde (17.6g, 585.8mmol), n,N-Dimethylformamide (400ml), after carrying out nitrogen displacement, It is cooled to less than 10 DEG C.Sodium ethoxide (1.80g, 27.9mmol) is added in, is warming up to room temperature (20 DEG C), progress 1 is stirred when small.It utilizes After HPLC confirms raw material disappearance, reaction solution is added drop-wise in 0.1N hydrochloric acid (440ml), stops reaction.To obtained suspension Solution is filtered, and is eluted using deionized water (100ml).Thereafter, obtained thick product is made to be dispersed in N, N- bis- In methylformamide (300ml), progress 1 is stirred when small.The hanging drop is added in 0.005N hydrochloric acid (1000ml), stirring 30 After minute, filtered.Obtained thick product is made to be dispersed in deionized water (500ml), progress 1 is stirred when small.To this After suspension is filtered, eluted using deionized water (200ml).Obtained thick product is made to be dispersed in toluene After in (500ml), it is dehydrated using Dean-Stark apparatus under heated reflux condition.Recover to room temperature (20 DEG C), into Row filters, and is dried under reduced pressure at 100 DEG C until reach constant, so as to obtain as 1,2- of white solid it is double (9- hydroxymethyls fluorenes- 9- yls) ethane (compound 10) 112.4g (yields：96.3%th, HPLC purity：99.1%).Sodium content in solid is less than 1ppm.Compound 10¹Chemical shift in H-NMR spectrum is as follows.

¹H-NMR(400MHz,DMSO-d₆) δ 7.91 (d, J=7.3Hz, 4H), 7.44 (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)

In addition, the UV-Vis spectrum (solvents of compound 10：THF the very big wavelength X of absorption in)_maxBe present in 264nm, 291nm and 302nm.In addition, the 5wt% weightless temperatures (under nitrogen atmosphere) of compound 10 are 301 DEG C, fusing point is 278 DEG C.

The synthesis of double (fluorenes -9- bases) butane (compound 11) of [synthesis example 11] 1,2-

[changing 135]

In the SUS316 autoclaves of capacity 70ml be packed into fluorenes (3.5g, 21mmol), 1,4- butanediols (4.9g, 54mmol), 85%KOH (1.52g, 23mmol), tetraethylene glycol dimethyl ether (4.9g) carry out 8 at 250 DEG C in a nitrogen atmosphere Hour reaction.After cooling, content is made to be dispersed in tetrahydrofuran and water, neutralized using dilute hydrochloric acid.It is molten by obtained suspension Powder is precipitated in filtering in liquid, is washed, so as to obtain the Isosorbide-5-Nitrae as white solid-bis- (fluorenes -9- bases) butane (compound 11) 1.7g (yields：41.9%th, HPLC purity：97.4%).Compound 11¹Chemical shift in H-NMR spectrum is as follows.

¹H-NMR(400MHz,CDCl₃) 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)

The synthesis of double (the 9- hydroxymethyl fluorenes -9- bases) butane (compound 12) of [synthesis example 12] 1,2-

[changing 136]

Be packed into 500mL four-hole boiling flasks double (fluorenes -9- bases) butane of 1,2- obtained above (compound 11,37.0g, 95.7mmol), paraformaldehyde (6.03g, 201mmol), n,N-Dimethylformamide (148ml), after carrying out nitrogen displacement, cooling To less than 10 DEG C.Sodium ethoxide (0.65g, 9.6mmol) is added in, is warming up to room temperature (20 DEG C), progress 1 is stirred when small.Pass through HPLC After confirming raw material disappearance, reaction solution is added drop-wise in 0.1N hydrochloric acid (162ml), stops reaction.To obtained aaerosol solution It is filtered, is eluted using deionized water (37ml).After obtained thick product is made to be dispersed in toluene (185ml), It is dehydrated using Dean-Stark apparatus under heated reflux condition.Recover to room temperature (20 DEG C), filtered, 80 It DEG C is dried under reduced pressure until reaching constant, so as to obtain (changing as double (the 9- hydroxymethyl fluorenes -9- bases) butane of 1,2- of white solid Close object 12) 39.8g (yields：93.1%th, HPLC purity：99.1%).Chemical shift in the 1H-NMR spectrum of compound 12 is such as Under.

¹H-NMR(400MHz,DMSO-d₆) 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)

In addition, the UV-Vis spectrum (solvents of compound 12：THF the very big wavelength X of absorption in)_maxBe present in 291nm and 302nm.In addition, the 5wt% weightless temperatures (under nitrogen atmosphere) of compound 12 are 314 DEG C, fusing point is 212 DEG C.

The synthesis of [synthesis example 13] α, α '-bis- (9- hydroxymethyl fluorenes -9- bases) -1,4- dimethylbenzene (compound 13)

[changing 137]

α, α '-bis- (fluorenes -9- bases) -1,4- dimethylbenzene ((130g, 0.3mol), poly first are packed into tetra- mouthfuls of eggplant-shape bottles of 1L Aldehyde (18.9g, 0.63mol), n,N-Dimethylformamide (520ml), carry out nitrogen displacement after add in sodium ethoxide (2.04g, 0.03mol), stirred when progress 1 is small under room temperature (20 DEG C).Deionized water 520ml and 1N hydrochloric acid are packed into 1L beakers (45ml) adds in reaction solution after being stirred, is quenched reaction.Obtained crystallization is filtered, utilizes deionized water (100ml) is eluted.After obtained thick product is made to be dispersed in deionized water (500ml), filtered, using go from Sub- water (100ml) is eluted.After obtained thick product is made to be dispersed in toluene (500ml), filled using Dean-Stark It puts and is dehydrated under heated reflux condition.Recover to after room temperature (20 DEG C), filtered, is dried under reduced pressure at 70 DEG C to reaching permanent Amount, so as to obtain white solid (compound 13) 130g (yields：87%th, HPLC purity：97.6%).Compound 13¹H-NMR Chemical shift in spectrum is as follows.

¹H-NMR(400MHz,CDCl₃) δ 7.62 (d, J=7.6Hz, 4H), 7.33 (t, J=8.0Hz, 4H), 7.25 (t, J =6.0Hz, 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).

In addition, the 5wt% weightless temperatures (under nitrogen atmosphere) of compound 13 are 327 DEG C, fusing point is 198 DEG C.

The synthesis of double (9- hydroxyphenyl fluorene -9- bases) ethane (compound 14) of [synthesis example 14] 1,2-

[changing 138]

Be packed into 1L four-hole boiling flasks obtained by the method for synthesis example 4 1,2- pairs of (fluorenes -9- bases) ethane (compound 4, 20g, 59mmol), n,N-Dimethylformamide (200ml), add in tributyl phosphite (37.9ml, 140mmol), carry out nitrogen After displacement, benzyltrimethylammonium hydroxide (40% methanol solution) (25ml) is added in, makes air (100ml/ minutes) and nitrogen The mixed gas of (300ml/ minutes) circulates in the reaction system.Stir 3 it is small when after, add in benzyltrimethylammonium hydroxide (40% methanol solution) (10ml), when stirring 5 is small.Further add in benzyltrimethylammonium hydroxide (40%MeOH solution) (10ml), so stir 1 it is small when.1N hydrochloric acid (200ml) is added in, stops reaction, adds in ethyl acetate (400ml), carries out liquid separation Operation.3 cleanings are further carried out to organic layer using saturated salt solution (100ml).After organic layer being dried using magnesium sulfate, It is filtered, vacuum distillation removes organic solvent.Toluene (100ml), hexane are added in obtained aaerosol solution (200ml) after stirring 30 minutes, is filtered, and is dried under reduced pressure at 80 DEG C until reaching constant, so as to obtain as white solid Double (9- hydroxyphenyl fluorene -9- bases) ethane (compound 14) 13.9g (yields of 1,2-：63.8%th, HPLC purity：92.5%).Chemical combination Object 14¹Chemical shift in H-NMR spectrum is as follows.

¹H-NMR(400MHz,CDCl₃) 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)

The synthesis of [synthesis example 15] double { [4- (2- hydroxyl-oxethyls) phenyl] fluorenes -9- bases } ethane (compound 15)

[changing 139]

Be packed into 300mL four-hole boiling flasks double (fluorenes -9- bases) ethane of the 1,2- obtained using the above method (compound 14, 17g, 45mmol), phenoxetol (37g, 267mmol), carry out nitrogen displacement after, be cooled to less than 10 DEG C.It adds in borontrifluoride Boron-diethyl ether complexes (5.6ml, 45mmol), under room temperature (20 DEG C) stir 3 it is small when after, further add in boron trifluoride-two Etherate (5.6ml, 45mmol), chloroform (35ml), at 40 DEG C stir 4 it is small when, at 60 DEG C stirring 2 it is small when.Into one Step adds in boron trifluoride-diethyl ether complexes (5.6ml, 45mmol), when overheat reflux 2 is small.After being cooled to room temperature (20 DEG C), make It is neutralized with saturated sodium bicarbonate aqueous solution, removes insoluble matter by filtering afterwards.Ethyl acetate (120ml) is added, will be had Machine layer is cleaned 2 times using saturated salt solution, is cleaned 1 time using deionized water, after being dried using magnesium sulfate, is filtered, is depressurized Organic solvent is distilled off.It is dissolved in again in ethyl acetate (150ml), addition activated carbon (Japanese NORIT Co., Ltd., SXPLUS, pH=7,2.5g), when progress 1 is small after stirring, diatomite filtering is carried out, vacuum distillation removes organic solvent.Add in first Alcohol (100ml) when stirring 1 is small, is filtered, and is dried under reduced pressure at 80 DEG C until reaching constant, so as to obtain as white solid Double { [4- (2- hydroxyl-oxethyls) phenyl] fluorenes -9- bases } ethane (compound 15) 15.8g (yields：56.1%th, HPLC purity： 86%).Compound 15¹Chemical shift in H-NMR spectrum is as follows.

¹H-NMR(400MHz,CDCl₃) 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).

The synthesis of [synthesis example 16] fluorenes -9,9- diethanols (compound 16)

[changing 140]

It is synthesized according to the method recorded in Japanese Unexamined Patent Publication 2010-261008 publications.

The shorthand notation of the compound used in following embodiments and comparative example etc. is as follows.

·BHEPF：Double [4- (2- hydroxyl-oxethyls) phenyl]-fluorenes (the OSAKA GAS CHEMICALS Co. Ltd. systems of 9,9- It makes)

·BCF：Double (4- hydroxy-3-methyls the phenyl)-fluorenes (manufacture of OSAKA GAS CHEMICALS Co., Ltd.) of 9,9-

·DPC：Diphenyl carbonate (Mitsubishi chemical Co., Ltd's manufacture)

·ISB：Isobide (manufacture of Roquette Freres societies, trade name：POLYSORB)

·CHDM：1,4 cyclohexane dimethanol (cis, trans mixture, the manufacture of society of SK Chemical)

·TCDDM：Tricyclodecane Dimethanol (manufacture of Oxea societies)

·SPG：The spiroglycol (Mitsubishi Gas Chemical Co., Ltd's manufacture)

·BPA：Double [4- hydroxy phenyls] propane (Mitsubishi chemical Co., Ltd's manufacture) of 2,2-

·PEG：Polyethylene glycol number-average molecular weight：1000 (Sanyo Chemical Industries Co., Ltd.'s manufactures)

·CHDA：1,4- cyclohexane dicarboxylic acids (cis, trans mixture, the manufacture of Eastman chemistry society)

·DMT：Dimethyl terephthalate (DMT) (Tokyo HuaCheng Industry Co., Ltd's manufacture)

[embodiment 1-1]

38.06 mass parts (0.059mol) of double [9- (the 2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 3) of general, ISB53.73 mass parts (0.368mol), 9.64 mass parts of CHDM (0.067mol), 81.28 mass parts of DPC (0.379mol) And the calcium acetate monohydrate 3.83 × 10 as catalyst^-4Mass parts (2.17 × 10^-6Mol) put into reaction vessel, To carrying out decompression nitrogen displacement in reaction unit.In a nitrogen atmosphere, make raw material molten in 150 DEG C of one side stir abouts, 10 minutes one side Solution.As the process of the 1st step of reaction, 220 DEG C were warming up to using 30 minutes, carries out reacting for 60 minutes under normal pressure.Next utilize Pressure was kept for 30 minutes in 13.3kPa by atmospheric depressurized to 13.3kPa, the phenol of generation is retracted to reactant in 90 minutes System is outer.Next, the process as the 2nd step of reaction, was warming up to 240 DEG C by heat medium temperature using 15 minutes, while utilizes 15 Minute by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction system.Stirring torque as defined in reaching Afterwards, recovered with nitrogen to normal pressure, terminate reaction, the polyestercarbonate of generation is expressed into water, cut strands and obtain particle. Above-mentioned various evaluations have been carried out using the particle of obtained polyestercarbonate.Evaluation result is listed in table 1.

On the polyestercarbonate of embodiment 1-1, the content of the oligomeric fluorene structural units from compound 3 is few, is 27.0 Quality %, the wavelength dispersion (R450/R550) of phase difference film are shown as 0.835, it will be understood that the expression power that inverse wave length is disperseed Height is 0.025.In addition, the photoelastic coefficient of the polyestercarbonate of embodiment 1-1 is low, glass transition temperature is 143 DEG C, it is The value of melt processable and the balancing good of heat resistance.

[comparative example 1-1]

Except using 1,2- 45.69 mass parts of double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] ethane (compound 6) (0.070mol), 43.13 mass parts of ISB (0.295mol), 15.64 mass parts of CHDM (0.108mol), 72.36 mass of DPC Part (0.338mol), calcium acetate monohydrate 3.55 × 10^-4Mass parts (2.02 × 10^-6Mol it is similary with embodiment 1-1 beyond) Ground is synthesized, and obtains the particle of polyestercarbonate.Above-mentioned various comment has been carried out using the particle of obtained polyestercarbonate Valency.Evaluation result is listed in table 1.

The expression power that the inverse wave length of the polyestercarbonate of comparative example 1-1 is disperseed is also high, it may have excellent mechanical properties, but Photoelasticity characteristic is poor.

[comparative example 1-2]

Except use double 35.02 mass parts (0.076mol) of [9- (3- hydroxypropyls)-fluorenes -9- bases] methane (compound 7), ISB40.75 mass parts (0.279mol), 12.71 mass parts of CHDM (0.088mol), 95.85 mass parts of DPC (0.447mol), calcium acetate monohydrate 3.90 × 10^-4Mass parts (2.22 × 10^-6Mol beyond), in the same manner as embodiment 1-1 It is synthesized, obtains the particle of makrolon.Above-mentioned various evaluations have been carried out using the particle of obtained makrolon.Evaluation The results are shown in tables 1.

The makrolon of comparative example 1-2 also has more excellent characteristic, but the expression power that inverse wave length is disperseed is poor.

[comparative example 1-3]

Except using 1,2- 37.92 mass parts of double [9- (3- hydroxypropyls)-fluorenes -9- bases] ethane (compound 8) (0.080mol), 42.45 mass parts of ISB (0.290mol), 8.47 mass parts of CHDM (0.059mol), 92.84 mass of DPC Part (0.433mol), calcium acetate monohydrate 3.78 × 10^-4Mass parts (2.15 × 10^-6Mol it is similary with embodiment 1-1 beyond) Ground is synthesized, and obtains the particle of makrolon.Above-mentioned various evaluations have been carried out using the particle of obtained makrolon.It comments The results are shown in tables 1 for valency.

Expression power that the inverse wave length of the makrolon of comparative example 1-3 is disperseed, photoelasticity characteristic are poor.

[comparative example 1-4]

Except using 28.19 mass parts (0.070mol) of double (9- hydroxymethyl fluorenes -9- bases) methane (compound 9), ISB 42.45 mass parts (0.290mol), 16.95 mass parts of CHDM (0.118mol), 103.35 mass parts of DPC (0.482mol), Calcium acetate monohydrate 1.68 × 10^-3Mass parts (9.55 × 10^-6Mol beyond), synthesized, obtained in the same manner as embodiment 1-1 To the particle of makrolon.Above-mentioned various evaluations have been carried out using the particle of obtained makrolon.Evaluation result is listed in table 1。

Compound 9 be can import it is similarly low with the fluorenes system monomer that is used in embodiment 1-1 or comparative example 1-1~1-3 The compound of polyfluorene structural unit, but do not show inverse wave length dispersiveness unexpectedly using the makrolon of compound 9.Speculate it The reason is that, the fluorenes ring of compound 9 is not to be orientated in vertical direction compared with draw direction.

[comparative example 1-5]

Except use double 47.08 mass parts (0.112mol) of (9- hydroxymethyl fluorenes -9- bases) ethane (compound 10) of 1,2-, ISB29.71 mass parts (0.203mol), 12.71 mass parts of CHDM (0.088mol), 87.40 mass parts of DPC (0.408mol), calcium acetate monohydrate 7.12 × 10^-4Mass parts (4.04 × 10^-6Mol beyond), in the same manner as embodiment 1-1 It is synthesized, obtains the particle of makrolon.Above-mentioned various evaluations have been carried out using the particle of obtained makrolon.Evaluation The results are shown in tables 1.

The resin of this example does not show inverse wave length dispersiveness in the same manner as comparative example 1-4.

[comparative example 1-6]

Except use double 32.13 mass parts (0.072mol) of (9- hydroxymethyl fluorenes -9- bases) butane (compound 12) of 1,2-, ISB43.30 mass parts (0.296mol), 12.71 mass parts of CHDM (0.088mol), 98.74 mass parts of DPC (0.461mol), calcium acetate monohydrate 8.04 × 10^-4Mass parts (4.56 × 10^-6Mol beyond), in the same manner as embodiment 1-1 It is synthesized, obtains the particle of makrolon.Above-mentioned various evaluations have been carried out using the particle of obtained makrolon.Evaluation The results are shown in tables 1.

[comparative example 1-7]

Except use double 33.85 mass parts (0.084mol) of (9- hydroxymethyl fluorenes -9- bases) methane (compound 9), CHDM28.97 mass parts (0.201mol), 48.03 mass parts of CHDA (0.279mol) and metatitanic acid four as catalyst are just Butyl ester 9.49 × 10^-3Mass parts (2.79 × 10^-5Mol beyond), synthesized in the same manner as embodiment 1-6, obtain of polyester Grain.Above-mentioned various evaluations have been carried out using the particle of obtained polyester.Evaluation result is listed in table 1.

In this example, polyester is synthesized by the compound 9 used in the makrolon of comparative example 1-4, but polyester is not also shown Go out inverse wave length dispersiveness.

[comparative example 1-8]

Except using α, 38.00 mass parts of α '-bis- (9- hydroxymethyl fluorenes -9- bases) -1,4- dimethylbenzene (compound 13) (0.077mol), 33.96 mass parts of ISB (0.232mol), 16.95 mass parts of CHDM (0.118mol), 92.32 mass of DPC Part (0.431mol), calcium acetate monohydrate 7.52 × 10^-4Mass parts (4.27 × 10^-6Mol it is similary with embodiment 1-1 beyond) Ground is synthesized, and obtains the particle of makrolon.Above-mentioned various evaluations have been carried out using the particle of obtained makrolon.It comments The results are shown in tables 1 for valency.

The resin of this example does not show inverse wave length dispersiveness in the same manner as comparative example 1-4.By the knot of comparative example 1-4~1-8 Fruit is believed that the distance of the carbonyl contained in carbonate group or ester group and fluorenes ring generates shadow to the presence or absence of inverse wave length dispersiveness It rings.It can speculate：If the hypotelorism of carbonyl and fluorenes ring, make fluorenes ring can not be in preferred side due to the steric hindrance of carbonyl To orientation, so as to which inverse wave length dispersiveness can not be shown.

[comparative example 1-9]

Except using 37.46 mass parts of double { [4- (2- hydroxyl-oxethyls) phenyl] fluorenes -9- bases } ethane (compound 15) (0.059mol), 39.05 mass parts of ISB (0.267mol), 12.71 mass parts of CHDM (0.088mol), 89.73 mass of DPC Part (0.419mol), calcium acetate monohydrate 7.31 × 10^-4Mass parts (4.15 × 10^-6Mol it is similary with embodiment 1-1 beyond) Ground is synthesized, and obtains the particle of makrolon.Above-mentioned various evaluations have been carried out using the particle of obtained makrolon.It comments The results are shown in tables 1 for valency.

The value of the wavelength dispersion (R450/R550) of the resin of this example has flat wavelength dispersibility close to 1.It can push away It surveys：In the resin of this example, inverse wave length dispersiveness is shown if the amount of the structural unit from compound 15 is increased, but can be sentenced The expression power that disconnected inverse wave length is disperseed is low.

[comparative example 1-10]

Except using 32.66 mass parts (0.128mol) of fluorenes -9,9- diethanols (compound 16), 54.34 mass parts of ISB (0.372mol), 109.30 mass parts of DPC (0.510mol), calcium acetate monohydrate 1.32 × 10^-3Mass parts (7.50 × 10^-6Mol beyond), synthesized in the same manner as embodiment 1-1, obtain the particle of makrolon.Use obtained makrolon Particle has carried out above-mentioned various evaluations.Evaluation result is listed in table 1.

The resin of this example shows inverse wave length dispersiveness, but the expression power of inverse wave length dispersiveness is poor, and photoelastic coefficient also becomes It is high.In addition, in this example, the foaming of resin during polymerization or during melted masking is slightly more, is the situation of thermal stability difference.

[comparative example 1-11]

Except using 68.07 mass parts of BHEPF (0.155mol), 22.84 mass parts of ISB (0.156mol), PEG 0.97 mass parts (9.75 × 10^-4Mol), 67.60 mass parts of DPC (0.316mol), magnesium acetate 4 hydrate 5.36 × 10^-4Matter Measure part (2.50 × 10^-6Mol beyond), synthesized in the same manner as embodiment 1-1, obtain the particle of makrolon.Obtained by use To the particle of makrolon carried out above-mentioned various evaluations.Evaluation result is listed in table 1.

In the resin of this example, the content of the structural unit from BHEPF is 67.8 mass %, very more, it is known that the structure The expression power that the inverse wave length of unit is disperseed is poor.In addition, the value of photoelastic coefficient is also high.

[comparative example 1-12]

Use 41.17 mass parts of BCF (0.109mol), 51.59 mass parts of SPG (0.170mol), 63.19 mass of DPC Part (0.295mol), calcium acetate monohydrate 4.90 × 10^-3Mass parts (2.78 × 10^-5Mol), it is 260 to make final polymerization temperature DEG C, it is synthesized in addition in the same manner as embodiment 1-1, obtains the particle of makrolon.Use obtained makrolon Particle carried out above-mentioned various evaluations.Evaluation result is listed in table 1.

The resin of this example shows more excellent optical characteristics, but obtained film is highly brittle, is easily broken, toughness Difference.

In following embodiment 1-2~6 and comparative example 1-13~1-17, synthesized using larger polymerization unit Resin is made long film by extrusion by melting, and has carried out the evaluation of various characteristics.Herein, it is particularly attached in fracture gauge It is stretched under conditions of near, has rated the birefringence (orientation) of stretched film.

[embodiment 1-2]

Gather in batches for what two vertical reactors of 100 DEG C of reflux condenser were formed using by possessing agitating paddle and control It attaches together and puts, polymerize.Input 36.94 mass parts of double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 3) (0.058mol), 64.02 mass parts of ISB (0.438mol), 82.43 mass parts of DPC (0.385mol) and as catalyst Calcium acetate monohydrate 3.86 × 10^-4Mass parts (2.19 × 10^-6mol).To carrying out decompression nitrogen displacement in reaction unit Afterwards, heated using thermal medium, start to stir at the time of temperature reaches 100 DEG C inside.Heating starts to make Nei Wenda after forty minutes It to 220 DEG C, is controlled to keep the temperature, starts simultaneously at decompression, with 90 minutes be 13.3kPa after reaching 220 DEG C.It will be with Polymerisation in the reflux condenser of 100 DEG C of the phenol vapor importing of by-product, makes the monomer contained on a small quantity in phenol vapor together Ingredient is back to reactor, and uncooled phenol vapor is imported in 45 DEG C of condenser and recycled.Nitrogen is imported to the 1st reactor And once recovering to atmospheric pressure, the reaction solution through oligomeric materialization in the 1st reactor is moved into the 2nd reactor.Next, it opens The heating and decompression begun in the 2nd reactor made interior temperature be 240 DEG C, pressure 0.2kPa with 50 minutes.Thereafter, it is polymerized to Reach defined stirring power.At the time of regulation power is reached, import nitrogen to reactor and recover pressure, by the polyester of generation Carbonic ester is squeezed out into water, is cut strands and is obtained particle.

Using above-mentioned extrusion by melting, long 3m, wide 200mm, 72 μm thick length are made by obtained polyestercarbonate Unstretching film.Next, carrying out vertical simple tension using the above method, phase difference is made under conditions of being broken near gauge Film.Various evaluations the results are shown in tables 2.

The phase difference film of this example shows inverse wave length dispersiveness, and then the degree of orientation, photoelastic coefficient, heat resistance, toughness etc. Complete characteristic is excellent.

[embodiment 1-3]

Use double 38.06 mass parts of [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 3) (0.059mol), ISB43.06 mass parts (0.295mol), 20.28 mass parts of CHDM (0.141mol), 81.46 mass of DPC Part (0.380mol), calcium acetate monohydrate 3.83 × 10^-4Mass parts (2.18 × 10^-6Mol), the thickness for making unstretching film is 66 μm, phase difference film is made in the same manner as embodiment 1-2 in addition.Various evaluations the results are shown in tables 2.

The phase difference film of this example birefringent value compared with embodiment 1-2 is big, it will be appreciated that the degree of orientation of polymer is high.

[embodiment 1-4]

Use double 31.02 mass parts of [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 3) (0.048mol), ISB43.08 mass parts (0.295mol), 25.26 mass parts of TCDDM (0.129mol), 81.26 mass of DPC Part (0.379mol), calcium acetate monohydrate 3.73 × 10^-4Mass parts (2.12 × 10^-6Mol), the thickness for making unstretching film is 73 μm, phase difference film is made in the same manner as embodiment 1-2 in addition.Various evaluations the results are shown in tables 2.

The phase difference film of this example has higher orientation, and photoelastic coefficient reduces.

[embodiment 1-5]

Use double 29.60 mass parts of [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 3) (0.046mol), ISB29.21 mass parts (0.200mol), 42.28 mass parts of SPG (0.139mol), 63.77 mass parts of DPC (0.298mol), calcium acetate monohydrate 1.19 × 10^-2Mass parts (6.78 × 10^-5Mol), the thickness for making unstretching film is 62 μ M makes phase difference film in the same manner as embodiment 1-2 in addition.Various evaluations the results are shown in tables 2.

The phase difference film of this example birefringence and photoelastic coefficient compared with embodiment 1-2 is excellent.

[embodiment 1-6]

Use double 29.18 mass parts of [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 3) (0.046mol), ISB30.38 mass parts (0.208mol), 41.27 mass parts of SPG (0.136mol), 64.55 mass parts of DPC (0.298mol), calcium acetate monohydrate 1.21 × 10^-2Mass parts (6.86 × 10^-5Mol), the thickness for making unstretching film is 58 μ M makes phase difference film in the same manner as embodiment 1-2 in addition.Various evaluations the results are shown in tables 2.

The phase difference film of this example is dispersed by weakening inverse wave length compared with embodiment 1-2, so as to compared with embodiment 1-2 Birefringent value can be increased, the degree of orientation of polymer can be improved.The phase difference film of this example deviates compared with embodiment 1-2 The ideal value of R450/R550, but according to the different phases that can be suitble to when paying attention to the filming of film using embodiment 1-6 of purposes Potential difference film.

[comparative example 1-13]

Use 63.72 mass parts of BHEPF (0.145mol), 26.74 mass parts of ISB (0.183mol), 0.97 matter of PEG Measure part (9.75 × 10^-4Mol), 71.24 mass parts of DPC (0.333mol), magnesium acetate 4 hydrate 7.06 × 10^-4Mass parts (3.29×10^-6Mol), the thickness of unstretching film is made to make phase difference film in the same manner as embodiment 1-2 in addition for 76 μm. Various evaluations the results are shown in tables 2.

The phase difference film of this example is compared with embodiment, it is known that the expression power and photoelastic coefficient that orientation, inverse wave length are disperseed Difference.

[comparative example 1-14]

Use 68.07 mass parts of BHEPF (0.155mol), 22.84 mass parts of ISB (0.156mol), 0.97 matter of PEG Measure part (9.75 × 10^-4Mol), 67.60 mass parts of DPC (0.316mol), magnesium acetate 4 hydrate 5.36 × 10^-4Mass parts (2.50×10^-6Mol), the thickness of unstretching film is made to make phase difference film in the same manner as embodiment 1-2 in addition for 87 μm. Various evaluations the results are shown in tables 2.

The phase difference film of this example makes the wavelength dispersibility of comparative example 1-13 close to the ideal value of R450/R550, but passes through increasing Strong inverse wave length is disperseed, and so as to which orientation reduces, the expression power that inverse wave length is disperseed is also poor.

[comparative example 1-15]

Use 32.20 mass parts of BCF (0.085mol), 60.43 mass parts of SPG (0.199mol), 64.40 mass of DPC Part (0.301mol), calcium acetate monohydrate 5.00 × 10^-3Mass parts (2.84 × 10^-5Mol), it is 260 to make final polymerization temperature DEG C, the thickness of unstretching film is made to make phase difference film in the same manner as embodiment 1-2 in addition for 76 μm.The knot of various evaluations Fruit is listed in table 2.

The expression power that the phase difference film of this example has the shortcomings that orientation and inverse wave length is disperseed is poor and film is crisp.

[comparative example 1-16]

Use 80.49 mass parts of BHEPF (0.184mol), 13.23 mass parts of BPA (0.058mol), 53.29 matter of DPC Measure part (0.249mol), calcium acetate monohydrate 2.13 × 10^-3Mass parts (1.21 × 10^-5Mol), the final polymerization temperature is made to be 260 DEG C, the thickness of unstretching film is made to make phase difference film in the same manner as embodiment 1-2 in addition for 98 μm.Various evaluations The results are shown in tables 2.

The birefringence compared with embodiment of the phase difference film of this example is greatly reduced.And photoelastic coefficient also becomes larger.It can examine Consider, since the amount of the aromatic structure on main chain is more, thus need to show the amount of the aromatic component of inverse dispersiveness It is more, therefore the reduction of optical characteristics can be caused.

[comparative example 1-17]

Use 86.84 mass parts of BHEPF (0.198mol), 14.95 mass parts of DMT (0.077mol), 28.90 matter of DPC Measure part (0.135mol), tetra-n-butyl titanate 1.35 × 10^-2Mass parts (3.96 × 10^-5Mol), it is 260 to make final polymerization temperature DEG C, the thickness of unstretching film is made to make phase difference film in the same manner as embodiment 1-2 in addition for 148 μm.The knot of various evaluations Fruit is listed in table 2.

The birefringence compared with embodiment of the phase difference film of this example is also greatly reduced, and photoelastic coefficient also becomes larger.

[table 1]

[table 2]

《Embodiment 2-1~2-2, reference example 2-1~2-2》

The quality evaluation and the evaluating characteristics of resin combination and hyaline membrane of the three fluorenes diester of the present invention pass through following sides Method carries out.It should be noted that evaluating characteristics gimmick is not limited to the following method, those skilled in the art can be suitable for choosing It selects.

In addition, shorthand notation of the compound used in following synthesis examples and embodiment etc. is as follows.

ISB：Isobide (manufacture of Roquette Freres societies, trade name：POLYSORB)

DPC：Diphenyl carbonate (Mitsubishi chemical Co., Ltd's manufacture)

CHDM：1,4 cyclohexane dimethanol (cis, trans mixture, the manufacture of society of SK Chemical)

SPG：The spiroglycol (Mitsubishi Gas Chemical Co., Ltd's manufacture)

BHEPF：Double [4- (2- hydroxyl-oxethyls) phenyl]-fluorenes (the OSAKA GAS CHEMICALS Co. Ltd. systems of 9,9- It makes)

THF：Tetrahydrofuran (manufactures) without stabilizer, WAKO societies

(1) heat decomposition temperature (TG-DTA) of oligomeric fluorenes monomer

The decomposition initial temperature of oligomeric fluorenes monomer, fusing point use differential thermogravimetric while analytical equipment (SII Nanotechnology societies manufacture TG-DTA6300) it is measured.About 4mg analysis samples are put into the aluminium dish of society manufacture simultaneously It is sealed, under the nitrogen stream of 200mL/ minutes, 600 is warming up to by room temperature (20~30 DEG C) for 10 DEG C/min with heating rate ℃.According to obtained TG data (Thermogravimetric Data), weight is reduced into the low temperature side baseline extrapolated baseline of behavior and weight is reduced The temperature for the intersection point that the tangent line of maximum inclination point intersects is as decomposition initial temperature.In addition, according to obtained TG data (thermogravimetric Data), using the reduction for not confirming sample weight and observe fusing point of the summit as sample of precipitous endothermic peak.

(2) content ratio of Na, K, Cs, Fe in resin combination

The accurate weighing about 0.5g resin combination samples in the microwave decomposition container of PerkinElmer societies manufacture add in 97% sulfuric acid the ultra-high purity sulfuric acid of manufacture (more rub chemistry) 2mL makes it for air-tight state, carried out at 230 DEG C 10 minutes it is micro- Wave heating.After being cooled to room temperature (less than 30 DEG C), 68% nitric acid (the ultra-high purity nitric acid for the chemistry manufacture that more rubs) 1.5mL is added in, It is made after carrying out microwave heating in 10 minutes at 150 DEG C, to be cooled to room temperature again (less than 30 DEG C) for air-tight state, is added in 68% nitric acid 2.5mL makes it carry out microwave heating in 10 minutes at 230 DEG C for air-tight state, content is made to divide completely again Solution.The Multiwave3000 that microwave applicator is manufactured using PerkinElmer societies, by defeated to being adjusted between 1000W in 300W Go out power to adjust temperature.After being cooled to room temperature (less than 30 DEG C), liquid obtained above using pure water is diluted, is utilized The ICP-MS of ThermoQuest societies manufacture is quantified.

(3) the remaining monohydroxy compound in resin combination

Accurate weighing about 1g resin combination samples, are dissolved in dichloromethane 5mL, add acetone afterwards, make the total amount be 25mL.Solution is filtered using 0.2 μm of disc filter, using liquid chromatography carry out phenol it is quantitative after, calculate Content ratio.

(4) toughness (crooked test) of film

The film of 100 μm~200 μm of thickness is molded by the above-mentioned method based on hot pressing, by the long 40mm of the film production, width The rectangle test film of 10mm.40mm is opened at the interval on vice or so composition surface, the both ends of test film are fixed on engagement In face.Then the interval for making left and right composition surface with the speed below 2 mm/seconds reduces, and connecing for vice is expressed into not making film In the case of outside conjunction face, the film reduced overall of " く " word will be bent in the composition surface.It is completely closely sealed between near composition surface to be Only test film is cleaved into the situation conduct " having crackle " of 2 (or 3 or more fragmentation) in bending section, even if will be between composition surface completely The situation that closely sealed test film does not also split and bends is used as " flawless ".Implement 5 repetitions for same kind of film to test, it will Wherein 4 times or more the situations for " having crackle " as " ×：Generation brittle break " makees less than the 3 times situations for " having crackle " For " zero：Brittle break does not occur ".

(5) refractive index and the measure of Abbe number

By cutting out the rectangle test film of long 40mm, width 8mm in the film by the above-mentioned method acquirement based on hot pressing, as Measure sample.Using multi-wavelength Abbe index meters (Co., Ltd. Atago DR-M4/1550), wavelength 656nm (C are used Line), 589nm (D lines), the interference light filter of 486nm (F lines), measure refractive index, nC, nD, nF of each wavelength.It is used in measure Single bromonaphthalene is measured as interface liquid at 20 DEG C.Abbe number ν d are calculated by following formula.

ν d=(1-nD)/(nC-nF)

Abbe number is bigger, represents that the wavelength dependency of refractive index is smaller.

The reduced viscosity of resin combination, glass transition temperature, melt viscosity, photoelastic coefficient measure with it is above-mentioned Embodiment 1-1 is identical.

Double { [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases]-methyl } fluorenes (compound 3) and double [9- (2- ethoxy carbonyls Ethyl) fluorenes -9- bases] methane (compound 2) synthesis

[changing 141]

Double (fluorenes -9- bases) methane (compound 1) 35.0g (102mmol), THF175mL are added in the removable flasks of 1L, It is stirred in a nitrogen atmosphere in 15 DEG C.Add 50wt% sodium hydrate aqueous solutions 28.68g, benzyltriethylammoinium chloride After 4.61g (20.2mL), stir 15 minutes.It is ripe at 16 DEG C after adding ethyl acrylate 22.4mL (224mmol) using 60 minutes Change 2 it is small when.Carried out the reaction terminating moment HPLC analysis, as a result compound 2 (13.5min) be 75.3 area %, compound 3 (15.2min) is 8.4 area %.After being neutralized using 3N hydrochloric acid, liquid separation and remove water layer.Toluene 70mL is added thereto, The cleaning of 5 organic layers has been carried out with water 105mL.After organic layer adds in toluene 35mL, THF35mL, interior temperature is remained 60 DEG C or more, while heating is concentrated under reduced pressure into 70mL.After adding in toluene 35mL, 45 DEG C are naturally cooled to, adds in methanol 210mL, Carry out the crystallization of double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (compound 2).Crystallization object is filtered, will be filtered Liquid is being stored at room temperature several days, and double { [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases]-methyl } fluorenes generated are recovered by filtration The white crystals of (compound 3).

Double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (compound 2)：37.47g (68.7mmol, yield： 67.6%), white powder

HPLC analysis results compound 2 (13.5min)：91.7 area %, compound 3 (15.2min)：5.2 area %

Decompose initial temperature (under nitrogen atmosphere)：295℃

m.p.：141℃

Double { [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases]-methyl } fluorenes (compound 3)：0.20g (0.3mmol, yield： 0.3%), white crystals

HPLC analysis results compound 2 (13.5min)：3.5 area %, compound 3 (15.2min)：92.6 area %

¹H-NMR(400MHz,CDCl₃)δ6.91-6.95(m,4H),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)

Decompose initial temperature (under nitrogen atmosphere)：364℃

m.p.：166℃

It should be noted that the HPLC after reaction terminating, after crystallization and filtering is implemented under the following conditions.

Column：Inertsil ODS-3V 150mm×4.8mmφ

Temperature：40℃

Eluent condition：0-5min：Tetrahydrofuran/water=50/50,20min：Tetrahydrofuran/water=100/0

Flow velocity：1.0ml/min

Injection rate：2μl

Double { [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases]-methyl } fluorenes (compound 5) and double [9- (2- phenyloxycarbonyls Ethyl) fluorenes -9- bases] methane (compound 4) synthesis

[changing 142]

In the removable flasks of 1L, to containing double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (compound 2, 84.1g, 154.5mmol) and double { [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases]-methyl } fluorenes (compound 3,3.3g, After adding diphenyl carbonate (147.5g, 5685.5mmol) in tetrahydrofuran 6.9mmol)/ortho-xylene mixed solution, by Temperature is warming up to 104 DEG C at leisure, is decompressed to 3kPa afterwards, solvent is distilled off.Recover pressure, add in original four-isopropyl titanate (2.45g, 8.61mmol) is decompressed to 3kPa, is warming up to 184 DEG C at leisure on one side again, while reaction distillate is distilled off. After reaching 184 DEG C, when reaction 3 is small, 90 DEG C are cooled to afterwards, recovers pressure, the progress of reaction has been analyzed to identify by HPLC.Add Enter ortho-xylene (144ml), be cooled to 41 DEG C, as a result confirm the precipitation of crystallization.After being cooled to 40 DEG C, methanol is added in (356mL), and then after being cooled to 5 DEG C, filtered.Obtained coarse crystallization is made to be dispersed in ortho-xylene (272mL), is added After water (0.32g), 80 DEG C are warming up to, makes its dissolving.After carrying out the cleaning of 2 organic layers with water (240mL), filtered with PTFE film (0.5 μm) of device carries out pressure filtration (0.25MPa).Thereafter, after solvent 110g being distilled off with evaporator, 50 DEG C are cooled to, knot Fruit observes the precipitation of crystallization.And then after being cooled to 40 DEG C, methanol (336mL) is added in, after being cooled to room temperature (20 DEG C), is taken out Filter is dried under reduced pressure at 80 DEG C until reaching constant, as double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compounds 4) 59.9g (yields：55.6%th, 46.8mmol) and double { [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases]-methyl } fluorenes (chemical combination Object 5) 0.2g (yields：2.2%th, 0.15mmol) mixture and obtain white solid.

HPLC analysis results compound 4 (15.3min)：98.17 area %, compound 5 (16.5min)：0.15 area %

Column：Inertsil ODS-3V 150mm×4.8mmφ

Temperature：40℃

Flow velocity：1.0ml/min

Injection rate：2μl

¹H-NMR measurement results compound 4

M.p. (compound 4)：176℃

LC/MS measurement results

Compound 4 (13.1min)：(exact mass) 640

(just) 663 [M+Na]⁺、679[M+K]⁺, (negative) 639 [M-H]^-

Compound 5 (14.2min)：(exact mass) 818

(just) 841 [M+Na]⁺、875[M+K]⁺, (negative) 817 [M-H]^-

It should be noted that LC-MS determination conditions are implemented under the following conditions.

LC systems：Agilent 1200

Column：Inertsil ODS-3 5μm 4.6×150mm No.2EI85047

Temperature：40℃

Flow velocity：1.0ml/min

Injection rate：0.2μl

Mass spectrograph：Agilent LC/MS 6130

Ion mode：AJS (positive/negative)

Capillary voltage：4500V(P/N)

Segment voltage：100V

Mass range：M/z=100-1500

Drive gas：N₂, DG=12L/min, NP=60psi, DGT=300 DEG C

Other conditions：SG=12L/min, ST=300 DEG C, NV=1000

[synthesis example of polymer]

0.05 mass parts of double { [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases]-methyl } fluorenes (compound 3) will be contained 26.44 mass parts (0.0489 of double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (compound 2) of (0.0001 mole) Mole), 10.37 mass parts of CHDM (0.072 mole) and the tetra-n-butyl titanate 14.65 × 10 as catalyst^-3Mass parts (4.30×10^-5Mole) put into reaction vessel, in a nitrogen atmosphere, reacted 120 minutes under normal pressure in 220 DEG C.Next, Using 30 minutes by pressure to 13.3kPa, kept for 30 minutes in 13.3kPa, the ethyl alcohol of generation is retracted to reaction vessel Outside.Thereafter, reaction solution is temporarily cooled to room temperature to (20 DEG C), by 31.43 mass parts of ISB (0.215 mole), DPC51.66 matter It measures in the identical reaction vessel of (0.241 mole) input of part, in a nitrogen atmosphere, makes heating tank temperature for 150 DEG C and according to need It is stirred, while makes dissolution of raw material (about 10 minutes).After dissolving, as the process of the 1st step of reaction, heated up using 30 minutes To 220 DEG C, react 60 minutes under normal pressure.Next pressure was made from atmospheric depressurized to 13.3kPa using 90 minutes, with 13.3kPa is kept for 30 minutes, and the phenol of generation is retracted to outside reaction vessel.

Next, the process as the 2nd step of reaction, 240 DEG C, while profit were warming up to using 15 minutes by the temperature of heating tank With 15 minutes by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction vessel.Torque as defined in arrival Afterwards, reaction is terminated, the polymer of generation is expressed into water, obtains the particle of polycarbonate resin.

The glass transition temperature of obtained resin combination when, carry out film shaping and the refraction of stretched film when stretching Rate anisotropy, phase difference ratio (Re450/Re550), the measurement results such as toughness of film are listed in table 3.

0.1 mass parts of double { [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases]-methyl } fluorenes (compound 5) will be contained (0.0458 rubs 29.5 mass parts of double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 4) of (0.0001 mole) You), SPG30.20 mass parts (0.099 mole), ISB40.34 mass parts (0.276 mole), DPC70.49 mass parts (0.329 Mole) and calcium acetate monohydrate 9.91 × 10 as catalyst^-4Mass parts (5.63 × 10^-6Mole) input reaction vessel In, in a nitrogen atmosphere, make heating tank temperature for 150 DEG C and be stirred as needed, while make (about 10 points of dissolution of raw material Clock).After dissolving, as the process of the 1st step of reaction, 220 DEG C were warming up to using 30 minutes, is reacted 60 minutes under normal pressure.It connects down Make within 90 minutes pressure from atmospheric depressurized to 13.3kPa to utilize, kept for 15 minutes with 13.3kPa, the phenol of generation is retracted to Outside reaction vessel.

Next, the process as the 2nd step of reaction, 245 DEG C, while profit were warming up to using 15 minutes by the temperature of heating tank With 15 minutes by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction vessel.Torque as defined in arrival Afterwards, reaction is terminated, the polymer of generation is expressed into water, obtains the particle of polyestercarbonate.

22.65 mass parts (0.042mol) of double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (compound 2) of general, CHDM10.77 mass parts (0.075mol) and the tetra-n-butyl titanate 15.54 × 10 as catalyst^-3Mass parts (4.57 × 10^-5Mol reaction vessel) is put into, in a nitrogen atmosphere, is reacted 120 minutes under normal pressure in 220 DEG C.It next, will using 30 minutes Pressure is kept for 30 minutes with 13.3kPa to 13.3kPa, the ethyl alcohol of generation is retracted to outside reaction vessel.It thereafter, will be anti- Liquid is answered temporarily to be cooled to room temperature, ISB33.58 mass parts (0.230mol), DPC56.96 mass parts (0.266mol) are put into phase In same reaction vessel, in a nitrogen atmosphere, make heating tank temperature for 150 DEG C and be stirred as needed, while make raw material It dissolves (about 10 minutes).After dissolving, as the process of the 1st step of reaction, 220 DEG C were warming up to using 30 minutes, is reacted under normal pressure 60 minutes.Next made pressure from atmospheric depressurized to 13.3kPa using 90 minutes, kept for 30 minutes with 13.3kPa, by generation Phenol is retracted to outside reaction vessel.

Next, the process as the 2nd step of reaction, 240 DEG C, while profit were warming up to using 15 minutes by the temperature of heating tank With 15 minutes by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction vessel.Torque as defined in arrival Afterwards, reaction is terminated, the polymer of generation is expressed into water, obtains the particle of polyestercarbonate resins.

By 62.40 mass parts (0.142mol) of double (4- (2- hydroxyl-oxethyls) phenyl) fluorenes (BHEPF) of 9,9-, ISB28.78 Mass parts (0.197mol), DPC73.40 mass parts (0.343mol) and as catalyst magnesium acetate 4 hydrate 7.28 × 10^-4Mass parts (3.39 × 10^-6Mol reaction vessel) is put into, in a nitrogen atmosphere, makes heating tank temperature for 150 DEG C and according to need It is stirred, while makes dissolution of raw material (about 10 minutes).After dissolving, as the process of the 1st step of reaction, heated up using 30 minutes To 220 DEG C, react 60 minutes under normal pressure.Next pressure was made from atmospheric depressurized to 13.3kPa using 90 minutes, with 13.3kPa is kept for 30 minutes, and the phenol of generation is retracted to outside reaction vessel.

Next, the process as the 2nd step of reaction, 240 DEG C, while profit were warming up to using 15 minutes by the temperature of heating tank With 15 minutes by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction vessel.Torque as defined in arrival Afterwards, reaction is terminated, the polymer of generation is expressed into water, obtains the particle of makrolon.

[table 3]

Table 3

In order to study the relation of the chemical constitution of oligomeric fluorenes and optical characteristics, as follows to deriving from the repetition of oligomeric fluorenes monomer The energy of the specific conformation (configuration) of unit is calculated and fluorenes ring in the conformation is calculated with main chain angulation.

On software, the PC Spartan Pro 1.0.5 manufactured in AM1 methods using Wavefunction societies of the U.S. (32 versions of Windows (registered trademark)).It should be noted that it is complete with the relevant input value of computational accuracy to focus on decision content etc. Portion uses the default value of the software.

It is calculated on the structure from following compounds represented 3, compound 2.Herein, on as diester Compound 3, the compound 2 of monomer, it is assumed that be the resin being polymerize by ester exchange reaction, for two ester groups are carried out methyl The structure formed is esterified to be calculated.

It is as follows, it is 180 ° (i.e. side chain is anti conformation) with dihedral angle formed by bonded B by following bonded A and is Balanced structure and its energy is obtained by AM1 methods as nascent structure in 60 ° and -60 ° (gauche conformations that i.e. side chain is two kinds) (generation heat), which is bonded between 9 carbon atoms of fluorenes and the carbon atom being bonded in adjacent fluorenes side with fluorenes, which is The atom for the side chain being bonded with fluorenes is the same as the interatomic bonded of the main chain with the atomistic binding.Herein, by the tool in each compound There is the substituent group with the methyl ester of 9 carbon atom bondings of fluorenes to be known as side chain.Herein, in order in the polymer to each repetitive unit Stereochemical structure speculated, makes present in each compound being both changed for 2 side chains.That is, the anti conformation in table 4 The two for referring to 2 side chains present in each monomer is the structure of anti conformation, and gauche conformation refers to present in each monomer 2 The two of side chain is the structure of gauche conformation.In addition, gauche conformation has 60 ° and -60 ° two kinds, the two for 2 side chains is 60 ° are calculated with -60 ° of both of these case.

At this point, calculating the two of 2 side chains present in each monomer is anti conformation and is the structure of two kinds of gauche conformations As the energy difference of isomers, most stable of conformation in this 3 kinds of conformations is set to 0 (kJ/mol), by energy difference (kJ/ at this time Mol) it is recorded in table 4.In addition, in the case where energy difference is more than 4kJ/mol, energy (generation heat) low conformation (is set to 0 (kJ/mol) conformation) it is used as Stable conformation.The reasonability of result on the AM1 methods in this calculating, in Japan's Patent In No. 2013-214986, it is thus identified that the calculating B3LYP/6-31G with more height^*Method shows same tendency.

In addition, on anti conformation and two kinds of gauche conformations, calculate main chain and fluorenes ring angulation and recorded.

It should be noted that main chain such as get off with fluorenes ring angulation it is definite.First, by the methine carbon atom of two ends The straight line being connected to each other will be used as fluorenes plane as main chain direction by the plane of the 3 of fluorenes, 6,9 carbon atoms.This When, the straight line in fluorenes plane intersected with main chain direction infinitely exists, but with the angle in main chain direction in minimum fluorenes plane Straight line uniquely determine.Using the angle as main chain and fluorenes ring angulation.Herein, due to compound 3 in the molecule With 3 fluorenyls, therefore, main chain and fluorenes ring angulation are calculated using the fluorenes ring at center.

[changing 143]

[table 4]

Table 4

Compound 3 and compound 2 are compared in table 4, be anti conformation energy (generation heat) and 2 kinds it is twisted Energy (generation heat) difference of conformation is on an equal basis or trans body is slightly stablized.

In the comparison of compound 3 and compound 2, on main chain and the fluorenes ring angulation of anti conformation, there are 3 The compound 3 of fluorenyl is 84.2 °, has the compound 2 of 2 fluorenyls for 74.6 °, compound 3 shows the value close to 90 °.

The inventors discovered that by making fluorenes ring orthogonal compared with main chain in resin combination, so as to show its optics Characteristic.In addition, confirm in Japan's Patent 2013-214986：By calculate the main chain in the Stable conformation that is obtained with Fluorenes ring angulation is related with the polarisation ATR difference spectras analyzed and inverse wave length dispersing characteristic, by calculating the angle being obtained Closer to 90 °, then the difference spectra of the polarisation ATR analyses observed is bigger, can obtain stronger inverse wave length dispersing characteristic.It is trans When the angle of conformation is 50 ° or more, preferably 60 ° or more, more preferably 70 ° or more, particularly preferably 80 ° or more, show Inverse wave length dispersiveness can predict that used repetitive structure shows inverse wave length dispersiveness.

According to the comparison of reference example 2-1 and reference example 2-2, assuming that the phase difference film for showing inverse wave length dispersiveness uses In the case of way, in order to show identical phase difference ratio (Re450/Re550) 0.90, the reference example 2-1 of two fluorenes diester is used (polyestercarbonate) with using BHEPF reference example 2-2 (makrolon) compared with, the much less of monomer containing fluorenes ring, thus it can be said that Using during compound 2 when using BHEPF compared with show inverse wave length dispersiveness effect it is high.It is thought that due to two fluorenes two The compound 2 of ester fluorenes ratio compared with BHEPF is high, moreover, compared with BHEPF, the ratio of soft alkylidene chain in compound 2 It is low thus upright and outspoken, so fluorenes ring is the state of straight trip easily with respect to main chain.

Think according to analog result, on compound 2, the stability of anti conformation and gauche conformation is equal or trans Conformation is slightly stablized, and in contrast, on compound 3, anti conformation is stablized, and there are ratio height.In addition, in compound 3 and change It closes in 2 respective anti conformation of object, main chain and fluorenes ring angulation are 70 ° or more, can predict and show high head sea Long dispersiveness.In addition, in compound 3, main chain is with fluorenes ring angulation more than 80 °, it is believed that shows compound more than 2 Inverse wave length dispersiveness, disperses it is thus regarded that can show the inverse wave length equal with compound 2 to be less than the dosage of compound 2 Property.

In addition, high 20 DEG C of the fusing point or more compared with compound 2 of compound 3, decomposition initial temperature is also high, thus assume that being made Glass transition temperature during resin is than using the resin of compound 2 high, it is believed that thermal stability is also high.

The chemical structural formula for the repetitive unit for showing the monomer source containing fluorenes ring synthesized in synthesis example 2-1 is arranged in table 5 With fluorenes ratio.It should be noted that fluorenes ratio is calculated by following formula.Wherein, the molecular weight of the fluorene skeleton in following formula is with 13 carbon What the form of atom (not including hydrogen atom) was calculated.

Molecular weight × 100 of molecular weight/repetitive unit of fluorenes ratio (%)=fluorene skeleton

[table 5]

Table 5

As noted above it is believed that by improving the ratio shared by the fluorenes in repetitive unit, can efficiently show desired Optical characteristics, compound 2, compound 3, the fluorenes ratio of compound 4 and compound 5 are more than 70%, it is taken as that using The resin combination of their present invention is suitable for efficiently showing desired optical characteristics.In contrast, the feelings of BHEPF Under condition, the fluorenes ratio in the repetitive unit in source is less than 50%, is not to have for the desired optical characteristics of performance Effect, in order to show desired optical characteristics, it is believed that need to improve the use ratio of the monomer with fluorenes.

According to the above, in the case where being assumed to show the phase difference film purposes of inverse wave length dispersiveness, contain tool The resin combination for having the polymer of three fluorene repeat units of the present invention is shown in the case of on a small quantity using three fluorenes diester i.e. Various physical property, just intrinsic birefringence, the phase difference ratios such as heat resistance can be achieved.

《Embodiment 3-1》

The shorthand notation of the compound used in following embodiments etc. is as follows.

ISB；Isobide (manufacture of Roquette Freres societies, trade name：POLYSORB)

DPC；Diphenyl carbonate (Mitsubishi chemical Co., Ltd's manufacture)

CHDM；1,4 cyclohexane dimethanol (cis, trans mixture, the manufacture of society of SK Chemical)

THF：Tetrahydrofuran (manufactures) without stabilizer, WAKO societies

[embodiment of monomer]

<Embodiment 3-1>The synthesis of 9- { [(2- ethoxycarbonylethyl groups) fluorenes -9- bases]-methyl } fluorenes (compound 2)

[changing 144]

<Synthesis example 3-1A>The synthesis of double (fluorenes -9- bases) methane (compound 1)

Fluorenes (120g, 722mmol), n,N-Dimethylformamide (480ml) are packed into 1L four-hole boiling flasks, nitrogen is carried out and puts Postcooling is changed to less than 5 DEG C.Add in sodium ethoxide (24.6g, 361mmol), several times, every time a small amount of addition paraformaldehyde (8.7g, 289mmol) so that temperature is no more than 10 DEG C, it is stirred.2 it is small when after, be added dropwise 1N hydrochloric acid (440ml), stop reaction.To gained To aaerosol solution filtered, eluted using deionized water (240ml).Thereafter, disperse obtained thick product In deionized water (240ml), progress 1 is stirred when small.After being filtered to the suspension, using deionized water (120ml) into Row elution.After obtained thick product is made to be dispersed in toluene (480ml), it is being heated to reflux using Dean-Stark apparatus Under the conditions of be dehydrated.Recover to room temperature (20 DEG C), filtered, is dried under reduced pressure at 80 DEG C until reaching constant, so as to obtain To double (fluorenes -9- bases) methane (compound 1) 84.0g (yields as white solid：84.5%th, HPLC purity：94.0%).

<Synthesis example 3-1B-1>The synthesis of 9- { [(2- ethoxycarbonylethyl groups) fluorenes -9- bases]-methyl } fluorenes (compound 2)

Be fitted into the removable flasks of 1L obtained in synthesis example 3-1A double (fluorenes -9- bases) methane (compound 1,34.0g, 98.7mmol), N- benzyls-N, N, N- triethyl ammonium chlorides (4.47g, 19.6mmol), tetrahydrofuran (170ml) carry out nitrogen After displacement, interior temperature control is made as 15 DEG C~18 DEG C, adds in 50wt/wt% sodium hydrate aqueous solutions (25.93g), afterwards solution Color becomes light yellow.Thereafter, ethyl acrylate (10.7ml, 103mmol) was added dropwise using 30 minutes, is carried out afterwards using HPLC Analysis.

(HPLC conditions)

Column：Inertsil ODS-3V 150mm×4.8mmφ

Temperature：40℃

Eluent condition：0~5min：Tetrahydrofuran/water=50/50,20min：Tetrahydrofuran/water=100/0

Flow velocity：1.0ml/min

Injection rate：2μL

(HPLC analysis results)

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 groups) fluorenes -9- bases]-methyl } fluorenes (compound 2)

In 50mL three-necked flasks add compound 1 (1.0g, 2.9mmol), benzyltriethylammoinium chloride (132mg, 0.58mmol), THF (5mL), is stirred in a nitrogen atmosphere in room temperature.Using 30 minutes addition ethyl acrylate (290mg, After 2.9mmol), when room temperature curing 3 is small.After when 16 DEG C of curings 1 are small, neutralized using 3N hydrochloric acid.Hitherward add first Benzene (5mL), 1 toluene phase is cleaned with saturated sodium bicarbonate aqueous solution (5mL), and 3 toluene phases are cleaned with water (5mL).Utilize steaming After hair device removes toluene distillation, residue is refined with silica gel chromatograph, obtains compound 2 (0.63g, 1.4mmol, yield： 49%th, white crystals).

¹H-NMR(400MHz,CDCl₃)δ7.74-7.80(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)

According to synthesis example 3-1B-1, using compound 1 as 1 equivalent ethyl acrylate of raw material and addition in the case of, third It, theoretically should be according to compound when the speed of the addition reaction of olefin(e) acid ethyl ester is identical in first addition and second addition 1：Compound 2：The ratio between compound 3 is 1：2：1 mode generates.However, surprisingly it was that the area of HPLC in the present reaction Than for 1：4：1, it is known that be selectively generating the compound 2 of single addition body.It is thought that because, for compound 3,2 The structure of a fluorenes ring accumulation is most rock-steady structure, in contrast, for compound 1 and compound 2, what 2 fluorenes rings inverted Structure is most rock-steady structure, thus during to the 2nd ethyl acrylate of 2 addition of compound, it is necessary to a fluorenes ring reversion and add Into.The proton in the fluorenes ring source of compound 1 and compound 2 exists¹On the whole in the downfield side of δ 6.60-7.80ppm in H-NMR It is observed, and the proton in the fluorenes ring source of compound 3 is observed in the highfield side of δ 6.77-7.03ppm, is observed strong The influence of strong screening effect, this also supports fluorenes ring and takes packed structures.

Usually at 2 in the case of substituent group imported parts, it is difficult to selectively import reactivity only at 1 sometimes Functional group, but in the case of specific Oligofluorenylene compounds, due to difference of three-dimensional reactivity etc., having can be easily selective Ground imports the tendency of specific reactive functional groups only at 1, it is believed that can also industrially be manufactured.

In addition, for the Oligofluorenylene compounds of compound 1 etc, importing reactivity takes in addition reaction or substitution reaction In the case of Dai Ji, it is believed that it is similary with the tendency that can be selectively generating the oligomeric fluorenes with 1 reactive functional groups, because And think to be widely used in beyond ethyl acrylate.

For example, the monoester on compound 2 etc, it is believed that it is used by the raw material for being used as polyester or polyestercarbonate, So as to be acted as end terminator, it is taken as that the molecular weight regulator as polyester or makrolon is useful.

For example, the monoester on compound 2 etc, hydroxyl is further imported as reactive substituents, so as to Oligofluorenylene compounds of the synthesis with 2 different reactive functional groups, only this can obtain the high polyester of fluorenes content, thus recognize To be useful.

《Embodiment 4-1~4-4, comparative example 4-1~4-2》

The quality evaluation and the evaluating characteristics of resin combination and hyaline membrane of the oligomeric fluorenes monomer of the present invention pass through following Method carries out.It should be noted that evaluating characteristics gimmick is not limited to the following method, those skilled in the art can be suitable for choosing It selects.

ISB：Isobide (manufacture of Roquette Freres societies, trade name：POLYSORB)

DPC：Diphenyl carbonate (Mitsubishi chemical Co., Ltd's manufacture)

(1) powder x-ray diffraction of oligomeric fluorenes diester

The x-ray diffractogram of powder spectrum of oligomeric fluorenes diester utilizes powder x-ray diffraction measurement device (SpectrisPANalitical division departments X-Pert ' Pro) is measured.

(2) particle size distribution of oligomeric fluorenes diester

On the size distribution of oligomeric fluorenes diester, laser diffraction and scattering formula particle size distribution analyzer is used (MicrotracBEL societies manufacture MT3300EX), is scattered in solvent methanol and is measured.

(3) the rotation angle of repose of oligomeric fluorenes diester

On the rotation angle of repose of oligomeric fluorenes diester, Three-wheel type angle of repose analyzer (cylinder well Physicochemical instrument society system is used Make), it is measured by cylinder rotary process.

(4) Evaluation of Thermal Stability of oligomeric fluorenes diester

Oligomeric fluorenes diester 500mg is added in 30mL flasks, is stirred in a nitrogen atmosphere when 185 DEG C of progress 7 are small.It is logical It crosses and visually confirms to heat front and rear tone.In addition, preparing the 1wt%THF solution of the front and rear oligomeric fluorenes diester of heating, purple is used Outer visible absorbance spectrophotometer (society of Shimadzu Seisakusho Ltd. manufactures UV-1650PC) determines the absorbance of the wavelength of 400nm.

[changing 145]

<Embodiment 4-1A>The synthesis of double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (compound 2)

Double (fluorenes -9- bases) methane (50g, 145.2mmol), benzyltriethylammoinium chlorides are packed into the removable flasks of 1L (6.6g, 29.0mmol), tetrahydrofuran (250mL) after carrying out nitrogen displacement, is 17 DEG C~19 DEG C using water-bath control, adds in 50wt/vol% sodium hydrate aqueous solutions (26.5mL), as a result the color of solution become pale red.Thereafter it was added dropwise using 30 minutes Ethyl acrylate (15.1mL, 145.2mmol).Thereafter, benzyltriethylammoinium chloride (6.6g, 29.0mmol) is added, further Ethyl acrylate (30.2mL, 290.2mmol) is added in, while being carried out with HPLC following responses, while when stirring 2 is small.Logical It crosses HPLC and confirms single addition body after less than 2%, to be cooled down using ice bath, control temperature that 3N hydrochloric acid is added dropwise (166.4mL), is quenched.After water layer is discarded, toluene 100mL is added, is cleaned with saturated sodium bicarbonate aqueous solution (150mL) After organic layer, further organic layer is cleaned with deionized water (150mL).Thereafter, after vacuum distillation removes tetrahydrofuran, first is added Alcohol (200mL) carries out crystallization.After suction filtration, it is dried under reduced pressure at 100 DEG C to constant is reached, so as to obtain as the double of white solid [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (compound 1) 61.9g (yields：78.0%th, HPLC purity：87.4 faces Product %).

Column：Inertsil ODS-3V 150mm×4.8mmφ

Temperature：40℃

Flow velocity：1.0mL/min

Injection rate：2μL

HPLC analysis results compound 4 (5.9min)：0.0 area % (0.0 mass %), compound 5 (10.4min)：3.0 Area % (2.9 mass %), compound 3 (13.5min)：87.4 area % (89.0 mass %)

The quantitative values calculated by calibration curve are represented in ().

m.p.：141℃

<Embodiment 4-1B>The synthesis of double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2)

Be packed into 1L four-hole boiling flasks double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (compound 1,49.7g, 91.2mmol), diphenyl carbonate (98.3g, 459mmol), original four-isopropyl titanate (1.3mL, 4.59mmol), by vacuum degree tune Whole is 3~2kPa, and by-product is distilled off in 140 DEG C~150 DEG C of temperature ranges, be carried out at the same time 10 it is small when stir.Cooling To 90 DEG C, after confirming reaction terminating by HPLC, toluene (100mL) is added in, is cooled to 50 DEG C.Methanol is added in thereto (250mL) is filtered after being cooled to room temperature.Obtained white solid is made to be dispersed in toluene (100mL), is heated to reflux 30 Minute.After being cooled to 50 DEG C, methanol (250mL) is added in.It after being cooled to room temperature (20 DEG C), is filtered, is dried under reduced pressure at 100 DEG C To constant is reached, so as to obtain double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2) as white solid 35.2g (yield：60%th, HPLC purity：98.4 area %).

m.p.：176℃

Ti content ratios：330 mass ppm

<Embodiment 4-2>The synthesis of double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2)

Diphenyl carbonate (74.9 mass parts) is added in 250L GL reactors, makes its dissolving at 120 DEG C.Thereto plus Enter double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (compound 1,38.1 mass parts), original four-isopropyl titanates (1.0 Mass parts), vacuum degree is adjusted to 3.0kPa, by-product is distilled off, while stirs 7 hours until interior temperature reaches 185 DEG C. After recovering normal pressure with nitrogen, 90 DEG C, after confirming reaction terminating by HPLC are cooled to, adds in toluene (66 mass parts), conveying Into 400L GL reactors, 50 DEG C are cooled to.Methanol (151 mass parts) is added in thereto, after being cooled to 5 DEG C, centrifuged Filter.Obtained thick product is made to be dispersed in toluene (66 mass parts), is heated to reflux 30 minutes.After being cooled to 50 DEG C, add in Methanol (151 mass parts) after being cooled to 22 DEG C, carries out centrifugal filtration.Obtained thick product is further made to be dispersed in toluene In (66 mass parts), it is heated to reflux 30 minutes.After being cooled to 50 DEG C, methanol (151 mass parts) is added in, after being cooled to 22 DEG C, into Row centrifugal filtration.It is dried under reduced pressure at 80 DEG C until reaching constant, so as to obtain double [9- (2- phenoxy group carbonyls as white solid Base ethyl) fluorenes -9- bases] methane (compound 2) 27.2g (yields：61%th, HPLC purity：99.5 area %).

Ti content ratios：40 mass ppm

<Embodiment 4-3>The synthesis of double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2)

Double [9- (the 2- phenyloxycarbonyls ethyl) fluorenes -9- bases] obtained in embodiment 4-2 is added in the removable flasks of 1L Methane (compound 2,60g), toluene (120mL), be warming up to 80 DEG C make its dissolve after, add in deionized water (180mL), carry out 30 After minute stirring, pass through liquid separation and operate discarded water layer.Deionized water (180mL) is added in again, after carrying out stirring in 30 minutes, is passed through After the discarded water layer of liquid separation operation, pressure filtration (0.2MPa, ADVANTEC PTFE film filter, 0.5 μ of aperture are carried out to organic layer m：H050A47A), organic layer is added in the removable flasks of 1L, stirs and is cooled to 40 DEG C.Methanol is added in thereto (300mL) is filtered after being cooled to 22 DEG C.It is dried under reduced pressure at 80 DEG C until reaching constant, so as to obtain as white solid Double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2) 54.1g (yields：90%).

Ti content ratios：<0.1 mass ppm

Double [9- (the 2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2,61.7g) that will be obtained in embodiment 4-2 It is dissolved in chloroform, utilizes silica gel column chromatography (eluent：Chloroform) it is refined.For obtained chloroformic solution, steaming is utilized It sends out device vacuum distillation and removes chloroform, add in MeOH (300mL).After being cooled to room temperature (20 DEG C), filtered, it is dry in 80 DEG C of decompressions It is dry until reach constant, so as to obtain double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (chemical combination as white solid Object 2) 59.8g (yields：97%th, HPLC purity：99.5 area %).

Ti content ratios：<0.1 mass ppm

<Comparative example 4-1>The synthesis of double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2)

Be packed into 500mL four-hole boiling flasks double [9- (2- ethoxycarbonylethyl groups) fluorenes -9- bases] methane (compound 1, 35.0g, 64.3mmol), diphenyl carbonate (68.8g, 321mmol), original four-isopropyl titanate (0.95mL, 3.24mmol), will Vacuum degree is adjusted to 2.8kPa~3.2kPa, and by-product is distilled off in 135 DEG C~150 DEG C of temperature ranges, is carried out at the same time 6 Hour stirring.90 DEG C, after confirming reaction terminating by HPLC are cooled to, toluene (70mL) is added in, is cooled to 50 DEG C.Thereto Methanol (175mL) is added in, after being cooled to 5 DEG C, is filtered.Obtained white solid is made to be dispersed in toluene (70mL), is added Heat reflux 30 minutes.After being cooled to 50 DEG C, methanol (175mL) is added in.It after being cooled to room temperature (20 DEG C), is filtered, at 80 DEG C It is dried under reduced pressure until reaching constant, so as to obtain double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] first as white solid Alkane (compound 2) 32.2g (yields：78%th, HPLC purity：99.0 area %).

Ti content ratios：770 mass ppm

[changing 146]

<Comparative example 4-2A>The synthesis of double [9- (2- dion es) fluorenes -9- bases] methane (compound 3)

Double (fluorenes -9- bases) methane (10.01g, 29.06mmol), N- benzyls-N, N, N- are packed into 200mL four-hole boiling flasks Triethyl ammonium chloride (1.32g, 5.78mmol), tetrahydrofuran (50mL) after carrying out nitrogen displacement, are controlled using water-bath at 15 DEG C ~20 DEG C, after adding in 50% sodium hydrate aqueous solution (8ml), the color of solution becomes light red.Thereafter ice bath is utilized by interior temperature Control at 17 DEG C~18 DEG C, using 3 it is small when be added dropwise methyl acrylate (7.8mL, 86mmol).While with HPLC following responses into Row when stirring 3 is small on one side, is cooled down using ice bath afterwards, control in it is warm no more than 18 DEG C while 3N hydrochloric acid is added dropwise (22mL), is quenched.Toluene (20mL) is added in the organic layer obtained to liquid separation, it, will after being cleaned using deionized water Solvent under reduced pressure is distilled off, and is concentrated.Concentrate is made to recover to room temperature (20 DEG C), methanol (40mL) is added in and carries out crystallization.It takes out After filter, it is dried under reduced pressure at 80 DEG C until reaching constant, so as to obtain double [9- (2- dion es) as white solid Fluorenes -9- bases] methane (compound 3) 7.05g (yields：47.0%th, HPLC purity：80.0 area %).

Column：Inertsil ODS-3V 150mm×4.8mmφ

Temperature：40℃

Flow velocity：1.0ml/min

Injection rate：2μL

HPLC analysis results compound 4 (5.9min)：12.8 area % (12.8 mass %), compound 6 (not detecting)：Not Detection, compound 3 (11.8min)：80.0 area % (84.6 mass %)

The quantitative values calculated by calibration curve are represented in ().

¹H-NMR(400MHz,CDCl₃)δ7.02(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>The synthesis of double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2)

Be packed into 50mL three-necked flasks double [9- (2- dion es) fluorenes -9- bases] methane (compound 3,6.0g, 11.6mmol), diphenyl carbonate (12.1g, 56.6mmol), original four-isopropyl titanate (0.16mL, 0.55mmol), are warming up to 145 DEG C, progress 1 is stirred when small.Confirm that reaction does not carry out by HPLC, therefore further add in original four-isopropyl titanate (0.32mL, 1.1mmol), 1 it is small when after carry out HPLC analyses again, as a result confirm the disappearance and reaction at the peak of compound 4 It carries out, therefore further when 145 DEG C of stirrings 1 are small.After confirming reaction terminating by HPLC, toluene (15ml), heating are added in Flow back 1 it is small when.After being cooled to 50 DEG C, methanol (18mL) is added in.After being cooled to room temperature (20 DEG C), filtered.Make obtained White solid is dispersed in toluene (12mL), be heated to reflux 1 it is small when.After being cooled to 50 DEG C, methanol (18mL) is added in.It is cooled to room It after warm (20 DEG C), is filtered, is dried under reduced pressure at 100 DEG C to constant is reached, so as to obtain double [9- (2- as white solid Phenyloxycarbonyl ethyl) fluorenes -9- bases] methane (compound 2) 5.39g (yields：64%th, HPLC purity：98.1 area %).

Ti content ratios：3300 mass ppm

In enamel 12m³In reactor will double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2, 1201 mass parts) 32.7wt% o-xylene solutions cool down at leisure from 86 DEG C, reach 60 DEG C at the time of add methanol (551 mass parts), and then crystal seed is added at the time of reaching 55 DEG C, crystallization is precipitated.Thereafter, using 5 it is small when be cooled to 40 DEG C, Using 1 it is small when add methanol (3548 mass parts), and then using 5 it is small when be cooled to 21 DEG C.It is divided into 10 batches by centrifugal filtration To crystallization, it is divided into 2 batches in 80 DEG C of dryings to constant is reached using cone drier, so as to obtain double [9- as white solid (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] 1125 mass parts (rate of recovery of methane (compound 2)：94%th, HPLC purity：99.8 faces Product %).

Average grain diameter：178 μm, 50 μm or more particle-size accumulation %：99%

Rotate angle of repose：55°

X-ray diffractogram of powder is composed：2 θ=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°

In enamel 12m³In reactor will double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2, 1224 mass parts) 32.0wt% o-xylene solutions cool down at leisure from 81 DEG C, reach 68 DEG C at the time of add crystal seed.Its Postcooling to 49 DEG C, using 1 it is small when add methanol (4579 mass parts), further using 5 it is small when be cooled to 21 DEG C, pass through centrifugation Filtering is divided into 6 batches and is crystallized, and is divided into 2 batches in 80 DEG C of dryings to constant is reached using cone drier, so as to obtain as white 1043 mass parts (the rate of recovery of double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2) of color solid：85%th, HPLC purity：99.8 area %).

Average grain diameter：44 μm, 50 μm or more particle-size accumulation %：30%

Rotate angle of repose：62°

To enamel 1m³After reactor carries out nitrogen displacement, double [9- (2- phenyloxycarbonyls ethyl) fluorenes -9- bases] first are added Alkane (compound 2,250 mass parts), ortho-xylene (450 mass parts), being warming up to 100 DEG C or more makes its dissolving.Thereafter it is cooled to 80 DEG C, after adding crystal seed, 20 DEG C are cooled to 10 DEG C of cooling velocity when small with 1, starts centrifugal filtration.

1st centrifugation can be filtered successfully, but the crystallization in reactor is gradually micronized, so as to slurry character sharp It is deteriorated, can be filtered until the 3rd time centrifuges, but extraction afterwards becomes difficult, has interrupted centrifugal filtration.It is obtained to the 3rd Substance until secondary centrifugation is dry to constant is reached at 80 DEG C, so as to obtain double [9- (2- phenyloxycarbonyls as white solid Ethyl) fluorenes -9- bases] 63.2 mass parts (rate of recovery of methane (compound 2)：25%).

1st centrifugation

X-ray diffractogram of powder is composed：2 θ=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 grain diameter：220 μm, 50 μm or more particle-size accumulation %：88%

3rd centrifugation

Average grain diameter：25 μm, 50 μm or more particle-size accumulation %：5%

Embodiment 4-1 and embodiment 4-2 are compared, it is known that：By increasing the crystallization number of toluene and methanol, target The Ti contents of oligomeric fluorene diaryl ester (compound 2) are reduced from 330ppm to 40ppm.In addition, to embodiment 4-1 and comparative example In the comparative example 4-1 that 4-1 is compared, it is known that：By the way that toluene and methanol recrystallization temperature is made to be reduced to 5 DEG C from room temperature, so as to yield It is 78% to improve from 60%, but the remaining quantity of Ti is significantly deteriorated from 330ppm as 770ppm.In addition, in comparative example 4-2, make In the case of containing the raw material of oligomeric fluorenes dicarboxylic acids to the ratio more than 10 mass %, urged using the ester exchange reaction of specified amount Agent can not carry out reaction, it is necessary to additional catalyst for ester exchange reaction.It is thought that because, oligomeric fluorenes dicarboxylic acids and transesterification The Ti compounds of catalysts form complex compound, so that it is inactivated.Thus, it can be known that obtained oligomeric fluorene diaryl ester The Ti contents of (compound 2) are significantly increased.In embodiment 4-3, washing work is implemented to the compound 2 obtained in embodiment 4-2 In embodiment 4-4, the compound obtained in embodiment 4-2 is refined with silica gel column chromatography for sequence and pressure filtration, so as to Ti contents can be reduced following to detection limit.Particularly, the cost of washing step and the process for purification of pressure filtration ratio is utilized It is relatively low, can also industrially it implement, thus can be described as excellent process for purification.

It is arranged in table 6 and Ti contents in the oligomeric fluorenes diester of each embodiment and comparative example and Evaluation of Thermal Stability is shown As a result.

[table 6]

Table 6

Then, the tone variations based on the crystallization under 6 pairs of table plus thermogenetic molten condition are discussed.Before heating Tone, be the light yellow of yellowish in embodiment 4-1, but be white in embodiment 4-2, embodiment 4-3 and embodiment 4-4 Color.In contrast, yellowly is coloured before heating in comparative example 4-1, comparative example 4-2.And then 185 DEG C carried out 7 it is small when It heats, does not observe coloring in acetonideexample 4-3, embodiment 4-4, obtained the crystallization of water white transparency.Embodiment 4-2, reality It applies in a 4-1, comparative example 4-1 and comparative example 4-2 as Ti contents increase, observes the tendency that coloring substantially deepens, particularly Comparative example 4-1, comparative example 4-2 heating after crystallization be brown.

The details of coloring is unclear, but thinks that one of reason is the chelating materialization of metal ingredient.

Then, based on Fig. 1, the absorbance change of the 400nm of the 1wt%THF solution tone variations front and rear to heating are passed through It discusses.As shown in Figure 1, embodiment 4-2 (40ppm), embodiment 4-3 (<0.1ppm), embodiment 4-4 (<0.1ppm) adding The absorbance of THF solution does not see variation substantially before and after heat.In embodiment 4-1 (330ppm) and comparative example 4-1 (770ppm) Middle Ti contents are 2 times or so, but observe that its absorbance difference has nearly 4 times of difference.It is possible thereby to confirm, Ti contents produce tone There is very big gap between the 770ppm of the 330ppm and comparative example 4-1 of embodiment 4-1 in raw influence.In addition, on comparing Example 4-2 (3300ppm), tone is deteriorated and the precipitation of insoluble component is violent, it is difficult to measure the absorbance of 400nm.

The above result shows that by using the oligomeric fluorenes diester of the present invention, also lack even if tone variations in the molten state, The coloring of producible resin combination when can thus inhibit by smelting process.

As shown in Fig. 2, in 12m³Enamel reactor in carried out the reference example 4-1 and reference example 4-2 of crystallization into Row compares, and the average grain diameter of obtained crystallization is small in reference example 4-2, is 44 μm, the rotation as powder fluidity index is stopped Angle till is 62 °, also shows that high level.In contrast, by being added separately methanol in reference example 4-1, the average grain diameter of crystallization becomes Greatly 178 μm, rotation angle of repose also improves as 55 °.The above result shows that by using the big knot of the average grain diameter of the present invention Crystalline substance, even if being used as resin raw material, feeding intake property also has no problem.

Crystallization has been carried out merely with the ortho-xylene as good solvent in reference example 4-3, has as a result understood, has obtained the 1st time Average grain diameter after centrifugal drying be 220 μm, big and good crystallization, the character of pulp solution timely changes to be sticky high Thick soup shape suspension, the average grain diameter after the 3rd centrifugal drying is micronized to 25 μm.In addition, the 3rd time flows after centrifugation Property be further deteriorated, therefore become difficult from the extraction in reaction solution, centrifugal filtration is interrupted, and is redissolved.In addition, to by Powder after 1 centrifugal drying implements XRD analysis, result viewing to 2 θ=5.6 °, 8.5 °, 11.0 °, 12.5 °, 12.9 °, 14.9 °, 16.3 °, 19.1 ° of peak do not observe the peak from by the powder after the 3rd centrifugal drying.It follows that the 1st time from The powder of the heart contains the crystallization of metastable setting, as phase transfer is into shape is stablized at leisure, so as to be micronized.

Reference example 4-1 good solvent using ortho-xylene, poor solvent using in the case of methanol, do not observe 2 θ= 5.6 °, 8.5 °, 11.0 °, 12.5 °, 12.9 °, 14.9 °, 16.3 °, 19.1 ° of peak, are not micronized, thus pass through good solvent The aromatic hydrocarbon using ortho-xylene as representative, poor solvent is used to use the alcohol series solvent using methanol as representative, it is thus regarded that can To obtain the big particle of average grain diameter.

[synthesis example of polymer]

26.63 mass parts (0.042 mole) of double [9- (the 2- phenyloxycarbonyls ethyl) fluorenes -9- bases] methane (compound 2) of general, CHDM10.78 mass parts (0.075 mole), ISB33.58 mass parts (0.230 mole), (0.263 rubs DPC56.33 mass parts You) and calcium acetate monohydrate 5.36 × 10 as catalyst^-4Mass parts (3.04 × 10^-6Mole) input reaction vessel, Heating tank temperature is made to be stirred as needed for 150 DEG C while making dissolution of raw material (about 10 minutes) under nitrogen atmosphere.It is molten As the process of the 1st step of reaction, 220 DEG C were warming up to using 30 minutes by Xie Hou, were reacted 60 minutes under normal pressure.Next, it utilizes Pressure was kept for 30 minutes from atmospheric depressurized to 13.3kPa in 13.3kPa in 90 minutes, the phenol of generation is retracted to reaction holds Outside device.

Next, the process as the 2nd step of reaction, 240 DEG C, while profit were warming up to using 15 minutes by the temperature of heating tank With 15 minutes by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction vessel.Torque as defined in arrival Afterwards, reaction is terminated, the polymer of generation is expressed into water, obtains the particle of polyestercarbonate.

Refractive anisotrop, the phase difference of stretched film when film shaping is carried out to obtained resin combination and being stretched Table 7 is listed in than measurement results such as (Re450/Re550).

By double 62.40 mass parts (0.142 mole) of (4- (2- hydroxyl-oxethyls) phenyl) fluorenes (BHEPF) of 9,9-, ISB28.78 mass parts (0.197 mole), DPC73.40 mass parts (0.343 mole) and four water of magnesium acetate as catalyst Close object 7.28 × 10^-4Mass parts (3.39 × 10^-6Mole) input reaction vessel, it is 150 to make heating tank temperature in a nitrogen atmosphere DEG C, it is stirred as needed while making dissolution of raw material (about 10 minutes).After dissolving, as the process of the 1st step of reaction, profit 220 DEG C were warming up to 30 minutes, is reacted 60 minutes under normal pressure.Next, using 90 minutes by pressure from atmospheric depressurized to 13.3kPa is kept for 30 minutes in 13.3kPa, the phenol of generation is retracted to outside reaction vessel.

[table 7]

Table 7

As shown in Table 7, the polyestercarbonate of compound 2 and the use BHEPF of reference example 4-5 are used to reference example 4-4 Makrolon be compared, amount of monomer is less in reference example 4-4, phase difference ratio (Re450/Re550) on an equal basis, thus it is shown that Strong inverse wave length dispersiveness.In addition, photoelastic coefficient is also the value of less than half.It can be said that oligomeric fluorenes of the invention Diester is very excellent monomer.

The present invention is described in detail with reference to particular implementation, but it is it will be understood by those skilled in the art that known Various changes, amendment can be imposed to the present invention without departing from the spirit and scope of the present invention.The application is based on 2014 Year 27 days 2 months Japanese patent applications (Japanese Patent Application 2014-037216) submitted, the Japan Patent submitted on March 19th, 2014 The Japanese patent application (Japanese Patent Application 2014-078068) that application (Japanese Patent Application 2014-056873), on April 4th, 2014 submit And the Japanese patent application (Japanese Patent Application 2014-084649) that on April 16th, 2014 submits, in reference form by its content Introduce this specification.

Claims

1. a kind of resin, for the resin of the polycondensation system with the constitutional repeating unit comprising aromatic structure, the spy of the resin Sign is,

The resin has selected from least one of the structural unit represented by following formula (1) and formula (2) structural unit,

5≤A≤-22.5×B+38.3 (I)

Wherein, 0.75≤B≤0.93,

A：The content of the aromatic structure in the constitutional repeating unit of resin is formed, unit is quality %,

B：The ratio between phase difference R450 of the stretched film made of resin in the 450nm and phase difference R550 in 550nm R450/ R550,

[changing 1]

In formula (1) and (2), R¹~R³It is each independently Direct Bonding or the carbon number with or without substituent group is 1~4 alkylidene,

R⁴~R⁹Be each independently hydrogen atom, with or without substituent group carbon number be 1~10 alkyl, have or Aryl that carbon number without substituent group is 4~10, with or without substituent group carbon number be 1~10 acyl Acyloxy that base, the carbon number with or without substituent group are 1~10, the carbon number with or without substituent group are 1~10 alkoxy, with or without substituent group carbon number be 1~10 aryloxy group, with or without substituent group Amino, with or without substituent group carbon number be 1~10 vinyl, the carbon atom with or without substituent group Number is 1~10 acetenyl, the sulphur atom with substituent group, the silicon atom with substituent group, halogen atom, nitro or cyano；Its In, R⁴~R⁹In, adjacent at least two group can be mutually bonded to form ring.

2. resin as described in claim 1, wherein, the content of the aromatic structure in the constitutional repeating unit meets following Formula (III), and the glass transition temperature of the resin is less than 110 DEG C or more 160 DEG C,

5≤A≤-22.5×B+34.8 (III)

Wherein, 0.75≤B≤0.93,

B：The ratio between phase difference R450 of the stretched film made of resin in the 450nm and phase difference R550 in 550nm R450/ R550。

3. resin as claimed in claim 1 or 2, wherein, the refractive index in sodium d lines (589nm) of the resin for 1.49~ 1.56。

4. resin as claimed in claim 1 or 2, wherein, the storage modulus of the resin is more than 1GPa below 2.7GPa.

5. resin as claimed in claim 1 or 2, wherein, the resin is in 240 DEG C of measuring temperature, shear velocity 91.2sec^-1Item Melt viscosity under part is more than 700Pas below 5000Pas.

6. resin as claimed in claim 1 or 2, wherein, the resin is selected from by makrolon, polyester, polyestercarbonate At least one of group of composition resin.

7. resin as claimed in claim 1 or 2, wherein, the aromatic structure that the constitutional repeating unit is included is only fluorenes.

8. resin as claimed in claim 1 or 2, wherein, which contains the structural unit represented by following formula (3),

[changing 2]

9. resin as claimed in claim 1 or 2, wherein, which contains the structural unit represented by the following general formula (8),

In above-mentioned general formula (8), R^1-14It represents to be 2~20 with or without the carbon number of substituent group with acetal ring Group.

10. a kind of hyaline membrane contains resin according to any one of claims 1 to 9.

11. a kind of phase difference film is obtained by being stretched to the hyaline membrane described in claim 10 at least one direction It arrives.

12. phase difference film as claimed in claim 11, wherein, which is made of simple layer, and film thickness is 10 μm or more Less than 60 μm.

13. a kind of circular polarizing disk, in the circular polarizing disk, phase difference film and light polarizing film lamination described in claim 11 or 12.