CN106062035A

CN106062035A - Polycondensation resin and optical film comprising same

Info

Publication number: CN106062035A
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: 2016-10-26
Anticipated expiration: 2035-02-26
Also published as: KR102341901B1; TW201540702A; CN106062035B; TWI673262B; KR20210020179A; CN108586723A; KR102278717B1; WO2015129833A1; KR20160126998A

Abstract

The purpose of the present invention is to provide a resin that has an excellent balance of a variety of properties, such as optical physical properties, heat resistance, mechanical properties, and heat stability, and to provide an optical film and a phase-difference film that are obtained using the resin. The present invention relates to a polycondensation resin that has a repeating structural unit that includes an aromatic structure, the resin being characterized by having a structural unit and by the content of the aromatic structure in the repeating structural unit satisfying formula (I). (I) 5<=A<=-22.5*B+38.3, wherein 0.75<=B<=0.93, A is the content (in mass%) of the aromatic structure in the repeating structural unit that constitutes the resin, and B is the ratio (R450/R550) of the phase difference (R450) at 450 nm and the phase difference (R550) at 550 nm of a stretched film that is produced from the resin.

Description

Polycondensation system resin and the blooming formed by it

Technical field

The present invention relates to the various excellents such as a kind of optics physical property, thermostability, mechanical properties, heat stability resin, And use the blooming that this resin obtains.

Moreover, it relates to three novel fluorenes diester, comprise the low polyfluorene diester compositions of this three fluorenes diester, Yi Jihan There is the resin combination of the polymer with the repetitive from three novel fluorenes diester, use this resin combination to obtain Stretched film, circular polarizing disk and image display device.

Moreover, it relates to novel low polyfluorene, the low polyfluorene compositions comprising this low polyfluorene and use this oligomeric The resin combination that fluorenes obtains.

Moreover, it relates to low polyfluorene diester and employ the manufacture method of resin combination of this low polyfluorene diester.

Background technology

In recent years, the optics used in the optical system of optical lens, blooming, optical record medium etc is with transparent The needing of resin increases.Wherein, particularly with liquid crystal display or organic el display, the thin flat as representative shows Popularizing of device (FPD) is notable, for improving contrast and colouring (color つ I), expand the angle of visual field, prevent external light reflection etc. The purpose of the raising of display quality, just at the various blooming of development and utilization.

In organic el display, employ 1/4 wavelength plate of reflection for preventing exterior light.In order to suppress coloring, Clean black display can be carried out, for the phase retardation film for 1/4 wavelength plate, it is desirable to can be at each wavelength of visibility region Under obtain wavelength dispersion characteristics preferable phase difference characteristics, wide band.

As the phase retardation film suitable with this, such as, disclose the description below: according to the mode pair that respective slow axis is orthogonal 2 kinds of phase retardation films that birefringent wavelength dispersion is different carry out lamination, thus obtain the phase retardation film (patent documentation of wide band 1).There is further disclosed herein following method: according to mode that respective slow axis is certain specific configuration to 1/2 wavelength plate and 1/4 Wavelength plate carries out lamination, thus can get phase retardation film (patent documentation 2).Furthermore disclosed by having specific degree of acetylation The wide band phase retardation film (patent documentation 3) that cellulose acetate is formed；By comprising the poly-carbon that side chain has the bis-phenol structure of fluorenes ring The phase retardation film that acid ester copolymer is formed, this phase retardation film demonstrates the inverse wave length dispersibility that the shortest then phase contrast of wavelength is the least (patent documentation 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 coming from fluorenes ring And the feature of thermostability etc, as material (patent documentation 5) useful in optical applications.

In these resins, commonly used be easier to obtain monomer, i.e. 9, double [4-(2-hydroxyl-oxethyl) benzene of 9- Base] fluorenes, double (the 4-hydroxy-3-methyl phenyl) fluorenes (patent documentation 6,7) of 9,9-.

Additionally, also have the resin of new construction in exploitation.Patent Document 8 discloses two aminations at side chain with fluorenes ring Compound, has further stated that the stretched film of the polyimide resin using this diamine compound.Patent Document 9 discloses and make Polycarbonate resin with the fluorene compound not containing aromatic rings on main chain.Patent Document 10 discloses in same intramolecular There is dihydroxy compounds or the diester compound of 2 fluorenes rings, further stated that use this dihydroxy compounds or class The stretched film of the polyester resin of compound.

The description below is disclosed: by by the repetition with fluorenes ring in polycarbonate resin in patent documentation 11,12 The content of unit controls to be particular range, this polycarbonate resin the stretched film formed demonstrates the shortest then phase contrast of wavelength more Little inverse wave length dispersibility, thus, there is the performance of excellence as phase retardation film.Demonstrate that the shortest then phase contrast of wavelength is the least The phase retardation film of so-called inverse wave length dispersibility can obtain preferable phase difference characteristics, as circle under each wavelength of visibility region Polaroid image display device prevent in external light reflection and angle of visual field correction etc. useful.

As having the dihydroxy compounds of fluorenes ring at side chain, 9 described in commonly used patent documentation 11 or 12,9-is double [4-(2-hydroxyl-oxethyl) phenyl) fluorenes, double (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-.Patent documentation 13 discloses same There is in a part the diester compound of 2 fluorenes rings, further stated that the polyester resin using this diester compound.In patent In document 10, disclose dihydroxy compounds or the diester compound in same intramolecular with 2 fluorenes rings, further state that Use the stretched film of the polyester resin of this dihydroxy compounds or diester compound.

Particularly, it is known that: the polyester employing two fluorene compounds with 2 fluorenes rings has the glass transition that comparison is high Temperature and negative birefringence, thus useful in reflecting polarizer purposes (patent documentation 10).The most known: as resinogen Material, share 2 kind of two fluorene compound that functional end-group is different.

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

As having the dihydroxy compounds of fluorenes ring at side chain, 9 described in commonly used patent documentation 11 or 12,9-is double [4-(2-hydroxyl-oxethyl) phenyl) fluorenes, double (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-.

The most known: although not being that inverse wave length disperses purposes, but to use specific diester compound as polyester In the case of carbonate source, from the aspect of light penetration, the content making the chlorine comprised in this compound is ormal weight Below (patent documentation 15).

Prior art literature

Patent documentation

Patent documentation 1: Japanese Laid-Open flat 5-27118 publication

Patent documentation 2: Japanese Laid-Open flat 10-68816 publication

Patent documentation 3: Japanese Laid-Open 2000-137116 publication

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

Patent documentation 5: Japanese Laid-Open flat 10-101786 publication

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

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

Patent documentation 8: Japanese Laid-Open 2008-112124 publication

Patent documentation 9: Japanese Laid-Open 2008-222965 publication

Patent documentation 10: No. 2012/0170118 description of U.S. Patent Application Publication No.

Patent documentation 11: International Publication the 2006/041190th

Patent documentation 12: International Publication the 2011/149073rd

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

Patent documentation 14: International Publication the 1991/08190th

Patent documentation 15: Japanese Laid-Open flat 2-20518 publication

Non-patent literature

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

Summary of the invention

The problem that invention is to be solved

The development in FPD field is surprising, for phase retardation film, it is desirable to improve optical characteristics, quality, reliability etc. further, And require the filming of film.And then, also require to reduce material cost, improve the production in each operations such as masking, stretching, lamination Rate.Accompany with this, it is desirable to phase retardation film has various characteristic concurrently.Such as, as the material for phase retardation film, need following material Material, this material has required wavelength dispersibility, has low photoelastic coefficient, high-fire resistance, melt processable, machinery simultaneously concurrently The various characteristic such as intensity, and intrinsic birefringence is big, and flexibility and draftability are excellent, by the available high molecularly oriented of stretching Degree.

But, as patent documentation 1 or patent documentation 2, phase retardation film being carried out in the method for lamination, polaroid can become Thick.Further it is necessary to each phase retardation film is carried out lamination according to the mode that slow axis is particular configuration, have polaroid productivity ratio or The problem that yield rate is deteriorated.Patent documentation 3, the phase retardation film of patent documentation 4 have inverse wave length dispersibility, the available width of sheet of membrane The phase difference characteristics of band domain, but the thermostability of the cellulose acetate of patent documentation 3 is not enough, and there is the chi caused because of moisture absorption Very little deformation and the problem that produces figure image patch (portrait speckle).

Known: the phase retardation film formed by the polycarbonate resin with fluorenes ring of patent documentation 4,6,7 is as demonstrating The phase retardation film of inverse wave length dispersibility or image display device useful for the circular polarizing disk that prevents external light reflection.But, According to the research of the present inventor, employing 9, the resin of double (the 4-hydroxy-3-methyl phenyl) fluorenes of 9-is crisp due to film, it is difficult to enter Row obtains the stretching of high-orientation, employs 9, and 9-double [4-(2-hydroxyl-oxethyl) phenyl] is although the resin draftability of fluorenes compares Excellence, but photoelastic coefficient is slightly higher, and the poor reliability under high temperature.

As the means that various characteristics are improved, it is contemplated that change copolymer composition or the ratio of adjustment, 9,9-double (4- Hydroxy-3-methyl phenyl) fluorenes on the one hand thermostability is the highest, has the characteristic that resin becomes fragile but then, it is difficult to keeping The flexibility of resin is improved while the thermostability of appropriateness.It addition, 9, the feelings of double [4-(2-hydroxyl-oxethyl) phenyl] fluorenes of 9- Under condition, in order to show desired inverse wave length dispersibility, need these monomers about containing 50 mass %～70 mass % Composition, the degree of freedom of MOLECULE DESIGN based on copolymerization is low, it is difficult to take into account the characteristic such as thermostability or mechanical strength and optical characteristics.

It addition, about the polycarbonate resin using the glycol containing fluorenes ring described in patent documentation 9, inverse wave length is disperseed Property, the characteristic such as photoelastic coefficient, thermostability is not enough.About the polyester described in patent documentation 10, describe negative index respectively to The refractive index of the opposite sex, i.e. draw direction is less than the refractive index of stretching right angle orientation.But, as phase retardation film, needs just have Refractive anisotrop, above-mentioned drawn polyester film condition is not satisfied.It addition, also not about phase contrast in patent documentation 10 The record of wavelength dependency.

As it has been described above, existing phase retardation film is difficult to balancedly obtain inverse wave length dispersibility, optical characteristics, thermostability, machine The various characteristics such as tool intensity.In order to thoroughly improve the characteristic of phase retardation film, it is desirable to by the new chemical combination of the balancing good of various characteristics Thing is used for raw material.

The first object of the present invention is to solve above-mentioned problem, it is provided that optics physical property, thermostability, mechanical properties, thermally-stabilised The resin of the various excellents such as property and use the blooming that this resin obtains.

Additionally, it is known that: the stretched film formed by the polycarbonate resin with fluorenes ring of patent documentation 11,12 is as display Go out the useful for the circular polarizing disk that prevents external light reflection of the phase retardation film of inverse wave length dispersibility or image display device.But Be, according to the research of the present inventor, patent documentation 11 employ 9,9-double (4-hydroxy-3-methyl phenyl) although the resin of fluorenes There is high-fire resistance, but in order to show desired inverse wave length dispersibility, needs raising has the repetitive of fluorenes ring Ratio, thus easily form crisp film, flexibility has problems.On the other hand, patent documentation 12 employ 9, the double [4-of 9- (2-hydroxyl-oxethyl) phenyl] although the resin flexibility of fluorenes is excellent, but in order to show desired inverse wave length dispersibility, Need to improve the ratio of the repetitive with fluorenes ring, it is difficult to take into account the various physical property such as thermostability and optics physical property.Therefore, in order to The optics physical property of further improved resin and the various physical property such as thermostability, flexibility, it is desirable to 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.

The polyester using two fluorene compounds to obtain is disclosed in patent documentation 13 and 10, but owing to two is fluorene structured, heat-resisting Property is the most unsatisfactory.In addition, being not used as film and use in patent documentation 13, optical characteristics etc. is the most indefinite, specially Not studying as phase retardation film in profit document 10, the wavelength dependency of phase contrast is the most indefinite.

The second object of the present invention is to provide a kind of novel fluorene compound, and it has sufficient thermostability, and few When amount uses this fluorene compound manufacture resin combination and carry out film molding, can be shown that the optical characteristics of excellence such that it is able to Improve the degree of freedom of resin design.Further it is provided that use the resin combination that novel fluorene compound obtains.

Additionally, as described in patent documentation 10, as the method giving specific physical property to resin, can enumerate by The method that the different two kinds of Oligofluorenylene compounds of the reactive functional groups of end carry out share.But, Oligofluorenylene compounds is difficult to Obtain, in order to manufacture the resin with desired physical property, need to synthesize two kinds of Oligofluorenylene compounds as raw material separately, need Want time and cost, as the practicality of industrial product it may be said that deficiency.

Present inventor has performed further investigation, it was found that high as practicality, to the resin desired physical property of imparting Method, the Oligofluorenylene compounds that use has different reactive functional groups at two ends is useful.As this low polyfluorene The manufacture method of compound, can enumerate following method: first, as raw material, manufactures and has the oligomeric of 1 reactive functional groups Fluorene compound, it follows that import the reactive functional groups different from above-mentioned reactive functional groups to above-mentioned Oligofluorenylene compounds.

As the manufacture method of the Oligofluorenylene compounds with 1 reactive functional groups, in the most known non-patent literature 1 The method recorded, but the method is difficult to optionally obtain the Oligofluorenylene compounds with 1 reactive functional groups, therefore deposit Being difficult to manufacture efficiently, there is at two ends the problem of Oligofluorenylene compounds of differential responses functional group.

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

Additionally, the resin combination that inverse wave length is disperseed by the present inventor conducts in-depth research, it was found that by making With specific low polyfluorene diester compound as starting monomer, even if the content ratio in resin is low, it is also possible to effectively earth's surface is existing Go out desired optical characteristics, the degree of freedom of resin design can be improved.

Generally, the aspect of resin combination is being manufactured, in order to make polymerization speed and the physical property of obtained resin combination For the situation of regulation, need to control closely the amount ratio of raw material.Low polyfluorene diester compound is normally solid, as resin group In order to control its amount ratio when the raw material of compound uses, preferably make it melted and use.Present inventor has performed further investigation, result The following situation of new discovery: according to the difference of amount of metal contained in this compound, through this compound meeting of smelting process Produce coloring, it is difficult to the monomer as the resin combination of optical applications uses.

On the other hand, the manufacture method using the polyestercarbonate resins of diester compound has various, as one As property method, it is known that by ester-interchange method with molten condition carry out glycols, diaryl carbonate and two esters being polymerized molten Melt condensation methods.In the method, in the case of using diaryl carbonate and the dialkyl as two esters, ester exchange reaction The most different from the response speed of polycarbonate polymerization, thus there is dialkyl and be difficult to introduce asking in polyestercarbonate resins Topic, as two esters, is preferably used diaryl ester.It addition, as manufacturing the oligomeric fluorene diaryl at two ends with aryl The method of compound, can enumerate the method that two ends of low polyfluorene diester compound are substituted by aryl, but new discovery is following Situation: according to the difference of the amount of carboxylic acid contained in this low polyfluorene diester compound, obtained oligomeric fluorene diaryl chemical combination Amount of metal in thing can raise, and can produce coloring through smelting process.

Therefore, the fourth object of the present invention is to provide a kind of low polyfluorene diester compound, and it is for can be suitable as light The monomer learning the resin combination of purposes the low polyfluorene diester of the degree of freedom that can improve resin design, it can suppress process Producible coloring during smelting process.

And then, it is an object of the invention to provide a kind of low polyfluorene diester compound, it may serve as manufacture can The raw material of the oligomeric fluorene diaryl ester compounds of suppression coloring.

For solving the scheme of problem

In view of above-mentioned first purpose, present inventor has performed in-depth study repeatedly, found that following resin can table Revealing optical characteristics and the mechanical properties of excellence, this completes the present invention, this resin is characterised by, constitutes the repetition of resin The content of the aromatic structure in construction unit is at particular range and can show desired wavelength dispersibility.That is, the present invention Main points as follows.

[1-1]

A kind of resin, it is the resin of the polycondensation system with the constitutional repeating unit comprising aromatic structure, this resin It is characterised by,

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

This resin has at least one construction unit in the construction unit represented by following formula (1) and formula (2).

5≤A≤-22.5×B+38.3(I)

Wherein, 0.75≤B≤0.93.

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

B: the stretched film the being formed from a resin phase contrast (R450) at 450nm and the ratio of the phase contrast (R550) at 550nm (R450/R550)

[changing 1]

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

R⁴～R⁹It is each independently hydrogen atom, the alkyl that carbon number is 1～10 with or without substituent group, tool There is or do not have the aryl that carbon number is 4～10 of substituent group, be 1～10 with or without the carbon number of substituent group Acyl group, the acyloxy that carbon number is 1～10 with or without substituent group, the carbon number with or without substituent group Be the alkoxyl of 1～10, with or without the aryloxy group that carbon number is 1～10 of substituent group, with or without replacement The amino of base, the vinyl that carbon number is 1～10, former with or without the carbon of substituent group with or without substituent group Subnumber is the acetenyl of 1～10, has the sulphur atom of substituent group, has the silicon atom of substituent group, halogen atom, nitro or cyano group. Wherein, R⁴～R⁹In, at least 2 adjacent groups can be mutually bonded formation ring.)

[1-2]

A kind of resin, it is the resin of the polycondensation system with the constitutional repeating unit comprising aromatic structure, this resin Being characterised by, the content of the aromatic structure in this constitutional repeating unit meets following formula (III), and the vitrification of this resin turns Temperature is more than 110 DEG C less than 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 at sodium d line (589nm) of this resin be 1.49～ 1.56。

[1-4]

Resin as according to any one of [1-1]～[1-3], wherein, the storage modulus of this resin is more than 1GPa 2.7GPa below.

[1-5]

Resin as according to any one of [1-1]～[1-4], wherein, this resin is measuring temperature 240 DEG C, shear rate 91.2sec^-1Under the conditions of melt viscosity be above below the 5000Pa s of 700Pa s.

[1-6]

Resin as according to any one of [1-1]～[1-5], wherein, above-mentioned resin for select free Merlon, polyester, At least one resin in the group of polyestercarbonate composition.

[1-7]

Resin as according to any one of [1-1]～[1-6], wherein, the aromatic series that above-mentioned constitutional repeating unit is comprised Structure is only fluorenes.

[1-8]

Resin as according to any one of [1-1]～[1-7], it contains the construction unit represented by following formula (3).

[changing 2]

[1-9]

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

[1-10]

A kind of phase retardation film, it is by obtaining at the hyaline membrane described at least one direction stretching [1-9].

[1-11]

Phase retardation film as described in [1-10], it is made up of simple layer, and thickness is below more than 10 μm 60 μm.

In view of above-mentioned second purpose, present inventor has performed in-depth study repeatedly, it was found that specific three fluorenes diester Compound has sufficient thermostability, and uses on a small quantity and manufacture resin combination and carry out demonstrating during film molding the light of excellence Learn characteristic, this completes the present invention.

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

[2-1]

A kind of three fluorenes diester, it is characterised in that it comprises 3 fluorenes unit a with or without substituent group,

The carbon atom of 9 of this fluorenes unit a 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 and with chain be bonded.

[2-2]

Three fluorenes diester as described in [2-1], it is characterised in that it is represented by following formula (1).

[changing 3]

(in formula,

R¹And R²It is each independently Direct Bonding or the Asia that carbon number is 1～4 with or without substituent group Alkyl.

R^3aAnd R^3bBe each independently the alkylidene that carbon number is 1～10 with or without substituent group, have or Not there is the arlydene that carbon number is 4～10 of substituent group or the carbon number with or without substituent group is 6～10 Sub-aralkyl.

R⁴～R⁹It is each independently hydrogen atom, the alkyl that carbon number is 1～10 with or without substituent group, tool There is or do not have the aryl that carbon number is 4～10 of substituent group, be 1～10 with or without the carbon number of substituent group Acyl group, the acyloxy that carbon number is 1～10 with or without substituent group, the carbon number with or without substituent group Be the alkoxyl of 1～10, with or without the aryloxy group that carbon number is 1～10 of substituent group, with or without replacement The amino of base, the vinyl that carbon number is 1～10, former with or without the carbon of substituent group with or without substituent group Subnumber is the acetenyl of 1～10, has the sulphur atom of substituent group, has the silicon atom of substituent group, halogen atom, nitro or cyanogen Base.Wherein, R⁴～R⁹In, at least 2 adjacent groups can be mutually bonded formation ring.)

R¹⁰Be carbon number be the organic substituent of 1～10.)

[2-3]

Three fluorenes diester as described in [2-2], it is characterised in that the R in above-mentioned formula (1)¹⁰It is with or without replacement The carbon number of base is the aryl of 4～10.

[2-4]

A kind of low polyfluorene diester compositions, it is for comprising the three fluorenes diester and two according to any one of [2-1]～[2-3] The low polyfluorene diester compositions of fluorenes diester, it is characterised in that

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

The carbon atom of 9 of this 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]

Low polyfluorene diester compositions as described in [2-4], it is characterised in that above-mentioned two fluorenes diester are by following formula (2) institute Represent.

[changing 4]

(in formula,

R¹～R³It is each independently Direct Bonding or the Asia that carbon number is 1～4 with or without substituent group Alkyl.

R¹⁰Be carbon number be the organic substituent of 1～10.)

[2-6]

Oligomeric fluorene diaryl ester compositions as described in [2-4] or [2-5], it is characterised in that total relative to compositions Quality, the content ratio of above-mentioned three fluorenes diester is more than 1 mass %.

[2-7]

A kind of resin combination, it be to be formed or contain this and gather by having three fluorenes of the divalent polymer as repetitive The resin combination of compound, this resin combination is characterised by,

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

[2-8]

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

[changing 5]

(in formula,

[2-9]

Resin combination as described in [2-7] or [2-8], it is characterised in that it has two fluorenes of divalent further as weight Multiple unit,

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

[2-10]

Resin combination as according to any one of [2-7]～[2-9], it is characterised in that in the phase that wavelength 450nm measures Potential difference (Re450) meets following formula (20) with the ratio of the phase contrast (Re550) measured at wavelength 550nm.

Re450/Re550≤1.0(20)

[2-11]

A kind of molded body, it is characterised in that it is by the resin combination molding according to any one of [2-7]～[2-10] And obtain.

[2-12]

A kind of optics, it is characterised in that it is by the resin combination shape according to any one of [2-7]～[2-10] Become.

[2-13]

A kind of film, it is characterised in that it is formed by the resin combination according to any one of [2-7]～[2-10].

[2-14]

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

[2-15]

A kind of 1/4 λ plate, it is characterised in that it is formed by the stretched film described in [2-14].

[2-16]

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

[2-17]

A kind of image display device, it is characterised 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 was found that by specific with having The olefin(e) compound of reactive functional groups replace the Oligofluorenylene compounds that two ends are hydrogen, can with high selectivity and efficiently To desired Oligofluorenylene compounds, and then, this Oligofluorenylene compounds is as the monomer of the resin combination of optical applications or list Body raw material is suitable, this completes the present invention.

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

[3-1]

A kind of low polyfluorene, this low polyfluorene comprises the carbon of 9 of the fluorenes unit a of more than 2 with or without substituent group Atom each other by the alkylidene with or without substituent group, the arlydene with or without substituent group or have or Not there is oligomeric fluorene structural units (hereinafter referred to " the oligomeric fluorene structured list that the sub-aralkyl of substituent group is bonded with chain Unit a "), this low polyfluorene is characterised by,

The carbon atom of 9 of the fluorenes unit a of any one end in this 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 has hydrogen atom.

[changing 6]

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

[3-2]

Low polyfluorene as described in [3-1], it is characterised in that it is represented by following formula (1).

[changing 7]

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

R⁴～R⁹It is each independently hydrogen atom, the alkyl that carbon number is 1～10 with or without substituent group, tool There is or do not have the aryl that carbon number is 4～10 of substituent group, be 1～10 with or without the carbon number of substituent group Acyl group, the acyloxy that carbon number is 1～10 with or without substituent group, the carbon number with or without substituent group Be the alkoxyl of 1～10, with or without the aryloxy group that carbon number is 1～10 of substituent group, with or without replacement The amino of base, the vinyl that carbon number is 1～10, former with or without the carbon of substituent group with or without substituent group Subnumber is the acetenyl of 1～10, has the sulphur atom of substituent group, has the silicon atom of substituent group, halogen atom, nitro or cyanogen Base.Wherein, R⁴～R⁹In, at least 2 adjacent groups can be mutually bonded formation ring.

R^a～R^cIt is each independently hydrogen atom, the alkyl that carbon number is 1～10 with or without substituent group, tool Have or do not have substituent group the aryl that carbon number is 4～10 or with or without the carbon number of substituent group be 6～ The aralkyl of 10.

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

N represents the integer value of 1～5.)

[3-3]

A kind of low polyfluorene, this low polyfluorene comprises the carbon of 9 of the fluorenes unit a of more than 2 with or without substituent group Atom each other by the alkylidene with or without substituent group, the arlydene with or without substituent group or have or Not having oligomeric fluorene structural units a that the sub-aralkyl of substituent group gets up with chain bonding, this low polyfluorene is characterised by,

The carbon atom of 9 of the fluorenes unit a of any one end in this 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 has different from this reactive functional groups Reactive functional groups.

[changing 8]

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

[3-4]

Low polyfluorene as described in [3-3], it is characterised in that it is represented by following formula (2).

[changing 9]

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

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

R^a～R^cIt is each independently hydrogen atom, the alkyl that carbon number is 1～10 with or without substituent group, tool Have or do not have substituent group the aryl that carbon number is 4～10 or with or without the carbon number of substituent group be 6～ The aralkyl of 10,

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

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

N represents the integer value of 1～5.)

[3-5]

A kind of low polyfluorene compositions, this low polyfluorene compositions is characterised by, it comprises any one of [3-1]～[3-4] Described low polyfluorene (hereinafter referred to " low polyfluorene A ") with there is the chemical constitution different from this low polyfluorene A low polyfluorene (under Referred to herein as " low polyfluorene B "),

Above-mentioned low polyfluorene B comprises the carbon atom of 9 of the fluorenes unit b of more than 2 with or without substituent group each other By the alkylidene with or without substituent group, the arlydene with or without 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 gets up with chain bonding,

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

[changing 10]

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

[3-6]

A kind of resin combination, it is characterised in that it is by the polymerization of the low polyfluorene according to any one of [3-1]～[3-4] The polymer of the low polyfluorene compositions described in thing or [3-5] is formed, or comprises this polymer.

[3-7]

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

[3-8]

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

[3-9]

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

[3-10]

A kind of manufacture method of low polyfluorene, it is characterised in that make in the presence of a base low polyfluorene represented by following formula (3) with The olefine reaction with electron-withdrawing group represented by following formula (4), obtains the low polyfluorene represented by following formula (1).

[changing 11]

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

N represents the integer value of 1～5.)

[3-11]

The manufacture method of a kind of low polyfluorene, it is characterised in that make above-mentioned formula (1) the institute table obtained by the method for [3-10] The low polyfluorene shown is reacted with having electrophilic compound, obtains the low polyfluorene represented by following formula (2).

[changing 12]

(in formula,

R³It is each independently Direct Bonding or the alkylene that carbon number is 1～4 with or without substituent group Base.

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

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

N represents the integer value of 1～5.)

In view of above-mentioned 4th purpose, present inventor has performed in-depth study repeatedly, it was found that by making low polyfluorene two The content ratio of the metal ingredient contained by ester compounds is that the stability under specific scope, molten condition improves, it is possible to press down System coloring.

Additionally, as the raw material for manufacturing the oligomeric fluorene diaryl ester compounds that can suppress coloring, utilize and make carboxylic acid The low polyfluorene diester compound that content ratio is particular range, such that it is able to institute in the diaryl ester compound obtained by Jiang Diing The content ratio of the metal ingredient contained.

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

[4-1]

A kind of low polyfluorene diester, it is the low polyfluorene two of the fluorenes unit comprising with or without substituent group more than 2 Ester, it is characterised in that

The carbon atom of 9 of this fluorenes unit be bonded directly with one another or by with or without substituent group alkylidene, Arlydene with or without substituent group or the sub-aralkyl with or without substituent group are bonded with chain, and,

The content ratio of metal is below 500 mass ppm.

[4-2]

Low polyfluorene diester as described in [4-1], wherein, above-mentioned metal is choosing free long period type periodic chart the 1st race, the 2nd At least one metal in the group of race, the 12nd race, the 14th race and transition metal composition.

[4-3]

Low polyfluorene diester as described in [4-1] or [4-2], it is characterised in that it is represented by following formula (1).

[changing 13]

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

R¹⁰Be carbon number be the organic substituent of 1～10.

N represents the integer value of 1～5.)

[4-4]

Low polyfluorene diester as described in [4-3], it is characterised in that the R in above-mentioned formula (1)¹⁰Be carbon number be 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]

Low polyfluorene diester as described in [4-5], it is characterised in that it is represented by following formula (1).

[changing 14]

R¹⁰Be carbon number be the organic substituent of 1～10.

N represents the integer value of 1～5.)

[4-7]

The manufacture method of a kind of oligomeric fluorene diaryl ester, it is characterised in that by the low polyfluorene diester described in [4-6] as former Material, replaces above-mentioned R with aryl¹⁰Base, obtains diaryl ester.

[4-8]

The manufacture method of a kind of resin combination, it is characterised in that oligomeric by according to any one of [4-1]～[4-6] Fluorenes diester is used as raw material.

The effect of invention

The balancing good of the various characteristics such as the optical characteristics of the resin of the present invention, thermostability, mechanical property, reliability.Cause This, the resin of the present invention can be suitable in the bloomings such as phase retardation film.

It addition, the novel fluorene compound of the present invention has sufficient thermostability, and this fluorene compound is used to manufacture resin Compositions also carries out demonstrating during film molding the optical characteristics of excellence, such that it is able to improve the degree of freedom of resin design.

It addition, the Oligofluorenylene compounds of the present invention optionally has desired reactive functional groups, can be suitable for using Make monomer or the raw material monomer of the resin combination of optical applications.

It addition, the low polyfluorene diester compound of the present invention can be suitable as the resin combination of optical applications monomer, Or the raw material of monomer, and the degree of freedom of resin design can be improved, and then can suppress producible through smelting process Coloring.

Accompanying drawing explanation

Before and after Fig. 1 is the tenor in the low polyfluorene diester to embodiment 4-1～4-4 and comparative example 4-1 and heating The curve chart that absorbance difference compares.

Fig. 2 is the curve chart of the particle diameter distribution of the low polyfluorene diester representing reference example 4-1 and reference example 4-2.

Detailed description of the invention

Below, embodiments of the present invention are described in detail, but the explanation of technical characteristic set forth below is only this One example (typical example) of the embodiment of invention, without departing from its main points, the then present invention is not limited to content below.

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 to constitute the construction unit of this resin by each carrying out linking.More specifically, such as at polycarbonate resin In the case of, including carbonyl, also it is referred to as constitutional repeating unit.

It addition, " construction unit " refers to constitute the part-structure of resin, it it is the specific portion contained by constitutional repeating unit Separation structure.Such as, 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 the polymerisation reactivity group of part and the linking group adjacent with this polymerism reactive group, more specifically Ground is said, such as in the case of polycarbonate resin, carbonyl is linking group, by by the part-structure clamped by adjacent carbonyl It is referred to as construction unit.

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

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

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

" invention 1 "

Below, resin and film to the present invention 1 are described in detail.

It should be noted that (formula) formula (1) set forth below～(9), (11)～(15) are for illustrating in the present invention 1 Each structure.

The 1st aspect of the present invention relates to a kind of resin, and it is the contracting with the constitutional repeating unit comprising aromatic structure The resin of poly-system, this resin is characterised by, the content of the aromatic structure in this constitutional repeating unit meets following formula (I), This resin has at least one construction unit in the construction unit represented by following formula (1) and formula (2).

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, carbon number with or without substituent group It it is the alkylidene of 1～4.

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

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 represents by Glossary of basic Defined in terms in polymer science (polymer science basic terminology compilation) (IUPAC recommends 1996) The resin that polycondensation (polycondensation) obtains, is that the intermolecular condensation reaction that grows through utilizing polymer chain is carried out Polymerization obtained by resin.The resin of the polycondensation system of the present invention preferably has at least 1 in carbonic acid ester bond and ester bond The resin of individual key, more particularly, it is preferable that be any one resin in Merlon, polyester and polyestercarbonate.About these Resin, can enumerate following advantage: thermostability, mechanical properties, melt processable are excellent, it addition, by the monomer of more than 2 is entered Row copolymerization, easily by various physical characteristics controls such as optics physical property, thermostability, mechanical properties in desired scope.

The resin of the present invention comprises aromatic structure, as aromatic structure, as long as have the circulus of armaticity Then can include any structure.More specifically, benzenoid aromatic rings, non-benzenoid aromatic rings, heteroaromatic can be enumerated Deng, the most preferred benzenoid aromatic rings or heteroaromatic.In the present invention, about the fragrance in the constitutional repeating unit constituting resin The computational methods of the content of race's structure, name out concrete example and illustrate.

[molecular weight in the calculating of various aromatic structures]

The molecular weight of the aromatic structure in the present invention comprises the carbon atom in the circulus with armaticity, hydrogen former Son, hetero atom.The carbon atom, the hetero atom that are bonded with the circulus with armaticity are not included in aromatic structure.It addition, Having in the circulus of armaticity when being bonded with vinyl, acetenyl, carbonyl etc., the conjugated system of aromatic rings extends to these Functional group, but the substituent group being bonded with the circulus with armaticity is not included 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 is tied 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 the aromatic structure in constitutional repeating unit: C₆H₄=76.10

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

[calculated example 2]

[changing 19]

Constitutional repeating unit A

Constitutional repeating unit B

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

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

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

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

Molecular weight=the C of the 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 Amount %]

The resin of the present invention is characterised by, the aromatic series knot in the calculated above constitutional repeating unit constituting resin The content of structure meets following (I) formula.Further preferably meet following (II) formula, 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 contrast has inverse wave length dispersibility, as 1/4 wavelength In the case of plate uses, can obtain close to preferable phase difference characteristics in wavelength region widely.As showing this head sea One of method of long dispersibility, can enumerate and make the wavelength dispersion of the backbone constituents phase specific refractivity with polymer chain (wavelength depends on Relying property) big composition is orientated in the vertical direction of main chain.Generally, the wavelength dispersion of the longest then refractive index of aromatic conjugated system The biggest, thus the resin with inverse wave length dispersibility preferably comprises aromatic structure.On the other hand, containing virtue 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 dispersion Property.If it addition, generally contain aromatic series in a large number, then photoelastic coefficient or refractive index can increase, and are the most preferred as optics physical property Direction.Above-mentioned formula (I) means to import the aromatic structure that inverse wave length scattered performance efficiency is high, by other aromatic component It is suppressed to required Min..By for such MOLECULE DESIGN, can obtain while there is inverse wave length dispersibility photoelastic The resin of the balancing good of the optical characteristics such as property coefficient or orientation.Hereinafter concrete preferred molecular structure is illustrated.

As the value of B (R450/R550), use the value of the wavelength dispersion measured in the evaluation employ stretched film, should Stretched film is obtained by the unstretching film utilizing pressure sintering to be made by resin.

The resin of the present invention preferably has choosing construction unit freely represented by following formula (1) and following formula (2) institute The construction unit of more than a kind in the group of the construction unit composition represented.Hereinafter, sometimes this construction unit is referred to as low polyfluorene knot Structure unit.

[changing 20]

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

R⁴～R⁹It is each independently hydrogen atom, the alkyl that carbon number is 1～10 with or without substituent group, tool There is or do not have the aryl that carbon number is 4～10 of substituent group, be 1～10 with or without the carbon number of substituent group Acyl group, the acyloxy that carbon number is 1～10 with or without substituent group, the carbon number with or without substituent group Be the alkoxyl of 1～10, with or without the aryloxy group that carbon number is 1～10 of substituent group, with or without replacement The amino of base, the vinyl that carbon number is 1～10, former with or without the carbon of substituent group with or without substituent group Subnumber is the acetenyl of 1～10, has the sulphur atom of substituent group, has the silicon atom of substituent group, halogen atom, nitro or cyanogen Base.

At R¹And R²In, as " with or without the alkylidene that carbon number is 1～4 of substituent group ", such as, can adopt With following alkylidene.The alkylidene of the straight-chain such as methylene, ethylidene, positive propylidene, positive butylidene；Methylmethylene, two Methylmethylene, ethyl methylene, propylmethylene, (1-Methylethyl) methylene, 1-methyl ethylidene, 2-methyl Asia second Base, 1-ethylethylene residue, 2-ethylethylene residue, 1-methyl propylene, 2-methyl propylene, 1,1-dimethylethylene, 2,2- Dimethylpropylidene, 3-methyl propylene etc. have the alkylidene of side chain.Herein, R¹And R²In the position of side chain by according to fluorenes The numbering that the carbon of ring side is given by the mode of 1 represents.

R¹And R²Select can on inverse wave length dispersibility performance produce particular importance impact.Above-mentioned resin is in fluorenes ring phase The strongest inverse wave length dispersibility is demonstrated under the state that main chain direction (draw direction) is vertical orientated.In order to make taking of fluorenes ring To state close to above-mentioned state, show strong inverse wave length dispersibility, it is preferred to use the carbon number on the main chain of alkylidene It is the R of 2～3¹And R².In the case of carbon number is 1, the most unexpectedly cannot demonstrate inverse wave length dispersibility.As it Main cause, it is considered to be sterically hindered due to the carbonate group of the linking group as oligomeric fluorene structural units or ester group, from And the orientation of fluorenes ring to be fixed in relative to main chain direction be not vertical direction etc..On the other hand, when carbon number is too much, The fixing of the orientation of fluorenes ring weakens, thus inverse wave length dispersibility likely weakens.It addition, the thermostability of resin also reduces.

As shown in above-mentioned formula (1) and formula (2), about R¹And R², one end of alkylidene and fluorenes ring key close, the other end with Oxygen atom contained by linking group or the bonding of any one in carbonyl carbon.From heat stability, thermostability and inverse wave length dispersibility Aspect set out, the preferably other end of alkylidene and carbonyl carbon.As described later, as having oligomeric fluorene structured monomer, Concrete it is contemplated that glycol or the structure of diester (hereinafter, diester also comprises dicarboxylic acids), but preferably diester is used for raw material and carries out Polymerization.

It addition, from make easy to manufacture from the standpoint of, preferably R¹And R²Use identical alkylidene.

At R³In, as " with or without the alkylidene that carbon number is 1～4 of substituent group ", such as, can use Following alkylidene.The alkylidene of the straight-chain such as methylene, ethylidene, positive propylidene, positive butylidene；Methylmethylene, diformazan Methylene, ethyl methylene, propylmethylene, (1-Methylethyl) methylene, 1-methyl ethylidene, 2-methyl ethylidene, 1-ethylethylene residue, 2-ethylethylene residue, 1-methyl propylene, 2-methyl propylene, 1,1-dimethylethylene, 2,2-diformazan Base propylidene, 3-methyl propylene etc. have the alkylidene of side chain.

R³The preferably carbon number on the main chain of alkylidene is 1～2, and particularly preferred carbon number is 1.Use on main chain The R that carbon number is too much³Time, with R¹And R²The similarly immobilization of fluorenes ring weakens, it is possible to cause the fall of inverse wave length dispersibility Low, the increase of photoelastic coefficient, the reduction etc. of thermostability.On the other hand, when the carbon number on main chain is few, optical characteristics or resistance to Hot well, but in the case of connecting with Direct Bonding at 9 of two fluorenes rings, heat stability is deteriorated.

At R¹～R³In, the substituent group can having as alkylidene, substituent group illustrated below can be used, it is also possible to Use the substituent group beyond these.Halogen atom in fluorine atom, chlorine atom, bromine atoms and atomic iodine；Methoxyl group, ethyoxyl Deng the alkoxyl that carbon number is 1～10；The carbon number such as acetyl group, benzoyl is the acyl group of 1～10；Acetamido, benzene The carbon numbers such as formamido are the amide groups of 1～10；Nitro；Cyano group；1～3 hydrogen atom can be by above-mentioned halogen atom, above-mentioned The carbon numbers such as alkoxyl, above-mentioned acyl group, above-mentioned amide groups, above-mentioned nitro, above-mentioned cyano group etc. are substituted, phenyl, naphthyl be 6～ The aryl of 10.

The quantity of above-mentioned substituent group is not particularly limited, preferably 1～3.In the case of substituent group is more than 2, The kind of substituent group can be the same or different.When the quantity of substituent group is too much, polymerization likely can suppress reaction, Or produce thermal decomposition.It addition, from the aspect that industrially can manufacture at low cost, preferably R¹～R³For unsubstituted.

At R⁴～R⁹In, as " with or without the alkyl that carbon number is 1～10 of substituent group ", such as, can adopt With following alkyl.The alkyl of the straight-chain such as methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, positive decyl；Isopropyl Base, 2-methyl-propyl, 2,2-dimethyl propyl, 2-ethylhexyl etc. have the alkyl of side chain；Cyclopropyl, cyclopenta, cyclohexyl, The isothrausmatic alkyl of ring octyl group.

The carbon number of abovementioned alkyl is preferably less than 4, more preferably less than 2.If in the range of Gai, then fluorenes ring be the most difficult Sterically hindered to produce, there is the tendency obtaining the desired optical characteristics from fluorenes ring.

The substituent group can having as abovementioned alkyl, can use substituent group illustrated below, it would however also be possible to employ these Substituent group in addition.Halogen atom in fluorine atom, chlorine atom, bromine atoms and atomic iodine；The carbon atom such as methoxyl group, ethyoxyl Number is the alkoxyl of 1～10；The carbon number such as acetyl group, benzoyl is the acyl group of 1～10；Acetamido, benzamido Deng the amide groups that carbon number is 1～10；Nitro；Cyano group；1～3 hydrogen atom can by above-mentioned halogen atom, above-mentioned alkoxyl, The virtues that carbon number is 6～10 such as above-mentioned acyl group, above-mentioned amide groups, above-mentioned nitro, above-mentioned cyano group etc. are substituted, phenyl, naphthyl Base

The quantity of above-mentioned substituent group is not particularly limited, preferably 1～3.In the case of substituent group is more than 2, The kind of substituent group can be the same or different.When the quantity of such substituent group is too much, likely can suppress in polymerization Reaction, or produce thermal decomposition.It addition, from the aspect that industrially can manufacture at low cost, preferably R⁴～R⁹For without taking Generation.As the concrete example of abovementioned alkyl, trifluoromethyl, benzyl, 4-methoxy-benzyl, methoxy etc. can be enumerated.

It addition, at R⁴～R⁹In, as " with or without the aryl that carbon number is 4～10 of substituent group ", such as may be used To use following aryl.The aryl such as phenyl, 1-naphthyl, 2-naphthyl；The heteroaryls such as 2-pyridine radicals, 2-thienyl, 2-furyl.

The carbon number of above-mentioned aryl is preferably less than 8, more preferably less than 7.If in the range of Gai, then fluorenes ring be the most difficult Sterically hindered to produce, there is the tendency obtaining the desired optical characteristics from fluorenes ring.

At R⁴～R⁹In, the substituent group can having as above-mentioned aryl, substituent group illustrated below can be used, it is possible to To use the substituent group beyond these.Halogen atom in fluorine atom, chlorine atom, bromine atoms and atomic iodine；Methyl, ethyl, The carbon numbers such as isopropyl are the alkyl of 1～10；The carbon number such as methoxyl group, ethyoxyl is the alkoxyl of 1～10；Acetyl group, The carbon numbers such as benzoyl are the acyl group of 1～10；The carbon number such as acetamido, benzamido is the amide groups of 1～10； Nitro；Cyano group.The quantity of above-mentioned substituent group is not particularly limited, preferably 1～3.In the situation that substituent group is more than 2 Under, the kind of substituent group can be the same or different.It addition, from the aspect that industrially can manufacture at low cost, Preferably R⁴～R⁹For unsubstituted.

As the concrete example of above-mentioned aryl, can enumerate 2-aminomethyl phenyl, 4-aminomethyl phenyl, 3,5-3,5-dimethylphenyl, 4- Benzoylphenyl, 4-methoxyphenyl, 4-nitrobenzophenone, 4-cyano-phenyl, 3-trifluoromethyl, 3,4-dimethoxy benzene Base, 3,4-methylene dihydroxyphenyl, 2,3,4,5,6-pentafluorophenyl group, 4-methylfuran base etc..

It addition, at R⁴～R⁹In, as " with or without the acyl group that carbon number is 1～10 of substituent group ", such as may be used To use following acyl group.Formoxyl, acetyl group, propiono, 2-methylpropionyl, 2,2-Dimethylpropanoyl, 2-ethyl hexyl The aliphatic acyl radicals such as acyl group；The aromatic acyls such as benzoyl, 1-naphthyl carbonyl, 2-naphthyl carbonyl, 2-furyl carbonyl.

The carbon number of above-mentioned acyl group is preferably less than 4, more preferably less than 2.If in the range of Gai, then fluorenes ring be the most difficult Sterically hindered to produce, there is the tendency obtaining the desired optical characteristics from fluorenes ring.

The substituent group can having as above-mentioned acyl group, can use substituent group illustrated below, it would however also be possible to employ these Substituent group in addition.Halogen atom in fluorine atom, chlorine atom, bromine atoms and atomic iodine；The carbon such as methyl, ethyl, isopropyl Atomic number is the alkyl of 1～10；The carbon number such as methoxyl group, ethyoxyl is the alkoxyl of 1～10；Acetamido, Benzoylamide The carbon numbers such as base are the amide groups of 1～10；Nitro；Cyano group；1～3 hydrogen atom can be by above-mentioned halogen atom, above-mentioned alcoxyl The carbon numbers such as base, acetyl group, benzoyl are that the acyl group of 1～10, above-mentioned amide groups, above-mentioned nitro, above-mentioned cyano group etc. replace , the aryl that carbon number is 6～10 such as phenyl, naphthyl.

The quantity of above-mentioned substituent group is not particularly limited, preferably 1～3.In the case of substituent group is more than 2, The kind of substituent group can be the same or different.It addition, from the aspect that industrially can manufacture at low cost, preferably R⁴～R⁹For unsubstituted.

As the concrete example of above-mentioned acyl group, chloracetyl, trifluoroacetyl group, Methoxyacetyl, phenoxy group can be enumerated Acetyl group, 4-anisoyl, 4-nitro benzoyl, 4-cyanobenzoyl, 4-TRIFLUOROMETHYLBENZOYL etc..

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

The substituent group can having as above-mentioned acyloxy, can use substituent group illustrated below, it would however also be possible to employ this Substituent group beyond Xie.Halogen atom in fluorine atom, chlorine atom, bromine atoms and atomic iodine；Methyl, ethyl, isopropyl etc. Carbon number is the alkyl of 1～10；The carbon number such as methoxyl group, ethyoxyl is the alkoxyl of 1～10；Acetamido, benzoyl The carbon numbers such as amido are the acylamino-of 1～10；Nitro；Cyano group；1～3 hydrogen atom can be by above-mentioned halogen atom, above-mentioned alcoxyl The carbon numbers such as base, acetyl group, benzoyl are that the acyl group of 1～10, above-mentioned acylamino-, above-mentioned nitro, above-mentioned cyano group etc. replace , the aryl that carbon number is 6～10 such as phenyl, naphthyl.

The quantity of above-mentioned substituent group is not particularly limited, preferably 1～3.In the case of substituent group is more than 2, take The kind of Dai Ji can be the same or different.It addition, from the aspect that industrially can manufacture at low cost, R⁴～R⁹ The most unsubstituted.As the concrete example of above-mentioned acyl group, chloracetyl, trifluoroacetyl group, Methoxyacetyl, benzene can be enumerated Epoxide acetyl group, 4-anisoyl, 4-nitro benzoyl, 4-cyanobenzoyl, 4-TRIFLUOROMETHYLBENZOYL Deng.

It addition, at R⁴～R⁹In, as " the alkoxyl that carbon number is 1～10 or the virtue oxygen with or without substituent group Base ", such as can use following alkoxyl and aryloxy group.Methoxyl group, ethyoxyl, isopropoxy, tert-butoxy, trifluoro methoxy The alkoxyls such as base；The aryloxy group such as phenoxy group.

Preferred alkoxyl in above-mentioned alkoxyl and above-mentioned aryloxy group, the carbon number of alkoxyl is preferably less than 4, more excellent Elect less than 2 as.If in the range of Gai, then fluorenes ring be difficult to produce sterically hindered each other, has obtain from fluorenes ring desired The tendency of optical characteristics.

It addition, at R⁴～R⁹In, as the concrete structure of " with or without the amino of substituent group ", such as, can use Following amino, it would however also be possible to employ the amino beyond these.Amino；N-methylamino, N, N-dimethylamino, N-ethyl ammonia Base, N, N-diethylamino, N, N-methylethylamine, N-propylcarbamic, N, N-dipropylamino, N-isopropylamino, N, The aliphatic amines such as N-diisopropylaminoethyl；N-phenyl amino, N, the aromatic series amino such as N-diphenyl amino；Formamido, second The amide groups such as amide groups, caprinoyl amido, benzamido, chloracetyl amido；Benzyoxycarbonylamino, tertbutyloxycarbonylamino Deng alkoxycarbonyl amido.

As above-mentioned amino, it is preferred to use do not have the high proton of acidity degree, molecular weight is little, have and can improve fluorenes ratio Tendency, N, N-dimethylamino, N-ethylamino or N, N-diethylamino, more preferably use N, N-dimethylamino.

It addition, at R⁴～R⁹In, as " the vinyl that carbon number is 1～10 or the acetylene with or without substituent group Base ", such as can use following vinyl and acetenyl, it would however also be possible to employ the vinyl etc. beyond these.Vinyl, 2-first Base vinyl, 2,2-dimethyl ethenyl, 2-phenyl vinyl, 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 Gai, then fluorenes ring be the most difficult Sterically hindered to produce, there is the tendency obtaining the desired optical characteristics from fluorenes ring.It addition, the conjugated system of fluorenes ring becomes Long, thus it is readily obtained strong inverse wave length dispersibility.

It addition, at R⁴～R⁹Middle as " there is the sulphur atom of substituent group ", such as can use following containing sulfenyl, it is possible to With use beyond these containing sulfenyl.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 group are sub- The alkyl sulphinyl such as sulfonyl, isopropylsulphinyl；The aryl sulfenyls such as phenylsufinyl, p-methylphenyl sulfinyl Base；The alkylthio group such as methyl mercapto, ethylmercapto group；The arylthios such as thiophenyl, p-methylphenyl sulfenyl；Methoxysulfonyl, ethyoxyl sulphonyl The alkyloxysulfonyl such as base；The aryloxy sulfonyls such as phenoxysulfonyl groups；Amino-sulfonyl；N-methylaminosulfonyl, N-second The alkane such as base amino-sulfonyl, N-tert-butylamino sulfonyl, N, N-dimethylamino-sulfonyl, N, N-diethylamino sulfonyl Base sulfonyl；N-phenylaminosulfonyl group, N, the n-aryl sulfonyl such as N-diphenyl amino sulfonyl.It should be noted that Sulfo group can also form salt with lithium, sodium, potassium, magnesium, ammonium etc..

Above-mentioned containing in sulfenyl, it is preferred to use do not have the high proton of acidity degree, molecular weight is little, can improve fluorenes ratio, Methylsulfinyl, ethylsulfinyl or phenylsufinyl, more preferably use methylsulfinyl.

It addition, at R⁴～R⁹In, as " there is the silicon atom of substituent group ", such as, can use following silicyl.Three The trialkylsilkls such as methyl silicane base, triethylsilyl；Trimethoxysilyl, triethoxysilyl Etc. trialkoxysilyl.Among these, the preferably trialkylsilkl of stably operable.

It addition, at R⁴～R⁹In, as " halogen atom ", fluorine atom, chlorine atom, bromine atoms, atomic iodine can be used.These Among, it is preferred to use it is easier to import and because having electron-withdrawing, there is improve the reactive tendency of fluorenes 9, fluorine Atom, chlorine atom or bromine atoms, more preferably use chlorine atom or bromine atoms.

It addition, at R⁴～R⁹In, 2 adjacent groups can be mutually bonded formation ring.As its concrete example, can enumerate There is the substituted fluorene structure of the skeleton illustrated in following [A] group.

[A]

[changing 21]

As it has been described above, by making R⁴～R⁹For above-mentioned specific atoms or substituent group, thus between main chain and fluorenes ring, fluorenes ring Each other sterically hindered few, has the tendency of the available desired optical characteristics from fluorenes ring.

Fluorenes ring contained by above-mentioned oligomeric fluorene structural units is preferably any one in following composition: R⁴～R⁹All hydrogen The composition of atom；Or, R⁴And/or R⁹For select free halogen, acyl group, nitro, cyano group and sulfo group composition group in arbitrary Plant and R⁵～R⁸Composition for hydrogen atom.When there is the former composition, can be derived by the fluorenes that industrial cost is the lowest and comprise The compound of above-mentioned oligomeric fluorene structural units.During it addition, have the composition of the latter, the reactive 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 being suitable for various induced reaction.Above-mentioned fluorenes ring More preferably any one in following composition: R⁴～R⁹The composition of all hydrogen atoms；Or, R⁴And/or R⁹For selecting free fluorine former Any one in the group of son, chlorine atom, bromine atoms and nitro composition and R⁵～R⁸Composition for 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 produce sky each other Between steric hindrance, also there is the tendency obtaining the desired optical characteristics from fluorenes ring.

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

[B] group

[changing 22]

The oligomeric fluorene structural units of the present invention with the most commonly used from double [4-(2-hydroxyl-oxethyl) benzene of 9,9- Base] construction unit (following structural formula (9)), (following from the construction unit of double (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-of fluorenes Structural formula (10)) compare, there is following characteristics.

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

The above-mentioned aromatic component being introduced into main chain demonstrates the positive wavelength dispersibility that the shortest then birefringence of wavelength is the biggest, Thus, the inverse wave length dispersibility from the fluorenes ring of side chain was cancelled in the past, and the inverse wave length dispersibility overall as resin reduces.With This is relative, and aromatic component is not introduced into main chain, such that it is able to show inverse wave length dispersibility more strongly.

By importing two fluorenes rings in a part, such that it is able to give high-fire resistance.

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

[changing 23]

The resin of the present invention contains at least one comprised in carbonic acid ester bond and ester bond and links group and above-mentioned low polyfluorene knot The resin of structure unit.As having the thermostability of the Merlon of resin, polyester and polyestercarbonate of above-mentioned link group, machine Tool characteristic, melt processable are excellent.It addition, by with other monomer copolymerization, such that it is able to by above-mentioned oligomeric fluorene structural units ratio Import in resin relatively easily, and have and easily the ratio of the oligomeric fluorene structural units in resin is controlled as desired model The advantage enclosed.

As above-mentioned oligomeric fluorene structural units being imported the method in resin, such as, can enumerate and will there is above-mentioned low polyfluorene The glycol of construction unit or diester and other glycol or the method for diester copolymerization.Specifically, by with glycol and following logical The combination of the carbonic diester represented by formula (11) is polymerized, such that it is able to obtain Merlon.It addition, by with glycol and The combination of diester is polymerized, and can obtain polyester.It addition, by carrying out with the combination of glycol, diester and carbonic diester Polymerization, can obtain polyestercarbonate.

[changing 24]

In above-mentioned formula (11), A¹And A²It is respectively the aliphatic that carbon number is 1～18 with or without substituent group Alkyl or the aromatic hydrocarbyl with or without substituent group, A¹And A²Can be the same or different.

As having the monomer of above-mentioned oligomeric fluorene structural units, that such as can enumerate represented by following formula (12) is specific Glycol or following formula (13) represented by specific diester.

[changing 25]

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

A³And A⁴For hydrogen atom or respectively with or without the aliphatic hydrocarbon that carbon number is 1～18 of substituent group Base or the aromatic hydrocarbyl with or without substituent group, A³And A⁴Can be the same or different.

As the above-mentioned monomer of the oligomeric fluorene structural units with above-mentioned divalent, above-mentioned formula (13) is preferably used represented Specific diester.Above-mentioned specific diester is compared with the specific glycol represented by above-mentioned formula (12), and heat stability compares Well, and the fluorenes ring in polymer is orientated in preferred direction, has the tendency demonstrating higher inverse wave length dispersibility.

On the other hand, if Merlon and polyester are compared, by obtained by being polymerized of glycol and carbonic diester Merlon has the tendency that thermostability is good with the balance of mechanical property.Accordingly, as the resin of the present invention, particularly preferably will Polyestercarbonate in the structure of the above-mentioned specific diester introducing Merlon with oligomeric fluorene structural units.

The A of above-mentioned formula (13)³And A⁴For hydrogen atom or in the case of being the aliphatic alkyl such as methyl or ethyl, logical Sometimes it is difficult under the polymerizing condition of the Merlon often used polyreaction.Therefore, the A of above-mentioned formula (13)³And A⁴Preferably For aromatic hydrocarbyl.

It addition, in the case of also using the carbonic diester represented by above-mentioned formula (11) to carry out polyreaction, if above-mentioned The A of formula (11)¹、A²A with above-mentioned formula (13)³、A⁴Being identical structure, the composition departed from the most in the polymerization is identical, Easily reclaim and recycle.It addition, the aspect of the serviceability from polymerisation reactivity and recycling, A¹～A⁴Particularly preferably For phenyl.It should be noted that A¹～A⁴In the case of phenyl, the composition departed from polyreaction is phenol.

In the resin of the present invention, in order to obtain positive refracting power anisotropy described later and sufficient inverse wave length dispersibility, need To be specific scope by the proportion adjustment of the above-mentioned oligomeric fluorene structural units in above-mentioned resin.As regulating in above-mentioned resin The method of the ratio of above-mentioned oligomeric fluorene structural units, such as, can enumerate: by have the monomer of above-mentioned oligomeric fluorene structural units with Other monomer carries out the method for copolymerization；The resin and other resin with above-mentioned oligomeric fluorene structural units are carried out the side being blended Method.Owing to can critically controlling the content of oligomeric fluorene structural units and available high transparent, can obtaining whole of film To uniform characteristic, thus the method preferably monomer with above-mentioned oligomeric fluorene structural units being carried out copolymerization with other monomer.

Relative to 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 %, it is more preferably more than below more than 10 mass % 35 mass %, more preferably 15 mass % 32 matter More than amount below %, particularly preferably 20 mass % below 30 mass %.When the content of oligomeric fluorene structural units is too much, photoelasticity Coefficient or reliability can be deteriorated, or likely cannot obtain high birefringence by stretching.Further, since oligomeric fluorene structured list The ratio shared in resin of unit raises, thus the scope of MOLECULE DESIGN narrows, and is difficult to improve when requiring resin modified.Separately On the one hand, it is assumed that obtained desired inverse wave length dispersibility even by very small amount of oligomeric fluorene structural units, these feelings Under condition, according to the slightly fluctuation of low polyfluorene content, optical characteristics can change sensitively, thus is difficult to limit various characteristics Manufacture in certain limit.

The resin of the present invention preferably obtains by having the monomer of above-mentioned oligomeric fluorene structural units and other monomer copolymerization Arrive.As carrying out other monomer of copolymerization, such as, can enumerate dihydroxy compounds, diester compound.

From aspects such as optical characteristics, mechanical property, thermostabilitys, the resin of the present invention preferably comprises following formula (3) Construction unit as copolymer composition.

[changing 26]

As the dihydroxy compounds of the construction unit that can import represented by above-mentioned formula (3), can enumerate and be in sky Between isomer relation, isosorbide (ISB), isomannite, different idose.They can be used alone a kind, it is also possible to will Two or more is applied in combination.Among these, from obtaining the aspect with polymerisation reactivity, most preferably with ISB.

Construction unit represented by above-mentioned formula (3) preferably comprise in above-mentioned resin more than 5 mass % 70 mass % with Under, further preferably containing more than 10 mass % 65 mass % below, particularly preferably containing more than 20 mass % 60 mass % with Under.If the content of the construction unit represented by above-mentioned formula (3) is very few, then thermostability may be insufficient.On the other hand, if above-mentioned The content of the construction unit represented by formula (3) is too much, then thermostability excessively raises, and mechanical property, melt processable are deteriorated.Separately Outward, the construction unit represented by above-mentioned formula (3) is bibulous structure, thus in the case of content is too much, tree The water absorption rate of fat raises, and is likely to occur size distortion in the environment of high humility.

It addition, the resin of the present invention can combine with the construction unit of above-mentioned formula (3), or do not use above-mentioned formula (3) structure and comprise other construction unit further.(hereinafter, sometimes this construction unit is referred to as " other structure list Unit ".)

As other construction unit above-mentioned, particularly preferably there is following formula (4)～(8) institute not containing aromatic component The construction unit represented.

[changing 27]

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

As the dihydroxy compounds of the construction unit that can import above-mentioned formula (4), such as, can use following two Hydroxy compounds.Ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,3 butylene glycol, 1,2-butanediol, 1,5- The dihydroxy of the straight-chain aliphatic hydrocarbon such as heptandiol, 1,6-HD, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol Based compound；The dihydroxy compounds of the branched chain aliphatic hydrocarbons such as neopentyl glycol, hexylene glycol.

[changing 28]

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

As the dihydroxy compounds of the construction unit that can import above-mentioned formula (5), such as, can use following two Hydroxy compounds.1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-diamantane (obsolete) glycol, hydrogenated bisphenol A, 2,2,4,4-tetramethyl- The secondary alcohol as ester ring type hydrocarbon illustrated in 1,3-cyclobutanediol etc. and the dihydroxy compounds of the tertiary alcohol.

[changing 29]

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

As the dihydroxy compounds of the construction unit that can import above-mentioned formula (6), such as, can use following two Hydroxy compounds.1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, Tricyclodecane Dimethanol, Pentacyclopentadecane dimethanol, 2,6-decahydronaphthalenes dimethanol, 1,5-decahydronaphthalenes dimethanol, 2,3-decahydronaphthalenes dimethanol, 2, The dihydroxy that 3-norcamphane dimethanol, 2,5-norcamphane dimethanol, 1,3-diamantane (obsolete) dimethanol, alkene etc. are derived by terpene compound Based compound etc. illustrated, as the dihydroxy compounds of primary alconol of ester ring type hydrocarbon.

[changing 30]

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

As the dihydroxy compounds of the construction unit that can import above-mentioned formula (7), such as, can use following two Hydroxy compounds.The oxyalkylene group glycolss such as diethylene glycol, triethylene glycol, TEG, Polyethylene Glycol, polypropylene glycol.

[changing 31]

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

As the dihydroxy compounds of the construction unit that can import above-mentioned formula (8), such as, can use following structure The spiroglycol represented by formula (14), the dioxane glycol etc. represented by following structural formula (15).

[changing 32]

It addition, in addition to above-mentioned dihydroxy compounds, it is also possible to use illustrated below containing the two of aromatic component Hydroxy compounds.Double (4-hydroxy phenyl) propane of 2,2-, 2,2-bis(3-methyl-4-hydroxyphenyl) propane, double (the 4-hydroxyl of 2,2- Base-3,5-3,5-dimethylphenyl) propane, double (4-hydroxyl-3,5-diethyl phenyl) propane of 2,2-, double (4-hydroxyl-(the 3-benzene of 2,2- Base) phenyl) propane, double (4-hydroxyl-(3,5-diphenyl) phenyl) propane of 2,2-, 2,2-be double (4-hydroxyl-3,5-dibromo phenyl) Double (4-hydroxy phenyl) ethane of propane, double (4-hydroxy phenyl) methane, 1,1-, double (4-hydroxy phenyl) butane of 2,2-, 2,2-are double (4-hydroxy phenyl) pentane, 1,1-double (4-hydroxy phenyl)-1-diphenylphosphino ethane, double (4-hydroxy phenyl) diphenyl methane, 1,1- Double (4-hydroxy phenyl) decane of double (4-hydroxy phenyl)-2-ethyl hexane, 1,1-, double (4-hydroxyl-3-nitrobenzophenone) methane, 3, Double (4-hydroxy phenyl) pentane of 3-, double (2-(4-the hydroxy phenyl)-2-propyl group) benzene of 1,3-, double (2-(4-the hydroxy phenyl)-2-of 1,3- Propyl group) benzene, double (4-hydroxy phenyl) HFC-236fa of 2,2-, 1,1-bis(4-hydroxyphenyl)-cyclohexane, double (4-hydroxy phenyl) sulfone, 2,4 '-dihydroxydiphenylsulisomer, double (4-hydroxy phenyl) thioether, double (4-hydroxy-3-methyl phenyl) thioether, double (4-hydroxy phenyls) Disulfide, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxy-3,3 ' the aromatic bisphenols compounds such as-Dichlorodiphenyl ether； Double (4-(2-hydroxyl-oxethyl) phenyl) propane of 2,2-, double (4-(2-hydroxy propyloxy group) phenyl) propane of 2,2-, double (the 2-hydroxyl of 1,3- Base oxethyl) benzene, 4,4 '-bis-(2-hydroxyl-oxethyl) biphenyl, double (4-(2-hydroxyl-oxethyl) phenyl) sulfone etc. have and be bonded to The dihydroxy compounds of the ether on aromatic group；Double (4-(2-hydroxyl-oxethyl) phenyl) fluorenes of 9,9-, double (the 4-hydroxyl of 9,9- Phenyl) fluorenes, double (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-, double (4-(2-hydroxy propyloxy group) phenyl) fluorenes of 9,9-, the double (4-of 9,9- (2-hydroxyl-oxethyl)-3-aminomethyl phenyl) fluorenes, double (4-(2-the hydroxy propyloxy group)-3-aminomethyl phenyl) fluorenes of 9,9-, the double (4-of 9,9- (2-hydroxyl-oxethyl)-3-isopropyl phenyl) fluorenes, double (4-(2-the hydroxyl-oxethyl)-3-isobutyl phenenyl) fluorenes of 9,9-, 9,9-be double Double (4-(2-the hydroxyl-oxethyl)-3-cyclohexyl phenyl) fluorenes of (4-(2-hydroxyl-oxethyl)-3-tert-butyl-phenyl) fluorenes, 9,9-, 9, Double (4-(2-the hydroxyl-oxethyl)-3-phenyl) fluorenes of 9-, 9,9-are double (4-(2-hydroxyl-oxethyl)-3,5-3,5-dimethylphenyl) Double (4-(2-the hydroxyl-oxethyl)-3-tert-butyl group-6-aminomethyl phenyl) 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.

It addition, as can with the copolymerization of the monomer with above-mentioned oligomeric fluorene structural units in use diester chemical combination Thing, such as, can use dicarboxylic acids etc. shown below.P-phthalic acid, 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 acid, 1,3-cyclohexane dicarboxylic acid, The ester ring type dicarboxylic acids such as 1,4-cyclohexane dicarboxylic acid；Malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, nonyl two The aliphatic dicarboxylic acids such as acid, decanedioic acid.It should be noted that these dicarboxylic acid component can using the form of dicarboxylic acids itself as The raw material of above-mentioned polyestercarbonate, according to autofrettage, it is also possible to by dicarboxylic ester or dicarboxylic dihydrazides such as methyl ester body, phenylester bodies The dicarboxylic acid derivatives such as halogen are as raw material.

From the aspect of optical characteristics, as above-mentioned other construction unit enumerated, it is preferably used and becomes without aromatic series The construction unit divided.If comprising aromatic component in the main chain of polymer, the inverse wave length dispersibility of fluorenes ring described above is cancelled, Thus must increase the content of oligomeric fluorene structural units, and photoelastic coefficient is also possible to be deteriorated.By using without fragrance Other construction unit above-mentioned of race's composition, is possible to prevent to be derived from this construction unit and makes aromatic component introduce main chain.

On the other hand, in order to keep and the balance of thermostability, mechanical property etc. while guaranteeing optical characteristics, sometimes to It is also effective that the main chain of polymer or side chain introduce aromatic component.In the case of Gai, such as by containing aromatic component Other construction unit above-mentioned, can import polymer by aromatic component.

From the standpoint of the balance keeping various characteristics, the construction unit comprising aromatic group in above-mentioned resin The content of (wherein, by except the construction unit represented by above-mentioned formula (1) and the construction unit represented by above-mentioned formula (2)) is excellent Elect below 5 mass % as.

As having the monomer of above-mentioned other construction unit enumerated, particularly preferably use 1,4-CHDM, three Cyclodecane dimethanol, the spiroglycol, 1,4-cyclohexane dicarboxylic acid (and derivant).Comprise the construction unit from these monomers The optical characteristics of resin or the balancing good of thermostability, mechanical property etc..

It addition, in for the present invention in the case of most preferred polyestercarbonate, due to the polyreaction of diester compound Property ratio relatively low, thus from improving from the standpoint of reaction efficiency, the most do not use except having the class of oligomeric fluorene structural units Diester compound beyond compound.

Requirement performance according to obtained resin, for importing the dihydroxy compounds of other construction unit or class Compound may be used singly or in combination of two or more.The content of other the construction unit in resin is preferably 1 mass % Below above 60 mass %, more preferably below more than 5 mass % 55 mass %, more than particularly preferably 10 mass % 50 Below quality %.Other construction unit owing to undertaking the thermostability adjusting resin especially or giving flexibility or the effect of toughness, If thus content is very few, then mechanical property or the melt processable of resin is deteriorated, if content is too much, then and thermostability or optical characteristics Likely it is deteriorated.

It is suitable for and the Merlon of resin use of the present invention, polyester, polyestercarbonate can utilize conventionally used gathering Conjunction method manufactures.That is, above-mentioned resin such as can use following method to manufacture: uses phosgene or carboxylic acid halide Solution polymerization process or interfacial polymerization；Or do not use solvent to carry out the melt phase polycondensation reacted.In these manufacture methods, molten Melt polymerization and do not use solvent or the high compound of toxicity, thus carrying capacity of environment can be reduced, and productivity ratio is the most excellent, thus Preferably manufactured by melt phase polycondensation.

It addition, in the case of using solvent in polymerization, the plasticization effect caused by the residual solvents in resin, resin Glass transition temperature reduce, therefore, be difficult in stretching process described later by molecularly oriented control be certain.It addition, In the case of in resin, remaining has the organic solvent of the halogen systems such as dichloromethane, if using the molded body of this resin to be introduced into electronics In equipment etc., also can become the reason of corrosion.Owing to the resin obtained by melt phase polycondensation is without solvent, thus for processing The stabilisation of operation or product property is the most favourable.

When manufacturing above-mentioned resin by melt phase polycondensation, will there is the monomer of oligomeric fluorene structural units, other glycol Or the comonomer of diester and polymerization catalyst mix, under melted, carry out ester exchange reaction, will be disengaged from composition and remove Outside system, gradually step up response rate simultaneously.Polymerization terminal stage, make under conditions of high temperature, fine vacuum reaction carry out to Target molecular weight.After having reacted, discharge the resin of molten condition from reactor, obtain the tree for products formeds such as phase retardation films Fat raw material.

In the present invention, Merlon or polyestercarbonate can by by least contain oligomeric fluorene structural units monomer, More than one dihydroxy compounds and carbonic diester, for raw material, make they polycondensations obtain.

As the carbonic diester for polycondensation reaction, the material represented by above-mentioned formula (11) generally can be enumerated.These Carbonic diester can be used alone a kind, it is also possible to two or more is used in mixed way.

[changing 33]

A¹And A²It is preferably replacement or unsubstituted aromatic hydrocarbyl, the most unsubstituted aromatic hydrocarbyl.Need 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 formula (11), such as, can exemplify diphenyl carbonate (DPC), carbonic acid diformazan Phenyl esters etc. replace diphenyl carbonate, dimethyl carbonate, diethyl carbonate and dimethyl dicarbonate butyl ester etc., preferably diphenyl carbonate, Replace diphenyl carbonate, particularly preferably diphenyl carbonate.It should be noted that carbonic diester sometimes to comprise chloride ion etc. miscellaneous Matter, suppresses polyreaction sometimes or makes the tone of obtained Merlon be deteriorated, being preferably used the most as required and pass through The material that distillation etc. is refined.

For polycondensation reaction, by adjusting whole dihydroxy compounds used in reaction and diester compound closely Molar ratio, can control response speed or the molecular weight of obtained resin.In the case of polycarbonate, preferably by carbonic acid Diester is adjusted to 0.90～1.10 relative to 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 relative to whole dihydroxy The molar ratio of compound is adjusted to 0.70～1.10, is more preferably adjusted to 0.80～1.05, be particularly preferably adjusted to 0.85～ 1.00.In the case of polyestercarbonate, preferably by the total amount of carbonic diester and whole diester compound relative to 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 the most significantly deviates, then cannot manufacture the resin of desired molecular weight.If it is it addition, above-mentioned Molar ratio too small, then the C-terminal of manufactured resin increases, and the heat stability of resin is deteriorated sometimes.If it addition, Above-mentioned molar ratio is excessive, then under identical conditions, the speed of ester exchange reaction reduces, or the carbonic acid in manufactured resin The remaining quantity of diester or diester compound increases, this remaining low molecular composition volatilization when masking or when stretching, it is possible to cause The defect of film.

Melt phase polycondensation is generally implemented with multistep operations more than two steps.Polycondensation reaction can use 1 polymer reactor, Change condition successively and implement with operations more than two steps；The reactor of more than 2 can also be used, change respective condition And implement with operations more than two steps, from the aspect of production efficiency, use the reaction of more than 2, preferably more than 3 Device is implemented.Polycondensation reaction can be batch-type, continuous way or batch-type and any one mode in the combination of continuous way, From the aspect of production efficiency Yu quality stability, preferably continuous way.

In polycondensation reaction, the temperature suitably controlled in reaction system is critically important with the balance of pressure.If make temperature and Any one in pressure changes too quickly, and the most unreacted monomer distillates outside reaction system.Its result, dihydroxy compounds Change with the molar ratio of diester compound, the resin of desired molecular weight may be can not get.

It addition, the polymerization speed of polycondensation reaction is controlled by the C-terminal balance with ester group end or with carbonate group end System.Therefore, particularly in the case of being polymerized with continuous way, if made end group by distillating of unreacted monomer Balance changes, then be difficult to the variation of the molecular weight that polymerization speed control is certain, obtained resin is likely become big. The molecular weight of resin is relevant with melt viscosity, and therefore when obtained resin carries out melted masking, melt viscosity becomes Dynamic, it is difficult to the qualities such as the thickness of film to be remained necessarily, the reduction of the quality of film, productivity ratio can be caused.

If additionally, unreacted monomer distillates, being not only the balance of end group, the copolymerization composition of resin also offsets from desired Composition, it is possible to also the optical quality of phase retardation film is produced impact.In the phase retardation film of the present invention, phase contrast described later The ratio that wavelength dispersibility is polymerized to point together by the low polyfluorene in resin controls, if therefore ratio is destroyed in polymerization, then without Method obtains optical characteristics as design, or in the case of obtaining long film, optical characteristics can become because of the position of film Change, it is possible to the polaroid that quality is certain cannot be manufactured.

Specifically, as the reaction condition in the reaction of the 1st step, following condition can be used.That is, polymer reactor Interior temperature maximum temperature generally more than 130 DEG C, preferably more than 150 DEG C, more preferably and generally exist more than 170 DEG C Less than 250 DEG C, preferably below 240 DEG C, more preferably scope below 230 DEG C is set.It addition, the pressure of polymer reactor Power generally below 70kPa (following, pressure representative absolute pressure), preferably below 50kPa, more preferably at below 30kPa and And generally at more than 1kPa, be preferably set at more than 3kPa, more preferably scope at more than 5kPa.It addition, the response time Generally more than 0.1 hour, preferably more than 0.5 hour and generally below 10 hours, preferably below 5 hours, more excellent The scope being selected in less than 3 hours is set.About the reaction of the 1st step, the list that produced diester compound is originated Hydroxy compounds distillation is removed to outside reaction system while implementing reaction.Such as using diphenyl carbonate as carbonic diester In the case of, being distilled the monohydroxy compound removed outside reaction system in the reaction of the 1st step is phenol.

In the reaction of the 1st step, more reduce reaction pressure and the most more can promote polyreaction, on the other hand unreacted monomer Distillate and more increase.In order to take into account distillating and promoting reaction based on decompression of suppression unreacted monomer, use and possess returned cold The reactor of condenser is effective.In particular it is preferred that use reflux condenser in the initial reaction stage that unreacted monomer is many.

About the reaction that the 2nd step is later, the pressure of reaction system is declined lentamente from the pressure of the 1st step, then by institute The monohydroxy compound produced be rejected to reaction system outer while, finally making the pressure of reaction system is below 5kPa, preferably For below 3kPa, more preferably below 1kPa.It addition, the maximum temperature of interior temperature generally more than 210 DEG C, preferably 220 DEG C with Upper and generally below 270 DEG C, preferably scope below 260 DEG C is set.It addition, the response time is generally little 0.1 More than time, preferably more than 0.5 hour, more preferably more than 1 hour and generally below 10 hours, preferably 5 hours with Under, more preferably scope below 3 hours is set.In order to suppress coloring or heat deterioration, obtain tone, good thermal stability Resin, preferably the maximum temperature of the interior temperature in the total overall reaction stage be less than 270 DEG C, be preferably less than 260 DEG C, the most excellent Elect less than 250 DEG C as.

During polymerization, spendable catalyst for ester exchange reaction (hereinafter sometimes called catalyst, polymerization catalyst) can The tone or the heat stability that on response speed or carry out the resin that polycondensation obtains bring the biggest impact.As urging of being used Agent, does not the most limit as long as the transparency of manufactured resin, tone, thermostability, heat stability and mechanical strength can be met Fixed, can enumerate 1 race in long period type periodic chart or the metallic compound of 2 races (being the most simply designated as " 1 race ", " 2 race "), The alkali compoundss such as alkalescence boron compound, alkaline phosphating compound, alkaline ammonium compound, amine compound.Choosing is preferably used freely The metallic compound of at least one in the group of the metal of long period type periodic chart the 2nd race and lithium composition.

As 1 above-mentioned race's metallic compound, such as, can use following compound, it would however also be possible to employ beyond these 1 race's metallic compound.Such as can enumerate: sodium hydroxide, potassium hydroxide, Lithium hydrate, Cesium hydrate., sodium bicarbonate, carbonic acid Hydrogen potassium, lithium bicarbonate, caesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, Quilonorm (SKB), acetic acid Caesium, sodium 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, phosphoric acid hydrogen two lithium, phosphoric acid hydrogen two caesium, disodium phenylphosphate, phosphenylic acid two Potassium, phosphenylic acid two lithium, phosphenylic acid two caesium；Sodium, potassium, lithium, the alkoxide of caesium, phenates；2 sodium salts of bisphenol-A, 2 potassium salt, 2 lithium salts, 2 cesium salts etc..Wherein, from the aspect of polymerization activity Yu the tone of obtained Merlon, lithium compound is preferably used.

As 2 above-mentioned race's metallic compounds, such as, can use following compound, it would however also be possible to employ beyond these 2 race's metallic compounds.Such as can enumerate: calcium hydroxide, barium hydroxide, magnesium hydroxide, Strontium hydrate., calcium bicarbonate, carbonic acid Hydrogen barium, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, brium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, Barium acetate, magnesium acetate, acetic acid Strontium, calcium stearate, barium stearate, magnesium stearate, Strontium bis(stearate) etc..Wherein, magnesium compound, calcium compounds, barium are preferably used Compound, from the aspect of polymerization activity Yu the tone of obtained Merlon, further preferably use magnesium compound and/or Calcium compounds, most preferably with calcium compounds.

It should be noted that can also be complementary together with 1 above-mentioned race's metallic compound and/or 2 race's metallic compounds Share the alkalescence alkali compounds such as boron compound, alkaline phosphating compound, alkaline ammonium compound, amine compound, particularly preferably Use the metallic compound of at least one in the group that the metal of choosing free long period type periodic chart the 2nd race and lithium form.

As above-mentioned alkaline phosphating compound, such as, can use following compound, it would however also be possible to employ beyond these Alkaline phosphating compound.Such as can enumerate triethyl phosphine, three n-pro-pyl phosphines, tri isopropyl phosphine, tri-n-butyl phosphine, triphenylphosphine, Tributylphosphine or quaternary salt etc..

As above-mentioned alkaline ammonium compound, such as, can use following compound, it would however also be possible to employ beyond these Alkaline ammonium compound.Such as can enumerate Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, the tetrabutyl Ammonium hydroxide, N, N, N-trimethyl ethanolamine (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, can use following compound, it would however also be possible to employ the amine beyond these Based compound.Such as can enumerate 4-aminopyridine, PA, N, N-dimethyl-4-aminopyridine, 4-diethylamino Pyridine, 2 hydroxy pyrimidine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylamino imidazoles, 2-methoxyl group imidazoles, imidazoles, 2-mercaptoimidazole, 2-methylimidazole, quinolin-2-ylamine, guanidine etc..

Generally, relative to the every 1mol of whole dihydroxy compounds used in polymerization, the consumption of above-mentioned polymerization catalyst is 0.1 μm ol～300 μm ol, preferably 0.5 μm ol～100 μm ol.As above-mentioned polymerization catalyst, select free long period using In the case of the metallic compound of at least one in the group of the metal of type periodic chart the 2nd race and lithium composition, particularly using In the case of magnesium compound and/or calcium compounds, as amount of metal, relative to the above-mentioned every 1mol of whole dihydroxy compounds, make With more than usually 0.1 μm ol, be preferably the above-mentioned polymerization catalyst of more than more than 0.3 μm ol, particularly preferably 0.5 μm ol. It addition, the consumption of above-mentioned polymerization catalyst to be below 30 μm ol preferable, below preferably 20 μm ol, particularly preferably 10 μm ol with Under.

It addition, in the case of diester compound being used for monomer and manufactures polyester or polyestercarbonate, it is also possible to Above-mentioned alkali compounds uses titanium compound, tin compound, germanium compound, antimony chemical combination in the case of share or not share The ester exchange catalysts such as thing, zirconium compounds, lead compound, osmium compound, zinc compound, manganese compound.Relative to institute in reaction Whole dihydroxy compounds 1mol, the consumption of these ester exchange catalysts with metal gauge generally at 1 μm ol～1mmol In the range of use, in the range of preferably 5 μm ol～800 μm ol, particularly preferably 10 μm ol～500 μm ol.

When catalytic amount is very few, polymerization speed is slow, thus in order to obtain the resin of desired molecular weight, it has to phase Polymerization temperature should be improved in ground.Therefore, the probability that the tone of obtained resin is deteriorated increases, and unreacted raw material is poly- Closing in way and volatilize, dihydroxy compounds is destroyed with the molar ratio of diester compound, it is possible to do not reach desired molecule Amount.On the other hand, when the consumption of polymerization catalyst is too much, it is possible to concurrent undesirable side reaction, obtained resin is caused Tone be deteriorated or the coloring of resin during processing and forming.

If the sodium in 1 race's metal, potassium, caesium contain in resin in a large number, then tone may be brought harmful effect.And And, these metals from not only the catalyst used, it is also possible to be mixed into by 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 relative to the above-mentioned every 1mol of whole dihydroxy compounds with metal gauge Elect below below below 2 μm ol, more preferably 1 μm ol, more preferably 0.5 μm ol as.

It should be noted that as having the monomer of oligomeric fluorene structural units, using represented by above-mentioned formula (13) In the case of diester compound manufactures polyestercarbonate, A is preferably used³And A⁴For the above-mentioned diester compound of aromatic hydrocarbyl, spy A is not preferably used³And A⁴Above-mentioned diester compound for phenyl.By using these diester compounds, polymerisation reactivity is good, The amount of used catalyst can be reduced, tone or the heat stability of obtained resin can be improved, and can reduce Foreign body in resin.

The resin of the present invention, after polymerization as mentioned above, generally can cool and solidify, and utilize rotary cutter etc. Carry out pelletize.The method of pelletize does not limit, and can enumerate following method: with molten from the polymer reactor of terminal stage State is extracted out, is allowed to cool solidification the method carrying out pelletize with the form of strands；With molten from the polymer reactor of terminal stage Melt in the extruder that resin is supplied to single screw rod or twin screw by state, after melt extruding so that it is cool and solidify and carry out pelletize Method；Or extract out with molten condition from the polymer reactor of terminal stage, be allowed to cool solidification with the form of strands, temporarily And again resin is supplied to after carrying out pelletize in the extruder of single screw rod or twin screw, it is allowed to cool solidification after melt extruding also The method carrying out pelletize；Etc..

The molecular weight of so obtained resin may utilize reduced viscosity and represents.When the reduced viscosity of resin is too low, molding The mechanical strength of product likely reduces.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 shaped reduces, and has productivity ratio or mouldability reduces inclines To.Therefore, reduced viscosity is usually below 1.20dL/g, is preferably below 1.00dL/g, more preferably below 0.80dL/g.Need It is noted that reduced viscosity measures as follows: use dichloromethane as solvent, by Merlon concentration fine setting be 0.6g/dL, uses Ubbelohde viscometer to be measured at temperature 20.0 DEG C ± 0.1 DEG C.

Above-mentioned reduced viscosity is relevant with the melt viscosity of resin, thus, generally the stirring of polymer reactor can be moved The output pressures of the gear pump of power or transporting molten resin etc. are as the index of running management.That is, at above-mentioned running device Indicated value arrives the stage of desired value, makes the pressure of reactor return to normal pressure, or discharges resin from reactor, thus stops Polyreaction.

About the melt viscosity of the resin of the present invention, in temperature 240 DEG C, shear rate 91.2sec^-1Condition determination under excellent Elect above below the 5000Pa s of 700Pa s as.More preferably above below the 4500Pa s of 800Pa s, more preferably Above below the 4000Pa s of 900Pa s, particularly preferably above below the 3500Pa s of 1000Pa s.It should be noted that Melt viscosity uses capillary rheometer (manufacture of Toyo Seiki Co., Ltd.) to be measured.

The glass transition temperature of the resin of the present invention be preferably more than 110 DEG C less than 160 DEG C, more preferably 120 DEG C with Upper less than 155 DEG C.When glass transition temperature is too low, then there is the tendency that thermostability is deteriorated, size after film molding, can be caused to become Changing, the reliability of phase retardation film quality under conditions of use likely can be deteriorated.On the other hand, glass transition temperature is too high Time, produce the inequality of film thickness during film molding sometimes, or film becomes fragile, or draftability is deteriorated, and damage 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, more preferably more than 1.2GPa below 2.3GPa, particularly preferably more than 1.3GPa below 2.2GPa.Storage modulus is During above-mentioned scope, the treatability of film and excellent strength.The assay method of storage modulus illustrates in the item of following embodiment.

In order to obtain the polycarbonate resin adipose membrane with the storage modulus of the particular range that present invention provide that, under can passing through The mode of stating realizes: uses and has the polycarbonate resin of the ad hoc structure of regulation in the present invention, and, melt for suitably adjusting it Melt-viscosity, suitably select its construction unit, regulate the ratio of its construction unit, polycarbonate resin adds plasticizer etc. enter Row is appropriately combined, or selects film forming condition or the stretching condition of appropriateness.

In the case of using diester compound in polycondensation reaction, by-product monohydroxy compound can remain in resin, Volatilization when the masking of film or during stretching, forms abnormal flavour, makes working environment be deteriorated, or likely pollution transfer roller etc., make film Appearance damage.In the case of using useful especially carbonic diester i.e. diphenyl carbonate (DPC), the boiling point of by-product phenol The highest, utilize the reaction under decompression also cannot fully remove, easily remain in resin.

Therefore, the monohydroxy compound in contained in the resin of present invention carbonic diester source is preferably 1500 mass Below ppm.More preferably below 1000 mass ppm, it is particularly preferably below 700 mass ppm.It should be noted that it is right For monohydroxy compound, in order to solve the problems referred to above, content is the fewest more good, is difficult to make remaining in the case of melt phase polycondensation Monohydroxy compound in macromolecule is zero, needs too much labour to be removed.Generally, by making monohydroxy chemical combination The content of thing is reduced to 1 mass ppm, can fully suppress the problems referred to above.

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

In the case of the pressure reducing polymerization terminal stage, if excessively reducing the pressure of reaction, then molecular weight is drastically gone up Rising, be sometimes difficult to control to reaction, the end group concentration the most preferably making resin is C-terminal excess or ester group end excess, Destroy end group balance to manufacture.Wherein from the aspect of heat stability, preferably making C-terminal amount is 50mol/ Ton is following, be particularly preferably below 40mol/ ton.C-terminal amount can utilize¹H-NMR etc. are carried out quantitatively.C-terminal amount can Regulate with the molar ratio by whole dihydroxy compounds with whole diester compounds.

As required, molecular weight during in order to prevent molding etc. reduces or tone is deteriorated, can be in the resin of the present invention Mixture heat stabilizer.As this heat stabilizer, commonly known hindered phenol system heat stabilizer can be enumerated and/or phosphorus system is thermally-stabilised Agent.

As hindered phenol based compound, such as, can use following compound.Can enumerate 2,6 di t butyl phenol, 2,4-DI-tert-butylphenol compounds, the 2-tert-butyl group-4-methoxyphenol, the 2-tert-butyl group-4,6-xylenol, 2,6-di-t-butyl- 4-methylphenol, 2,6-di-t-butyl-4-ethyl-phenol, 2,5 di tert butyl hydroquinone, n-octadecane base-3-(3 ', 5 '- Di-t-butyl-4 '-hydroxy phenyl) propionic ester, the 2-tert-butyl group-6-(3 '-tert-butyl group-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-butyl-4 '-hydroxyl Phenyl) propionic ester] methane, 1,3,5-trimethyl-2,4,6-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene etc..Wherein, preferably Be four [methylene-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane, n-octadecane base-3-(3 ', 5 '-two The tert-butyl group-4 '-hydroxy phenyl) propionic ester, 1,3,5-trimethyl-2,4,6-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene.

As phosphorus series compound, such as can use phosphorous acid shown below, phosphoric acid, phosphonous acid, phosphonic acids and they Ester etc., it would however also be possible to employ the phosphorus series compound beyond these compounds.Such as can enumerate triphenyl phosphite, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, tridecyl phosphite, tricresyl phosphite monooctyl ester, tricresyl phosphite (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 oxide (4,6-di-tert-butyl-phenyl) octyl group phosphite ester, double (nonyl Phenyl) pentaerythritol diphosphites, double (2,4-di-tert-butyl-phenyl) 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, 4,4 '-biphenylene diphosphinic acid four (2,4-di-tert-butyl Base) ester, phenyl-phosphonic acid dimethyl ester, phenyl-phosphonic acid diethylester, phenyl-phosphonic acid dipropyl etc..These heat stabilizers can be used alone a kind, also Two or more can be share.

This heat stabilizer can add in reactant liquor when melt polymerization, it is possible to use extruder adds in resin And carry out mixing.When film being filmed by extrusion by melting, above-mentioned heat stabilizer etc. can be added in an extruder and enter Row masking, it is also possible to use extruder to add above-mentioned heat stabilizer etc. in resin in advance, make the shapes such as granule and use.

About the combined amount of these heat stabilizers, in the case of resin used in the present invention is set to 100 mass parts, It is preferably more than more than more than 0.0001 mass parts, more preferably 0.0005 mass parts, more preferably 0.001 mass parts, Additionally it is preferably below below below 1 mass parts, more preferably 0.5 mass parts, more preferably 0.2 mass parts.

In the resin of the present invention, as required, for antioxidative purpose, it is also possible to the antioxidation that mixture is commonly known Agent.As this antioxidant, such as, can use compound shown below, it would however also be possible to employ the compound beyond these.Example As tetramethylolmethane four (3-thiopropionate), tetramethylolmethane four (3-lauryl thiopropionate), glycerol-3-tristearin can be enumerated Base thiopropionate, triethylene glycol-bis-[3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic esters], 1,6-HD-bis- [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], tetramethylolmethane-four [3-(3,5-di-tert-butyl-hydroxy phenyl) third Acid esters], octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, 1,3,5-trimethyl-2,4,6-three (3,5-bis- Tertiary butyl-4-hydroxy benzyl) benzene, N, N-hexa-methylene double (3,5-di-t-butyl-4-hydroxy-hydrocineamide), 3,5-bis- Tertiary butyl-4-hydroxy-benzylphosphonic acid ester-diethyl ester, three (3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 4,4 '- Double { 1,1-dimethyl-2-[β-(the 3-tert-butyl group-4-the hydroxyl of biphenylene diphosphinic acid four (2,4-di-tert-butyl-phenyl) ester, 3,9- Base-5-aminomethyl phenyl) propiono epoxide] ethyl }-2,4,8,10-four oxa-volution (5,5) hendecane etc..Above-mentioned antioxidation Agent can be used alone a kind, it is also possible to share two or more.Set the resin of the present invention as 100 mass parts in the case of, these The combined amount of antioxidant is preferably more than more than 0.0001 mass parts, and preferably 0.5 mass parts.

Further, in the resin of the present invention, it is also possible to generally make containing in the range of the object of the invention UV absorbent, antitack agent, antistatic additive, lubrication prescription, lubricant, plasticizer, bulking agent, nucleator, fire retardant, inorganic Filler, modified impact agent, foaming agent, dyes/pigments etc..

It addition, for the purpose that the characteristics such as the mechanical property of resin or solvent resistance are modified, the resin of the present invention Can also be with aromatic copolycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic (third Olefin(e) acid), amorphous polyolefin, ABS, AS, polylactic acid, in synthetic resin or the rubber etc. such as poly butylene succinate a kind or 2 Plant carried out above mixing and make polymer alloy.

Mentioned component simultaneously or can be utilized rotary drum mixer, V by above-mentioned additive or modifying agent in any order The mixers such as type mixer, nauta mixer (NAUTA MIXER), Banbury, mill, extruder are blended in this In bright resin, manufacture, wherein, from the aspect of raising dispersibility, double preferably by extruder, particularly preferably utilization Screw extruder carries out mixing.

The birefringence of the resin obtained as mentioned above is little, and thermostability and mouldability are the most excellent, and then coloring is few, has concurrently high saturating Bright property, thus may be used for blooming, CD, optical prism, take object lens etc., it is especially suitable for use as phase retardation film.

As the method using the resin of the present invention that unstretching film is filmed, can use: make above-mentioned resin dissolve In a solvent and remove after pouring into a mould solvent the tape casting, do not use solvent and make above-mentioned resin melting and be filmed molten Melt masking method.As melted masking method, specifically have use the extrusion by melting of T mould, 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, owing to the tape casting can Can produce the problem caused by residual solvents, thus preferred molten masking method, wherein from the easiness carrying out stretch processing afterwards From the standpoint of, the extrusion by melting of T mould is preferably used.

In the case of utilizing melted masking method to carry out the molding of unstretching film, forming temperature be 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 too high, in obtained film by foreign body or bubble Defect caused by generation may increase or film may coloring.But, when forming temperature is too low, the melt viscosity of resin Too high, it is difficult to carry out the molding of base film, it may be difficult to manufacture unstretching film in uniform thickness, thus the lower limit of forming temperature is usual It is more than 200 DEG C, is preferably more than 210 DEG C, more preferably more than 220 DEG C.Herein, the forming temperature of unstretching film refers to melt Temperature during molding in masking method, usually the mould outlet temperature to resin melt extrusion is measured the value obtained.

If it addition, film exists foreign body, in the case of using as polaroid, as shortcoming quilts such as printing opacities (light け) Recognize.In order to remove the foreign body in resin, the most following method: install polymer filter after above-mentioned extruder, right After resin filters, carry out film molding from mould extrusion.At this time, it may be necessary to pipe arrangement connecting extruder or polymer filtration Device, mould, thus transporting molten resin, but in order to do one's utmost suppression heat deterioration in pipe arrangement, according to the side that the time of staying is the shortest It is critically important that formula configures each equipment.It addition, the transmission of film after Ji Chu and coiling process are carried out in toilet, it is desirable to as far as possible Note non-cohesive on film having foreign body.

The thickness of unstretching film comes according to stretching conditions such as the design of thickness of the phase retardation film after stretching or stretching ratios Determine, if but blocked up, the most easily produce uneven thickness (deviation), if the thinnest, then may cause fracture during stretching, thus thickness Usually more than 30 μm, be preferably more than more than 40 μm, more preferably 50 μm, and usually below 200 μm, be preferably Below 160 μm, more preferably below 120 μm.It addition, when unstretching film has uneven thickness (deviation), may cause The phase contrast of phase retardation film is uneven, thus the thickness of the part used as phase retardation film preferably set below thickness ± 3 μm, More preferably set below thickness ± 2 μm, particularly preferably set below thickness ± 1 μm.

The length of the length direction of unstretching film is preferably more than 500m, more preferably more than 1000m, particularly preferably For more than 1500m.From productivity ratio and the aspect of quality, when manufacturing the phase retardation film of the present invention, preferably continuously carry out Stretching, but generally when stretching starts for the phase contrast calibration with regulation, need regularization condition, when the length of film is too short, adjust After shelf-regulating Conditions, the amount of obtainable goods reduces.Refer to it should be noted that this specification " is grown ", with the width phase of film Ratio, the size of length direction is sufficiently large, and substantially referring to can be for the shape of the degree of band web-like when length direction winds.More Specifically, the shape of bigger than the size of width more than 10 times of the size of the length direction of film is referred to.

The internal haze of the unstretching film obtained as mentioned above is preferably less than 3%, more preferably less than 2%, the most excellent Elect less than 1% as.If the internal haze of unstretching film more than above-mentioned higher limit, then can occur scattering of light, such as with polarization During element lamination, become the reason producing depolarization sometimes.The lower limit of internal haze do not had special provision, usually More than 0.1%.In the mensuration of internal haze, the hyaline membrane having carried out the band sticker that mist degree measures in advance is pasted and does not draws Stretch the two sides of film, use the sample of the state of the impact eliminating outside mist degree, the haze value of the hyaline membrane of band sticker is subtracted The value going the measured value of above-mentioned sample and obtain is as the value of internal haze.

The b* value of unstretching film is preferably less than 3.When the b* value of film is excessive, the problems such as coloring can be produced.B* value is more preferably It is less than 2, particularly preferably less than 1.

About unstretching film, no matter thickness, the total light transmittance of this film itself is preferably more than 80%, further It is preferably more than 90%, more preferably more than 91%, particularly preferably more than 92%.Transmitance is more than above-mentioned lower limit Time, can obtain colouring few film, when fitting with polaroid, form degree of polarization and the high circular polarizing disk of transmitance, scheme being used for During as display device, it is possible to realize high display grade.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* value, and then reduce the refractive index of resin, it is also possible to the reflection on suppression film surface, Improve total light transmittance.In the case of the resin of the present invention is used for preventing the circular polarizing disk of external light reflection, improve Total light transmittance is relevant with the reflectance reducing exterior light.The refraction at sodium d line (589nm) of resin used in the present invention Rate is preferably 1.49～1.56.It addition, above-mentioned refractive index is more preferably 1.50～1.55, more 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 whole aliphatic poly Compound phase specific refractivity raises, but does not uses aromatic compound in copolymer composition, such that it is able to refractive index be restricted to above-mentioned Scope.

The photoelastic coefficient of the resin of the present invention is preferably 25 × 10^-12Pa^-1Below, more preferably 20 × 10^-12Pa^-1Below, particularly preferably 15 × 10^-12Pa^-1Below.When photoelastic coefficient is excessive, when phase retardation film is pasted polaroid, It may happen that turn white around picture, the reduction of fuzzy such image quality.Particularly in the feelings for large-scale display device Under condition, this problem significantly occurs.

In crooked test described later, preferably there is not brittle break in above-mentioned unstretching film.Occur the film of brittle break at film Masking time or be susceptible to the fracture of film during stretching, the yield rate of manufacture may be made to be deteriorated.Fragility is not occurred to break in order to make Bad film, is designed to above-mentioned preferred by the molecular weight of resin used in the present invention or melt viscosity, glass transition temperature Scope is critically important.Additionally, by copolymerization, be blended and can give the method for the physical property that the composition of flexibility adjusts film and also have 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 when being fitted with other film etc. by this film, there is the tendency that can readily insure that cementability.Such as, fitting with polaroid Time, owing to film is hydrophilic, thus the contact angle of water is the lowest, the most freely designs cement, available higher bonding Design.In the case of saturated water absorption is below 1.0 mass %, film is hydrophobic, and the contact angle of water is the highest, it is difficult to carry out The design of cementability.And film is the most charged, has and can produce being involved in etc. of foreign body and be assembled into circular polarizing disk, image display dress When putting middle, open defect becomes the tendency of many problems.On the other hand, if saturated water absorption is more than 3.0 mass %, then humidity environment Under the durability of optical characteristics have the tendency of variation, thus the most preferred.The saturated water absorption of the resin of the present invention is preferably greater than More than 1.0 mass %, more preferably 1.1 mass %, and below preferably 3.0 mass %, more preferably 2.5 mass % with Under.On the other hand, according to film or the difference of the use condition of the image display device using film, saturated water absorption can also be Below 1.0 mass %.

By above-mentioned unstretching film is carried out stretch orientation, phase retardation film can be obtained.As drawing process, it is possible to use Longitudinal simple tension, utilize the horizontal simple tension of stenter etc. or they be combined while biaxial tension, gradually The known method such as biaxial tension.Stretching can be carried out with batch-type, but is preferably carried out continuously from productivity ratio aspect.Enter And, compared with batch-type, during continuous way, can get the phase retardation film that the deviation of phase contrast in face is few.

Relative to 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 in the range of (Tg-10 DEG C)～(Tg+20 DEG C), more preferably (Tg-5 DEG C)～(Tg+15 DEG C). Stretching ratio is determined by target phase difference, longitudinal and transverse is respectively 1.2 times～4 times, more preferably 1.5 times～3.5 times, enters one Step is preferably 2 times～3 times.When stretching ratio is too small, the effective range obtaining the desired degree of orientation and the angle of orientation narrows.Another Aspect, when stretching ratio is excessive, in stretching, film may rupture, or produces fold.

Draw speed takes the circumstances into consideration to select also according to purpose, in terms of the strain rate represented by following mathematical expression, and can be according to logical Be often 50%～2000%, be preferably 100%～1500%, more preferably 200%～1000%, particularly preferably 250%～ The mode of 500% selects.When draw speed is excessive, fracture during stretching may be caused, or the most long-term The variation using caused optical characteristics may increase.If it addition, draw speed is too small, not only productivity ratio can reduce, and In order to obtain desired phase contrast, stretching ratio sometimes must be made excessive.

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

After stretched film, heating furnace can be utilized as required to carry out heat fixation process, it is also possible to control the width of stenter Degree or adjustment roller peripheral speed carry out relaxing operation.The temperature processed as heat fixation, used relative in unstretching film The glass transition temperature (Tg) of resin, is carried out at 60 DEG C～(Tg), preferably scope at 70 DEG C～(Tg-5 DEG C).Heat treatment temperature When spending high, the molecularly oriented obtained by stretching is disorderly, it is possible to be greatly reduced from desired phase contrast.It addition, setting In the case of putting mitigation operation, the width of the film extended with respect to stretching, it is retracted to 95%～100%, such that it is able to Remove the stress produced in stretched film.The treatment temperature now applied film is identical with heat fixation treatment temperature.By carry out as Upper described heat fixation processes or relaxes operation, it is possible to suppress the change of optical characteristics caused by life-time service under the high temperature conditions Dynamic.

The phase retardation film using the resin of the present invention can be by carrying out as one sees fit the treatment conditions in such stretching process Select and adjust to make.

Use birefringence in the face of wavelength 550nm of the phase retardation film of resin of the present invention (Δ n) be preferably 0.002 with Above, more preferably more than 0.0025, particularly preferably more than 0.003.(Δ n) becomes for the thickness (d) of phase contrast and film and birefringence Ratio, therefore, by making birefringence in above-mentioned specific scope, it is possible to utilizes thin film to show phase contrast as design, Can easily make the film being suitable for thin devices.In order to show high birefringence, it is necessary to reduce draft temperature, improve stretching Multiplying powers etc. improve the degree of orientation of polymer molecule, but film is easily broken off under this stretching condition, the resin therefore used Toughness the most excellent the most favourable.

Additionally depend on the design load of phase contrast, but use the thickness of the phase retardation film of the resin of the present invention be preferably 60 μm with Under.It addition, the thickness of phase retardation film be more preferably below below 50 μm, more preferably 45 μm, particularly preferably 40 μm with Under.On the other hand, when thickness is crossed thin, the difficult treatment of film, fold can be produced in the mill or rupture, accordingly, as this The lower limit of the thickness of the phase retardation film of invention, more than preferably 10 μm, more than more preferably 15 μm.

To use the present invention resin phase retardation film for, wavelength 450nm measure phase contrast (R450) relative to Value in the ratio i.e. wavelength dispersion (R450/R550) of the phase contrast (R550) of wavelength 550nm mensuration is less than more than 0.75 0.93. More preferably less than more than 0.78 0.91, particularly preferably less than more than 0.80 0.89.If the value of above-mentioned wavelength dispersion is at this model Enclose, it is possible to the wide wave-length coverage in visibility region obtains preferable phase difference characteristics.Such as 1/4 wavelength plate, making has The phase retardation film of such wavelength dependency is also fitted with polaroid, such that it is able to make circular polarizing disk etc., it is possible to achieve tone The few polaroid of wavelength dependency and display device.On the other hand, when aforementioned proportion is outside this scope, the wavelength dependence of tone Property becomes greatly, cannot be carried out optical compensation under all wavelengths of visibility region, can produce light through polaroid or display device institute The problems such as the coloring caused or contrast reduction.

Above-mentioned phase retardation film is by carrying out lamination laminating with known light polarizing film, and cuts into desired size, thus Form circular polarizing disk.This circular polarizing disk such as may be used for various display screen (liquid crystal indicator, organic EL display, etc. Gas ions display device, FED field emission display device, SED surface field display device) angle of visibility compensate with, prevent outside Luminous reflectance is used, tone compensation is used, circularly polarized light is used to the conversion of linearly polarized photon.Particularly, if for organic el display panel The circular polarizing disk preventing external light reflection, then can carry out clean black display, the reliability of quality is the most excellent.And then Having can also be corresponding to the performance of equipment slimming from now on.

As above-mentioned light polarizing film, the either direction in width or length direction can be used to have and to absorb the inclined of axle Light film.Specifically, can enumerate and make polyvinyl alcohol mesentery, part formalizing polyvinyl alcohol mesentery, ethane-acetic acid ethyenyl ester The hydrophilic macromolecule film absorption dichroic substance such as iodine or dichroic dye such as the partly-hydrolysed film of copolymer system have also carried out unidirectional The film of stretching；The polyenoid system alignment films etc. such as the processed thing of polyvinyl alcohol or the desalination acid treatment thing of polrvinyl chloride.These it In, make the dichroic substance such as polyvinyl alcohol mesentery absorption iodine and carried out the long light polarizing film of simple tension due to polarized light dichromatic Ratio is high and particularly preferred.The thickness of these long light polarizing film is not particularly limited, usually about 1 μm～80 μm.

Make polyvinyl alcohol mesentery absorption iodine and carried out the light polarizing film of simple tension and such as can make as follows: by polyethylene Alcohol is impregnated in the aqueous solution of iodine and dyes, and is stretched to 3～7 times of former length, thus can make this light polarizing film.Above-mentioned water-soluble Liquid can comprise boric acid, zinc sulfate, zinc chloride etc. as required.Alternatively, it is also possible to polyvinyl alcohol is impregnated into potassium iodide etc. In aqueous solution.

It addition, polyvinyl alcohol mesentery can be impregnated in water before dyeing as required, wash.By to poly-second Enol mesentery is washed, and can clean dirt or the anti-blocking agent on polyvinyl alcohol mesentery surface.Additionally, due to polyethenol series Film occurs swelling, the most also has and prevents the unequal uneven effect that dyes.Stretching can carried out with after iodine staining, it is possible to With an Edge Coloring while stretching, additionally can also dye with iodine after the stretch.Can also be at the water of boric acid or potassium iodide etc. Stretch in solution or in water-bath.

In above-mentioned circular polarizing disk, the slow axis of above-mentioned phase retardation film is preferred with the width angulation of above-mentioned light polarizing film It it is more than 38 ° less than 52 °, more preferably more than 40 ° less than 50 °, particularly preferably more than 42 ° less than 48 °.Outside above-mentioned scope Time, external light reflection rate described later increases, or reflection optical colour, thus the display quality of image is likely to decrease.

Above-mentioned phase retardation film and above-mentioned light polarizing film can carry out lamination by bonding/binding agent.As bonding/binding agent, As long as the optical characteristics not damaging above-mentioned laminated film just can use known bonding/binding agent.

As it has been described above, above-mentioned circular polarizing disk is constituted in the following manner: possess sufficient optical characteristics, and can be suitable for For requiring elaboration, equipment slim, homogeneous.Therefore, above-mentioned circular polarizing disk can be suitable for such as at liquid crystal display Liquid crystal panel used in screen, organic EL panel etc. used in organic el display panel.Particularly organic EL panel possesses appearance Easily reflect the metal level of exterior light, the most easily produce external light reflection or background such as mirrors at the problem.In order to prevent such outside Portion's luminous reflectance etc., above-mentioned circular polarizing disk is arranged at light-emitting area is effective.

" invention 2 "

Below, the low polyfluorene diester compositions that to the three fluorenes diester of the present invention 2, comprises this three fluorenes diester and containing tool The resin combination having the polymer of the repetitive in three novel fluorenes diester sources, the stretching using this resin combination to obtain Film, circular polarizing disk and image display device are described in detail.

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

<1 three fluorenes diester>

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

In three fluorenes diester, in fluorenes unit a, the carbon atom of 9 is 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.

So, the three fluorenes diester of the present invention make structure upright and outspoken, it is thus regarded that have ratio two by the laminated structure of fluorenes ring The thermostability that fluorene compound is good.

<1.1 alkylidenes, arlydene, sub-aralkyl>

In the three fluorenes diester of the present invention, the alkylidene that fluorenes unit a is bonded is not particularly limited, from improving fluorenes ratio described later The aspect of example is set out, its carbon number is usually more than 1 and usually less than 10, is preferably less than 5, more preferably 3 with Under.

Enumerate the concrete structure of above-mentioned alkylidene below, but be not limited to this, methylene, ethylidene, positive Asia third can be enumerated The alkylidene of the straight-chain such as base, positive butylidene, positive pentylidene, positive hexylidene；Methylmethylene, dimethylated methylene base, ethyl are sub- Methyl, propylmethylene, butyl methylene, (1-Methylethyl) methylene, 1-methyl ethylidene, 2-methyl ethylidene, 1-second Base ethylidene, 2-ethylethylene residue, 1-methyl propylene, 2-methyl propylene, 1,1-dimethylethylene, 2,2-dimethyl are sub- Propyl group, 3-methyl propylene etc. comprise the alkylidene (numerical value of the position of substitution is counting from the carbon of fluorenes ring side) of side chain；Following There is at any 2 of alicyclic structure shown in [A] group the ester ring type alkylene of the associative key of the alkylidene of straight-chain or branched 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 at any 2 of heterocycle structure shown in following [B] group straight-chain or branched 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 alicyclic structure shown in above-mentioned [A] group or the heterocycle structure shown in above-mentioned [B] group, have at any 2 Straight-chain or the concrete structure of associative key of alkylidene of branched can enumerate following structure, but be not limited to these: sub- The alkylidene of the straight-chain such as methyl, ethylidene, positive propylidene, positive butylidene, positive pentylidene, positive hexylidene；1-methyl ethylidene, 2-methyl ethylidene, 1-ethylethylene residue, 2-ethylethylene residue, 1-methyl propylene, 2-methyl propylene, 1,1-dimethyl are sub- Ethyl, 2,2-dimethylpropylidene, 3-methyl propylene etc. comprise the alkylidene of side chain, and (numerical value of the position of substitution is from upper herein The carbon stating ring structure bonding plays counting).

The substituent group can having as this alkylidene, can enumerate halogen atom (such as fluorine atom, chlorine atom, bromine atoms, Atomic iodine)；Carbon number is the alkoxyl (such as methoxyl group, ethyoxyl etc.) of 1～10；Carbon number is the acyl group (example of 1～10 Such as acetyl group, benzoyl etc.)；Carbon number is the amide groups (such as acetamido, benzamido etc.) of 1～10；Nitro； Cyano group；With or without being 1～10 selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine), carbon number Alkyl (such as methyl, ethyl, isopropyl etc.), carbon number be 1～10 alkoxyl (such as methoxyl group, ethyoxyl etc.), Amide groups (the such as acetyl that acyl group (such as acetyl group, benzoyl etc.) that carbon number is 1～10, carbon number are 1～10 Amido, benzamido etc.), nitro, aryl (the such as benzene that carbon number is 6～10 of 1～3 substituent group in cyano group etc. Base, naphthyl etc.) etc..The quantity of this substituent group is not particularly limited, preferably 1～3.In the case of substituent group is more than 2, take The kind of Dai Ji can be the same or different.It addition, from the industrial aspect that can manufacture at low cost, preferably without Replace.

As the concrete example of the alkylidene with or without substituent group, cyclobutyl methylene, cyclopenta Asia can be enumerated The alkyl substituted alkylenes such as methyl, cyclohexylmethylene, 1-cyclohexylpropylene；Phenylmethylene, 1-phenyl-ethylene, 1-benzene The aryl substituted alkylenes such as base propylidene；The halogen such as 1,1,2,2-tetrafluoro ethylidene, trichloromethyl methylene, trifluoromethyl methylene Atom substituted alkylene；(numerical value of the position of substitution is certainly for the alkoxyl substituted alkylenes such as 2-methoxy-2-methyl propylene etc. The carbon of fluorenes ring side plays counting).

It addition, in the three fluorenes diester of the present invention, the arlydene of bonding fluorenes unit a is not particularly limited, described later from improving The aspect of fluorenes ratio is set out, and its carbon number is usually more than 4, and usually less than 10, be preferably less than 8, more preferably 6 Below.

Hereinafter enumerate the concrete structure of above-mentioned arlydene, but be not limited to this, can enumerate 1,2-phenylene, 1,3-Asia benzene The phenylenes such as base, 1,4-phenylene；The naphthylenes such as 1,5-naphthylene, 2,6-naphthylene；2,5-pyridylidene, 2,4-Asia thiophene The heteroarylidenes such as base, 2,4-furylidene.

The substituent group can having as this arlydene, can enumerate halogen atom (such as fluorine atom, chlorine atom, bromine atoms, Atomic iodine)；Carbon number is the alkyl (such as methyl, ethyl, isopropyl etc.) of 1～10；Carbon number is the alkoxyl of 1～10 (such as methoxyl group, ethyoxyl etc.)；Carbon number is the acyl group (such as acetyl group, benzoyl etc.) of 1～10；Carbon number is The amide groups (such as acetamido, benzamido etc.) of 1～10；Nitro；Cyano group etc..The quantity of this substituent group limits the most especially Fixed, preferably 1～3.In the case of substituent group is more than 2, the kind of substituent group can be the same or different.It addition, from The industrial aspect that can manufacture at low cost is set out, the most unsubstituted.

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

Additionally, in the three fluorenes diester of the present invention, the sub-aralkyl of bonding fluorenes unit a is not particularly limited, aftermentioned from improving The aspect of fluorenes ratio set out, its carbon number is usually more than 6, and usually less than 10, be preferably less than 9, more preferably It is less than 8.

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

[changing 36]

[C]

The substituent group can having as this Asia aralkyl, (such as fluorine atom, chlorine atom, bromine are former can to enumerate halogen atom Son, atomic iodine)；Carbon number is the alkyl (such as methyl, ethyl, isopropyl etc.) of 1～10；Carbon number is the alkane of 1～10 Epoxide (such as methoxyl group, ethyoxyl etc.)；Carbon number is the acyl group (such as acetyl group, benzoyl etc.) of 1～10；Carbon atom Number is the amide groups (such as acetamido, benzamido etc.) of 1～10；Nitro；Cyano group；Have or do not have selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine), carbon number are alkyl (such as methyl, ethyl, the isopropyl of 1～10 Deng), carbon number be 1～10 alkoxyl (such as methoxyl group, ethyoxyl etc.), carbon number be 1～10 acyl group (such as second Acyl group, benzoyl etc.), carbon number be 1～10 amide groups (such as acetamido, benzamido etc.), nitro, cyano group The aryl that carbon number is 6～10 (such as phenyl, naphthyl etc.) etc. of 1～3 substituted base in Deng.The quantity of this substituent group It is not particularly limited, preferably 1～3.In the case of substituent group is more than 2, the kind of substituent group can identical can not also With.It addition, from the industrial aspect that can manufacture at low cost, the most unsubstituted.

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

Among these, from improving fluorenes ratio, for upright and outspoken aspect, preferably alkylidene, more preferably methylene, Asia Ethyl, phenylene or Isosorbide-5-Nitrae-xylylene, more preferably methylene.Particularly in the case of for methylene, select Property the ground low polyfluorene with a reactive functional groups synthesis easy, thus particularly preferably.

In the three fluorenes diester of the present invention, the substituent group can having as above-mentioned fluorenes unit a, halogen atom can be enumerated (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine)；Carbon number is alkyl (such as methyl, ethyl, the isopropyl of 1～10 Deng)；Carbon number is the alkoxyl (such as methoxyl group, ethyoxyl etc.) of 1～10；Carbon number is acyl group (the such as second of 1～10 Acyl group, benzoyl etc.)；Carbon number is the amide groups (such as acetamido, benzamido etc.) of 1～10；Nitro；Cyanogen Base；With or without being 1～10 selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine), carbon number Alkyl (such as methyl, ethyl, isopropyl etc.), carbon number are alkoxyl (such as methoxyl group, ethyoxyl etc.), the carbon of 1～10 Amide groups (the such as acetamide that acyl group (such as acetyl group, benzoyl etc.) that atomic number is 1～10, carbon number are 1～10 Base, benzamido etc.), nitro, 1～3 substituent group in cyano group etc. the aryl that carbon number is 6～10 (such as phenyl, Naphthyl etc.) etc..The quantity of this substituent group is not particularly limited, preferably 1～3.In the case of substituent group is more than 2, replace The kind of base can be the same or different.It addition, from the industrial aspect that can manufacture at low cost, be preferably without taking Generation.

<1.3 ester group>

The three fluorenes diester of the present invention can be: in 3 fluorenes unit a, and the carbon of be positioned at two ends 9 of fluorenes unit a is former Substituents alpha it is bonded with respectively on son¹And α², in this substituents alpha¹And α²On be bonded with ester group.In this case, α¹And α²Can phase Together can also be different.It addition, substituents alpha¹And α²In comprise Direct Bonding, i.e. can be direct on the carbon atom of 9 of fluorenes unit a It is bonded with ester group.

The ester group being had as the three fluorenes diester of the present invention, is not particularly limited, and can obtain at low cost from industrial Aspect set out, preferably end group be carbon number be the ester group of the organic substituent of 1～10.

Hereinafter enumerate the concrete example of the organic substituent that carbon number is 1～10, but be not limited to these, first can be enumerated The alkyl of the straight-chain such as base, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, positive decyl；Isopropyl, 2-methyl-propyl, 2, 2-dimethyl propyl, 2-ethylhexyl etc. comprise the alkyl of side chain；Cyclopropyl, cyclopenta, cyclohexyl, the isothrausmatic alkane of ring octyl group Base；The aryl such as phenyl, 1-naphthyl, 2-naphthyl；The heteroaryls such as 2-pyridine radicals, 2-thienyl, 2-furyl；Benzyl, 2-phenyl second Base, to aralkyl etc. such as methoxy-benzyls.

Among these, it is the alkane of 1～6 from the industrial aspect that can obtain at low cost, preferably carbon number Base.In this case, from being easily subject to hydrolysis in synthesis, easily generating the aspect of carboxylic acid, carbon number be preferably 2 with On；It addition, from by remove with the ester exchange of dihydroxy compounds generate lower boiling alcohol it is thus possible to close efficiently From the standpoint of becoming polyester and polyestercarbonate, preferably less than 4, more preferably less than 2.Particularly preferred substituent group is second Base.

On the other hand, in the case of the aryl that carbon number is 6～8, ester exchange reaction is easily carried out, thereby through inciting somebody to action The diester compound of the present invention and dihydroxy compounds, carbonic diester put in reactor by adding in the lump such that it is able to One-step synthesis is as the polyestercarbonate of preferred polymers, thus is preferred.In this case, little from molecular weight, easily steam The aspect evaporating removing is set out, and carbon number is preferably less than 8, more preferably less than 6.Particularly, it is particularly preferably at polyester carbon The phenyl that can remove as phenol distillation after acid esters synthesis.It addition, the reactive side in the case of aryl, when polymerization Setting out in face, described later diaryl carbonate esters is preferably used as carbonic diester, from can easily remove by-product in terms of go out Sending out, the more preferably aryl of the aryl in ester group and diaryl carbonate apoplexy due to endogenous wind is identical.

< 1.4 substituents alpha¹And α²>

Alternatively base α¹And α², it is not particularly limited, Direct Bonding, carbon with or without substituent group can be enumerated Atomic number be 1～10 alkylidene, with or without the arlydene that carbon number is 4～10 of substituent group or have or Not there is the sub-aralkyl that carbon number is 6～10 or the free carbon atom with or without substituent group of choosing of substituent group Number is the alkylidene of 1～10, with or without the arlydene that carbon number is 4～10 of substituent group with or without taking The carbon number of Dai Ji is that the group of more than 2 in the group of the sub-aralkyl composition of 6～10 passes through oxygen atom, has 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 " with or without the alkylidene that carbon number is 1～10 of substituent group ", it may be preferred to use as key Close the group illustrated in alkylidene of fluorenes unit a.In this case, from showing the aspect of inverse wave length dispersibility, preferably Using carbon number is the alkylidene of more than 2.On the other hand, from showing the aspect of smooth dispersibility, its carbon is preferably made Atomic number is 1.Additionally, in the case of showing inverse wave length dispersibility, easily fix relative to main chain from the orientation making fluorenes ring, The aspect that can be efficiently obtained by inverse wave length dispersing characteristic is set out, carbon number is preferably less than 5, more preferably less than 4, further It is preferably less than 3, particularly preferably less than 2.On the other hand, from the aspect to resin combination imparting flexibility, its carbon Atomic number is preferably more than 2, more preferably more than 3, more preferably more than 4.

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

Hereinafter enumerate and " select the free alkylidene that carbon number is 1～10 with or without substituent group, have or do not have The carbon number of substituted base is the arlydene of 4～10 and with or without the sub-virtue that the carbon number of substituent group is 6～10 Alkyl composition group in more than 2 group pass through oxygen atom, with or without substituent group sulphur atom, have or do not have The group that the nitrogen-atoms of substituted base or carbonyl are formed by connecting " concrete structure, but be not limited to these, can enumerate following Divalent group shown in [D] group.

[changing 37]

[D]

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

[changing 38]

[E]

It addition, from the aspect of raising fluorenes ratio, in the case of for these groups through being formed by connecting, its 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 1 be Direct Bonding or substituents alpha¹And α²In at least 1 In the case of individual carbon number is more than 2, due to fluorenes ring, (fluorenes unit a) is generally perpendicularly orientated relative to main chain, thus is Just the ratio of three fluorenes of the divalent in resin combination is few, it may have easily show the tendency of inverse wave length dispersibility.The latter's In the case of, from same aspect, preferably make α¹And α²Both carbon numbers are more than 2.On the other hand, substituent group is made α¹And α²In the case of both carbon numbers are 1 (that is, with or without the methylene of substituent group), fluorenes ring (fluorenes unit) phase It not generally perpendicularly to be orientated for main chain, and be orientated the most obliquely, so even in wide range resin combination The ratio of three fluorenes of divalent, it may have be easily formed at the tendency of the little smooth dispersibility of the difference of phase contrast in wide band.

Among these, preferably Direct Bonding, with or without substituent group the alkylidene that carbon number is 1～10, The arlydene that carbon number is 4～10 or choosing with or without substituent group are freely with or without the carbon of substituent group Atomic number is the alkylidene of 1～10, with or without the arlydene that carbon number is 4～10 of substituent group with have or do not have The carbon number of substituted base be 6～10 sub-aralkyl composition group in more than 2 group pass through oxygen atom, have or The sulphur atom without substituent group, the group being formed by connecting with or without nitrogen-atoms or the carbonyl of substituent group.

It is more preferably Direct Bonding, the alkylidene of straight-chain, comprises the alkylidene of side chain, at the fat shown in above-mentioned [A] group There is at any the 2 of ring structure the ester ring type alkylidene of the associative key of the alkylidene of straight-chain or branched, phenylene, or The choosing freedom alkylidene with or without the carbon number 1～10 of substituent group, the carbon number 4 with or without substituent group ～the arlydene of 10 and with or without substituent group carbon number 6～10 sub-aralkyl composition group in more than 2 The group that is formed by connecting by oxygen atom of group.

It may further be preferable that have the low photoelasticity system being capable of required by blooming owing to not there is aromatic rings Number tendency, Direct Bonding, methylene, ethylidene, positive propylidene, positive butylidene, methylmethylene, 1-methyl ethylidene, 2-methyl ethylidene, 2,2-dimethylpropylidene, 2-methoxy-2-methyl propylene or the alicyclic ring shown in 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.)

Further preferably Direct Bonding, methylene, ethylidene, positive propylidene, positive butylidene, methylmethylene, 1-first Base ethylidene, 2-methyl ethylidene or 2,2-dimethylpropylidene.Particularly preferably methylene, ethylidene or positive propylidene.

Owing to having the tendency that glass transition temperature reduces when chain length is longer, thus the shortest chain-like groups, example If preferred carbon number is the group of less than 2.Further, owing to molecular structure diminishes, thus have and can improve repetition list The tendency of the concentration (fluorenes ratio) of the fluorenes ring in unit such that it is able to efficiency shows desired optics physical property well.It addition, It is preferably methylene, even if this group contains with any quality relative to the quality of resin combination entirety, it may have available The smooth scattered tendency that the wavelength dispersibility of phase contrast is little, and then also have can be with shorter process and industrial low cost Ground carries out the superiority imported.

On the other hand, for the mechanical strength of film obtained by improving, the purpose of reliability under high temperature, it is preferably able to carry The glass transition temperature of high resin compositions, carbon number be 4～10 arlydene or choosing freely with or without The carbon number of substituent group is the alkylidene of 1～10 and with or without the arlydene that carbon number is 4～10 of substituent group The group that is formed by connecting by oxygen atom of more than 2 groups in the group of composition, more preferably Isosorbide-5-Nitrae-phenylene, 1,5-Asia naphthalene Divalent group shown in base, 2,6-naphthylene or following [D2] group.

[changing 40]

[D21

It addition, in the case of being applied to have the phase retardation film of inverse wave length dispersibility, suitably select substituents alpha¹And α²It is Important.Such as, due to the group that carbon number is 1 with methylene as representative, to have unforeseeable inverse wave length dispersibility low Tendency, thus R¹And R²Be preferably Direct Bonding or its at least any one be carbon number be the group of more than 2.

More preferably Direct Bonding, with or without substituent group the alkylidene that carbon number is 2～10, have or not The arlydene that carbon number is 4～10 or the free carbon number with or without substituent group of choosing with substituent group are 1 ～the alkylidene of 10, with or without the arlydene that carbon number is 4～10 of substituent group with or without substituent group The sub-aralkyl that carbon number is 6～10 composition group in more than 2 group pass through 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.

More preferably Direct Bonding, the alkylidene of straight-chain, comprise side chain alkylidene, above-mentioned [A] group shown in Alicyclic structure any 2 at there is the ester ring type alkylidene of associative key of alkylidene of straight-chain or branched, phenylene, Or for choosing freely with or without the alkylidene that carbon number is 1～10 of substituent group, with or without substituent group Carbon number be 4～10 arlydene and with or without substituent group the sub-aralkyl that carbon number is 6～10 form The group that the group of more than 2 in group is formed by connecting by oxygen atom.

It is even furthermore preferable that be capable of the low photoelastic coefficient required by blooming owing to not there is aromatic rings , Direct Bonding, ethylidene, positive propylidene, positive butylidene, methylmethylene, 1-methyl ethylidene, 2-methyl ethylidene, 2, Ester ring type alkylidene shown in 2-dimethylpropylidene, 2-methoxy-2-methyl propylene or above-mentioned [F] group；Or Can increase resin combination glass transition temperature, 1,4-phenylene, choosing is freely with or without the carbon of substituent group Atomic number be 1～10 alkylidene and with or without substituent group the arlydene that carbon number is 4～10 form group in The group that is formed by connecting by oxygen atom of the group of more than 2.

Particularly preferably Direct Bonding, ethylidene, positive propylidene, positive butylidene, methylmethylene, 1-methyl ethylidene, 2-methyl ethylidene or 2,2-dimethylpropylidene.

Most preferably ethylidene or positive propylidene.Owing to having inclining of glass transition temperature reduction when chain length is longer To, thus the shortest chain-like groups, such as carbon number are the group of less than 3.Further, subtract due to molecular structure Little, it is thus possible to the concentration (fluorenes ratio) of the fluorenes ring in raising repetitive such that it is able to efficiency shows desired well Optics physical property.

It addition, for reasons of easy to manufacture, preferred substituents α¹And α²Identical.

<1.5 concrete structure>

As the three fluorenes diester of the present invention, specifically, it may be preferred to use the material represented by following formula (1).

[changing 41]

(in formula,

R¹⁰Be carbon number be the organic substituent of 1～10.)

It should be noted that in formula (1) R^3aAnd R^3bCan be the same or different respectively.It addition, in formula (1) In be respectively provided with the R of 3⁴～R⁹Can be the same or different respectively.Similarly, there is in formula (1) R of 2¹⁰Respectively Can be the same or different.

R in above-mentioned formula (1)¹And R²In, as " the alkylene that carbon number is 1～4 with or without substituent group Base ", it may be preferred to use the R in above-mentioned " invention 1 "¹And R²This base in illustrated group.

Similarly, as R^3aAnd R^3b, it may be preferred to use in<1.1 alkylidenes, arlydene, sub-aralkyl>illustrated Group.It should be noted that sometimes by R in this specification^3aAnd R^3bIt is designated as R in the lump³。

It addition, as R¹⁰, it may be preferred to use in<1.3 ester group>as the organic substituent that carbon number is 1～10 Illustrated group.

Hereinafter enumerate at R⁴～R⁹In the concrete knot of " with or without the alkyl that carbon number is 1～10 of substituent group " Structure, but it is not limited to these, the straight chains such as methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, positive decyl can be enumerated The alkyl of shape；Isopropyl, 2-methyl-propyl, 2,2-dimethyl propyl, 2-ethylhexyl etc. comprise the alkyl of side chain；Cyclopropyl, Cyclopenta, cyclohexyl, the isothrausmatic alkyl of ring octyl group.

Be preferably less than 4 with or without the carbon number in the alkyl that carbon number is 1～10 of substituent group, more excellent Elect less than 2 as.If in the range of Gai, then fluorenes ring be difficult to produce sterically hindered each other, has obtain from fluorenes ring desired The tendency of optical characteristics.

The substituent group can having as this alkyl, can enumerate halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine Atom)；Carbon number is the alkoxyl (such as methoxyl group, ethyoxyl etc.) of 1～10；Carbon number be 1～10 acyl group (such as Acetyl group, benzoyl etc.)；Carbon number is the amide groups (such as acetamido, benzamido etc.) of 1～10；Nitro；Cyanogen Base；With or without being 1～10 selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine), carbon number Alkyl (such as methyl, ethyl, isopropyl etc.), carbon number are alkoxyl (such as methoxyl group, ethyoxyl etc.), the carbon of 1～10 Amide groups (the such as acetamide that acyl group (such as acetyl group, benzoyl etc.) that atomic number is 1～10, carbon number are 1～10 Base, benzamido etc.), nitro, 1～3 substituent group in cyano group etc. the aryl that carbon number is 6～10 (such as phenyl, Naphthyl etc.) etc..The quantity of this substituent group is not particularly limited, preferably 1～3.In the case of substituent group is more than 2, replace The kind of base can be the same or different.It addition, from the industrial aspect that can manufacture at low cost, be preferably without taking Generation.

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

Hereinafter enumerate R⁴～R⁹In the concrete structure of " with or without the aryl that carbon number is 4～10 of substituent group ", But it is not limited to these, the aryl such as phenyl, 1-naphthyl, 2-naphthyl can be enumerated；2-pyridine radicals, 2-thienyl, 2-furyl etc. Heteroaryl.

Be preferably less than 8 with or without the carbon number in the aryl that carbon number is 4～10 of substituent group, more excellent Elect less than 7 as.If in the range of Gai, then fluorenes ring be difficult to produce sterically hindered each other, has obtain from fluorenes ring desired The tendency of optical characteristics.

The substituent group can having as this aryl, can enumerate halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine Atom)；Carbon number is the alkyl (such as methyl, ethyl, isopropyl etc.) of 1～10；Carbon number is the alkoxyl of 1～10 (such as methoxyl group, ethyoxyl etc.)；Carbon number is the acyl group (such as acetyl group, benzoyl etc.) of 1～10；Carbon number is The amide groups (such as acetamido, benzamido etc.) of 1～10；Nitro；Cyano group etc..The quantity of this substituent group limits the most especially Fixed, preferably 1～3.In the case of substituent group is more than 2, the kind of substituent group can be the same or different.It addition, from The industrial aspect that can manufacture at low cost is set out, the most unsubstituted.

As the concrete example of the aryl with or without substituent group, can enumerate 2-aminomethyl phenyl, 4-aminomethyl phenyl, 3, 5-3,5-dimethylphenyl, 4-benzoylphenyl, 4-methoxyphenyl, 4-nitrobenzophenone, 4-cyano-phenyl, 3-trifluoromethylbenzene Base, 3,4-Dimethoxyphenyl, 3,4-methylene dihydroxyphenyl, 2,3,4,5,6-pentafluorophenyl group, 4-methylfuran base etc..

Hereinafter enumerate R⁴～R⁹In the concrete structure of " with or without the acyl group that carbon number is 1～10 of substituent group ", But be not limited to these, can enumerate formoxyl, acetyl group, propiono, 2-methylpropionyl, 2,2-Dimethylpropanoyl, 2- The aliphatic acyl radicals such as ethyl hexyl acyl group；The aromatic series acyls such as benzoyl, 1-naphthyl carbonyl, 2-naphthyl carbonyl, 2-furyl carbonyl Base.

Be preferably less than 4 with or without the carbon number in the acyl group that carbon number is 1～10 of substituent group, more excellent Elect less than 2 as.If in the range of Gai, then fluorenes ring be difficult to produce sterically hindered each other, has obtain from fluorenes ring desired The tendency of optical characteristics.

The substituent group can having as this acyl group, can enumerate halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine Atom)；Carbon number is the alkyl (such as methyl, ethyl, isopropyl etc.) of 1～10；Carbon number is the alkoxyl of 1～10 (such as methoxyl group, ethyoxyl etc.)；Carbon number is the amide groups (such as acetamido, benzamido etc.) of 1～10；Nitre Base；Cyano group；With or without selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine), carbon number be 1～ The alkyl (such as methyl, ethyl, isopropyl etc.) of 10, carbon number are alkoxyl (the such as methoxyl group, ethyoxyl of 1～10 Deng), carbon number be 1～10 acyl group (such as acetyl group, benzoyl etc.), carbon number be 1～10 amide groups (such as Acetamido, benzamido etc.), nitro, the aryl (example that carbon number is 6～10 of 1～3 substituent group in cyano group etc. Such as phenyl, naphthyl etc.) etc..The quantity of this substituent group is not particularly limited, preferably 1～3.Substituent group is the situation of more than 2 Under, the kind of substituent group can be the same or different.It addition, from the industrial aspect that can manufacture at low cost, excellent Elect 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-anisoyl, 4-nitro benzoyl, 4-cyanobenzoyl, 4-fluoroform Base benzoyl etc..

Hereinafter enumerate R⁴～R⁹In " with or without the alkoxyl that carbon number is 1～10 or the aryloxy group of substituent group " Concrete structure, but be not limited to these, can enumerate methoxyl group, ethyoxyl, isopropoxy, tert-butoxy, trifluoromethoxy, The alkoxyls such as phenoxy group；The aryloxy group such as phenoxy group.

With or without in the alkoxyl that carbon number is 1～10 of substituent group or aryloxy group, preferably alkoxyl, alkane The carbon number of epoxide is preferably less than 4, more preferably less than 2.If in the range of Gai, then fluorenes ring be difficult to produce space bit each other Resistance, has the tendency obtaining the desired optical characteristics from fluorenes ring.

Hereinafter enumerate R⁴～R⁹In the concrete structure of " with or without the amino of substituent group ", but be not limited to these, can To enumerate amino；N-methylamino, N, N-dimethylamino, N-ethylamino, N, N-diethylamino, N, N-Methylethyl ammonia The aliphatic amines such as base, N-propylcarbamic, N, N-dipropylamino, N-isopropylamino, N, N-diisopropylaminoethyl；N-phenyl Amino, N, the aromatic series amino such as N-diphenyl amino；Formamido, acetamido, caprinoyl amido, benzamido, chloracetyl The amide groups such as amido；The alkoxycarbonyl amido such as Benzyoxycarbonylamino, tertbutyloxycarbonylamino etc..

Among these, owing to not having the high proton of acidity degree, molecular weight is little, have and can improve the tendency of fluorenes ratio, excellent Elect N, N-dimethylamino, N-ethylamino or N, N-diethylamino, more preferably N, N-dimethylamino as.

Hereinafter enumerate R⁴～R⁹In the concrete structure of " there is the sulphur atom of substituent group ", 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 Deng alkyl sulphinyl；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 alkyloxysulfonyl such as methoxysulfonyl, ethoxysulfonyl；Benzene oxygen The aryloxy sulfonyls such as base sulfonyl；Amino-sulfonyl；N-methylaminosulfonyl, N-ethylaminosulfonyl, the N-tert-butyl group Amino-sulfonyl, N, N-dimethylamino-sulfonyl, N, the alkyl sulphonyl such as N-diethylamino sulfonyl；N-phenyl amino sulphur Acyl group, N, the n-aryl sulfonyl etc. such as N-diphenyl amino sulfonyl.It should be noted that sulfo group can also with lithium, sodium, Potassium, magnesium, ammonium etc. form salt.

Among these, owing to not having the high proton of acidity degree, molecular weight is little, have and can improve the tendency of fluorenes ratio, excellent Elect methylsulfinyl, ethylsulfinyl or phenylsufinyl, more preferably methylsulfinyl as.

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

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

So, by making R⁴～R⁹For specific atom as described above or substituent group, between main chain and fluorenes ring, fluorenes ring Each other sterically hindered few, has the tendency that can obtain the desired optical characteristics from fluorenes ring.

These R⁴～R⁹In, the most all hydrogen atoms, or R⁴And/or R⁹For selecting free halogen, acyl group, nitro, cyanogen Any one and R in the group of base and sulfo group composition⁵～R⁸For hydrogen atom.In the case of all hydrogen atoms, in industry On also be able to be derived by the fluorenes of low cost.It addition, at R⁴And/or R⁹For selecting free halogen, acyl group, nitro, cyano group and sulphur Any one in the group of basis set one-tenth and R⁵～R⁸In the case of hydrogen atom, due to the reactive raising of fluorenes 9, thus there is energy Enough adapt to the tendency of various induced reaction.The most all hydrogen atoms, or R⁴And/or R⁹For selecting free fluorine atom, chlorine former Any one and R in the group of son, bromine atoms and nitro composition⁵～R⁸For hydrogen atom, particularly preferred all hydrogen atoms Situation.Additionally, by for above-mentioned group, it is possible to increase fluorenes ratio, and fluorenes ring is difficult to produce sterically hindered each other, and also having can Obtain the tendency of the desired optical characteristics from fluorenes ring.

As the concrete example of the three fluorenes diester of the present invention, the structure shown in following [H] group can be enumerated.

[changing 42]

[changing 43]

The physics value of the three fluorenes diester of the present invention is not particularly limited, and preferably meets 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 mass.Enter one Step is preferably below 10 mass ppm.In the case of the content ratio of chlorine component is many, catalyst used in polyreaction can be made to lose Living, polymerization cannot be carried out to desired molecular weight, and reaction, in destabilization, has the probability that productivity ratio is deteriorated.And Obtained polymer also has chlorine component remaining, the heat stability of polymer may be made to reduce.

The content ratio of three fluorenes monoesters bodies in the three fluorenes diester of the present invention is preferably the quality of whole three fluorene compounds Below 10 mass %.More preferably below 2 mass %.The meeting when the three fluorenes aggregated reactions of monoesters body are incorporated in polymer Formed end envelope chain group, if thus three fluorenes monoesters bodies increase, then polymerization carry out less than desired molecular weight or polymer In the remaining quantity of the low molecular composition such as oligomer increase, mechanical strength or the thermostability fall of obtained polymer may be made Low.In addition it is believed that also low molecular composition from molded body, the probability making the quality of goods reduce such as ooze out.Need explanation , monoesters body refers to the thing that any one is the group beyond polymerisation reactivity group in the end ester group of three fluorenes diester Matter.

In the three fluorenes diester of the present invention, may be containing deriving from the sodium of following operation or potassium isometric preiodic type periodic chart the The group II metals such as 1 race's metal or calcium, this operation is to make formaldehydes have an effect in the presence of a base to carry out the work of HM Sequence；The content ratio of these metals is preferably below below 500 mass ppm, more preferably 200 mass ppm, more preferably Below 50 mass ppm, below particularly preferably 10 mass ppm.If metal ingredient is many, then add man-hour in polyreaction or resin, Polymer may become easy coloring.Additionally, contained metal ingredient demonstrates catalyst action or catalysqt deactivation effect, also May make polymerization is destabilization.

In the three fluorenes diester, particularly three fluorene diaryl esters of the present invention, may containing brought by following operation titanium, Group II metal, zinc, the cadmiums etc. such as the transition metal such as copper, ferrum, sodium, potassium isometric preiodic type periodic chart the 1st race, magnesium, calcium the 12nd race's gold 14th race's metals such as genus or stannum, this operation is for make diaryl carbonates esters have an effect in the presence of catalyst for ester exchange reaction Carry out the operation of ester exchange；The content ratio of these metals is preferably below 500 mass ppm, more preferably 200 mass ppm Below, more preferably below 50 mass ppm, below particularly preferably 10 mass ppm.If metal ingredient is many, then in polymerization Reaction or resin add man-hour, and polymer may become easy coloring.Additionally, contained metal ingredient demonstrate catalyst action or Catalysqt deactivation effect, it is also possible to making polymerization is destabilization.

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 It is less than 10.The absorption edge of three fluorenes diester extends close to the region of visible ray, has and is exposing because of polymerization or resin processing The character easily coloured when high temperature.The polymer good in order to obtain tone, three fluorenes diester used in preferred polymeric reaction Coloring as far as possible is few.Owing to tone is proportional to concentration, thus can be to be measured under variable concentrations and be standardized as 10 Quality % concentration and the value that obtains.Herein, the tone (APHA value) of three fluorenes diester can be measured: according to JIS-K0071-1 (1998), color standard liquid (1000 degree) dilution that Kishida Chemical society is manufactured, by made diluent and Three fluorenes diester are encased in the color comparison tube of internal diameter 20mm and compare, and thus measure this tone.

The three fluorenes diester of the present invention, 5% weightless temperature in thermogravimetric measures is preferably more than 230 DEG C, is more preferably 250 More than DEG C.The most particularly preferably more than 270 DEG C.Fluorenes is the structure very rich in electronics, is bonded in the substituent group on fluorenes ring Reactive high, easily produce thermal decomposition.If using the three fluorenes diester that heat decomposition temperature is low in the polymerization, then when polymerization Can produce thermal decomposition, polymerization may colour less than desired molecular weight or obtained polymer.

It addition, the decomposition temperature that the three fluorenes diester of the present invention measure in a nitrogen atmosphere be preferably more than 250 DEG C, more preferably It it is more than 300 DEG C, more preferably more than 330 DEG C, usually less than 380 DEG C.The three fluorenes diester of the present invention are by fluorenes ring Laminated structure and make structure upright and outspoken, therefore there is decomposition temperature and meet the tendency of above-mentioned scope.Met by such decomposition temperature Above-mentioned scope, has and can improve polyester, the tendency of heat stability of Merlon obtained by three fluorenes diester.Decomposition temperature is such as Can be measured by TG-DTA.

Additionally, the fusing point (m.p.) of the three fluorenes diester of the present invention is preferably more than 120 DEG C, more preferably more than 130 DEG C, enters One step is preferably more than 150 DEG C, 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 has fusing point and meets the tendency of above-mentioned scope.Meet above-mentioned scope by such fusing point, have and can improve by three Polyester that fluorenes diester obtains, the tendency of the glass transition temperature of Merlon.Fusing point such as can be surveyed by TG-DTA Fixed.

The manufacture method of three fluorenes diester represented by three fluorenes diester used in the present invention, the most above-mentioned formula (1) is also Without any restriction, such as, can be manufactured by methods such as autofrettage A shown in following formula or autofrettages B.

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

[changing 44]

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

R^3aAnd R^3bBe each independently the alkylidene that carbon number is 1～10 with or without substituent group, have or Not there is the arlydene that carbon number is 4～10 of substituent group or the carbon number with or without substituent group is 6～10 Sub-aralkyl,

R⁴～R⁹It is each independently hydrogen atom, the alkyl that carbon number is 1～10 with or without substituent group, tool There is or do not have the aryl that carbon number is 4～10 of substituent group, be 1～10 with or without the carbon number of substituent group Acyl group, the alkoxyl that carbon number is 1～10 with or without substituent group, the carbon number with or without substituent group Be 1～10 aryloxy group, with or without substituent group amino, there is the sulphur atom of substituent group, halogen atom, nitro or cyanogen Base.Wherein, at R⁴～R⁹In, at least 2 adjacent groups can be mutually bonded formation ring.

R¹⁰Be carbon number be the organic substituent of 1～10.

<1.8.1 autofrettage A>

Autofrettage A is following method: using fluorenes class (I) as raw material, is converted to 9-hydroxymethyl fluorenes class (IV), passes through afterwards Dehydration synthesis alkene body (V), makes alkene body (V) react with fluorenyl anion, refines etc. by the mixing of low polyfluorene by post Thing refines, manufactures R³Three fluorene compounds (IIa) for methylene.It should be noted that unsubstituted 9-hydroxymethyl Fluorenes can be bought as reagent.Also three fluorene compounds (II) that thus place obtains ester group can be imported according to the operation (ii) of autofrettage C Make three fluorenes diester (1).

The most known have 9-hydroxymethyl fluorenes is converted into 9-methylene-9H-fluorenes after synthesized by anionic polymerisation low The method (J.Am.Chem.Soc., 123,2001,9182-9183.) of the mixture of polyfluorene.It is referred to these methods, by mixing Compound refines, thus manufactures three fluorene compounds (II).

<1.8.2 autofrettage B>

Autofrettage B is following method: synthesize three fluorenes by the cross-linking reaction (operation (i)) carrying out raw material fluorenes class (I) Compound (II), manufactures three fluorenes diester (1) thereafter by importing ester group (operation (ii)).

[changing 45]

In formula, R¹～R¹⁰With the R in formula (1)¹～R¹⁰Implication is identical.

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

[changing 46]

In formula, R³～R⁹With the R in formula (1)³～R⁹Implication is identical.

Below the manufacture method of three fluorene compounds (II) in operation (i) is divided into R³Situation record.

<1.8.3.1R³Situation for Direct Bonding: 9,9 ': 9 ', 9 " manufacture method of-three difluorenes >

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

< 1.8.3.2 operation (ia): R³The manufacture method of situation for methylene >

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

[changing 47]

In formula, R⁴～R⁹With the R in formula (1)⁴～R⁹Implication is identical.

<1.8.3.2.1 formaldehydes>

Operation (ia) is as long as the middle formaldehydes used is can to supply the material of formaldehyde in reaction system the most especially Limit, the formaldehyde of gaseous state, formalin, the paraformaldehyde of oxymethylene polymerization, trioxane etc. can be enumerated.From work Industry low cost and due to for powder thus operability easily, can be from the standpoint of accurate weighing, more preferably paraformaldehyde. On the other hand, low from industrial cost and due to for liquid thus add time expose danger few from the standpoint of, more preferably first Aldehyde.

(definition of theoretical amount)

In the case of being manufactured as three fluorene compounds (IIa) of target, formaldehydes is relative to the theory of raw material fluorenes class (I) Amount (mol ratio) is represented by 2/3.

(the preferably more than reason of theoretical amount)

In the case of the formaldehydes that fluorenes class (I) uses more than theoretical amount, have and can generate and as the three of target Fluorene compound (IIa) compares the tendency of the Oligofluorenylene compounds that fluorenes cross-links further.Fluorenes ring due to Oligofluorenylene compounds Number more increases dissolubility and more can reduce, thus there are the Oligofluorenylene compounds of more than 4 fluorenes ring crosslinkings in goal object In the case of, it is known that there is the tendency that refined load increases.Therefore it is usually preferred to the consumption of formaldehydes is as goal theory amount Less than 2/3 times mole.

(not the most being significantly less than the reason of theoretical amount)

If it addition, the consumption of formaldehydes is significantly less than theoretical amount 2/3, then with three fluorene compounds (IIa) phase as target Two fluorene compounds fewer than the number of crosslinks of fluorenes ring are main product or raw material fluorenes class (I) unreacted has residual, it will be appreciated that There is the tendency that yield is greatly reduced.

Thus, about the optimum amount of formaldehydes, specifically, relative to raw material fluorenes class (I), usually 0.5 times mole Above, be preferably more than 0.55 times mole, more preferably more than 0.6 times mole, other be usually less than 0.67 times mole, It is preferably less than 0.65 times mole, more preferably less than 0.63 times mole.So understand, according to the consumption of formaldehydes, main Great changes have taken place with the ratio of product for the structure of product, by using under conditions of limiting formaldehydes consumption, and tool There is the tendency that can obtain three fluorene compounds (IIa) as target using high yield.

<1.8.3.2.2 alkali>

As the alkali used in operation (ia), use the alkali metal hydroxide such as Lithium hydrate, sodium hydroxide, potassium hydroxide Thing；The hydroxide of the alkaline-earth metal such as calcium hydroxide, barium hydroxide；The alkali-metal carbonic acid such as sodium carbonate, sodium bicarbonate, 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 salt such as butyl lithium, tert-butyl lithium；The alkali alcoholates such as Feldalat NM, Sodium ethylate, potassium tert-butoxide；Sodium hydride, hydrofining Deng hydrogenated alkali metal salt；The tertiary amines such as triethylamine, diazabicyclo endecatylene；Tetramethylammonium hydroxide, TBAH Deng quaternary ammonium hydroxide etc..They can be used alone one, it is also possible to share two or more.

When utilizing homogeneous system to react, it is preferably among these and there is abundant alkalescence alkali-metal in the reaction Feldalat NM that alkoxide, more preferably industrial cost are low and Sodium ethylate.Alkali alcoholate herein can use the material of powdery, also The liquids such as alcoholic solution can be used.And alkali metal can be made to react with alcohol prepare.

On the other hand, when utilizing two coating systems to react, it is preferably among these and there is abundant alkalescence in the reaction The aqueous solution of alkali metal hydroxide, sodium hydroxide that more preferably industrial cost is low or the aqueous solution of potassium hydroxide, enter One step is preferably the aqueous solution of sodium hydroxide.

It addition, about the concentration of aqueous solution, in the case of using particularly preferred sodium hydrate aqueous solution, when concentration is low Response speed significantly reduces, thus generally uses more than 10wt/wt%, is preferably more than 25wt/wt%, more preferably 40wt/ The aqueous solution of more than wt%.

When utilizing homogeneous system to react, the consumption of alkali there is no the special upper limit relative to raw material fluorenes class (I), if but consumption Too much, then there is stirring or tendency that reacted refined load increases, thus usually less than 10 times moles of fluorenes class (I), It is preferably less than 5 times moles, more preferably less than 1 times mole.On the other hand, if the consumption of alkali is very few, then there is reaction Carry out slow tendency, thus as lower limit, be commonly angled relative to raw material fluorenes class (I) and be more than 0.01 times mole, be preferably 0.1 Times mole more than, more preferably more than 0.2 times mole.

On the other hand, when utilizing two coating systems to react, the consumption of alkali there is no relative to raw material fluorenes class (I) and goes up especially Limit, if but consumption is too much, then there is stirring or tendency that reacted refined load increases, thus usually fluorenes class (I) 10 Times mole following, preferably less than 5 times moles, more preferably less than 2 times moles.On the other hand, if the consumption of alkali is very few, Then have reaction carries out slow tendency, thus as lower limit, be commonly angled relative to raw material fluorenes class (I) be more than 0.1 times mole, It is preferably more than 0.3 times mole, more preferably more than 0.4 times mole.

<1.8.3.2.3 solvent>

Operation (ia) is preferably used solvent and carries out.As the concrete example of the solvent that can use, can enumerate: as alkyl The acetonitrile of nitrile series solvent, propionitrile etc.；As the diethyl ether of ether series solvent, oxolane, 1,4-dioxane, methylcyclopentyl Ether, t-butyl methyl ether etc.；As the 1,2-dichloroethanes of halogen series solvent, dichloromethane, chloroform, 1,1,2,2-sym-tetrachloroethane Deng；As the chlorobenzene of halogen system aromatic hydrocarbon, 1,2-dichloro-benzenes etc.；As N,N-dimethylformamide, the N of amide series solvent, N-dimethyl acetylamide, N-Methyl pyrrolidone etc.；As the dimethyl sulfoxide of sulfoxide series solvent, sulfolane etc.；As ring type The monocyclic aliphatic hydrocarbon such as the Pentamethylene. of aliphatic hydrocarbon, hexamethylene, cycloheptane, cyclooctane, for its derivant methyl cyclopentane, Ethyl cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-dimethyl Hexamethylene, isopropyl cyclohexane, n-pro-pyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene, 1,2, 4-trimethyl-cyclohexane, 1,3,5-trimethyl-cyclohexane etc.；The polycycle aliphatic hydrocarbons such as decahydronaphthalenes；Pentane, normal hexane, just The non-ring type aliphatic hydrocarbons such as heptane, normal octane, isobutyltrimethylmethane., n-nonane, n-decane, n-dodecane, n-tetradecane；As aromatic series The toluene of hydrocarbon, xylol, o-Dimethylbenzene, meta-xylene etc.；As the methanol of alcohol series solvent, ethanol, isopropanol, n-butyl alcohol, The tert-butyl alcohol, hexanol, capryl alcohol, Hexalin etc..

In the reaction of homogeneous system, the dissolubility of the anion owing to being generated by fluorenes class (I) is high, have reaction carries out good Good tendency, thus the preferably amide series solvent of polar solvent or sulfoxide series solvent.Wherein, particularly preferably N, N-bis- Methylformamide.This is because, the dissolubility that three fluorene compounds (IIa) are in DMF is low, raw in goal object Separate out rapidly after one-tenth, suppress the carrying out of its above reaction, there is the tendency that the selectivity of goal object increases.

In the reaction of two coating systems, form 2 layers with alkaline aqueous solution, fluorenes class (I) dissolubility of the anion generated Height, has reaction and carries out good tendency, thus the preferably ether series solvent of polar solvent or halogen series solvent.Wherein special You Xuanwei oxolane.This is because, the dissolubility that three fluorene compounds (IIa) are in oxolane is low, generate in goal object Rear precipitation rapidly, suppresses the carrying out of its above reaction, has the tendency that the selectivity of goal object increases.

These solvents can be used alone one, it is also possible to two or more is used in mixed way.

As the upper limit of the consumption of solvent, generally use and reach 10 times of volumes of raw material fluorenes class (I), preferably 7 times of bodies The amount of accumulated amount, more preferably 4 times of volumes.On the other hand, if the consumption of solvent is very few, then stirring becomes difficult, has simultaneously The carrying out of reaction is inclined to slowly, thus reaches 1 times of volume of raw material fluorenes class (I) as lower limit, generally use, be preferably 2 The amount of times volume, more preferably 3 times of volumes.

<1.8.3.2.4 reaction formation>

When carrying out operation (ia), the form of reaction can use batch-type reaction, circulation type reaction or their combination and The form become, is not particularly limited its form.

<1.8.3.2.5 reaction condition>

For operation (ia), in order to suppress the generation of the compound of fluorenes ring crosslinking compared with three fluorene compounds (IIa), React the most at low temperatures.On the other hand, if temperature is too low, then sufficient response speed may be can not get.

Accordingly, as concrete reaction temperature, generally it is 40 DEG C in the upper limit, is preferably the temperature of 30 DEG C, more preferably 20 DEG C Under implement.On the other hand ,-50 DEG C, preferably-20 DEG C, more preferably 0 DEG C of enforcement carried out above within the range having a lower limit of.

General reactions time usual lower limit in operation (ia) is 30 minutes, be preferably 60 minutes, more preferably 2 little Time, the upper limit without particular limitation of, but usually 20 hours, be preferably 10 hours, more preferably 5 hours.

After termination of the reaction, reactant liquor can be added in the acid waters such as dilute hydrochloric acid, or the acid waters such as dilute hydrochloric acid are added It is added in reactant liquor, makes goal object three fluorene compound (IIa) separate out, thus separate.

Additionally, after termination of the reaction, it is possible to the solvent of solubilized goal object three fluorene compound (IIa) and water are added to instead Answer in liquid, extract.Utilize the goal object that solvent extraction goes out can be by by the method for solvent concentration or add poor solvent Method etc. separate.But, the dissolubility at room temperature having in a solvent due to three fluorene compounds (IIa) is low-down Tendency, thus generally preferably contact the method making it separate out with acid water.

Obtained three fluorene compounds (IIa) also can use directly as the raw material of operation (ii), it is possible to is refining Afterwards in operation (ii).As method for refining, common method for refining, such as recrystallization, reprecipitation method, extraction essence can be used System, column chromatography etc., and unrestrictedly.

< 1.8.3.3 operation (ib): R³Manufacture method for the situation beyond Direct Bonding >

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

[changing 48]

In formula, R³、R^3a、R^3bFor with or without the alkylidene that the carbon number of substituent group is 1～10, have or do not have The carbon number of substituted base is the arlydene of 4～10 or with or without the Asia that carbon number is 6～10 of substituent group Aralkyl, R⁴～R⁹With the R in formula (1)⁴～R⁹Implication is identical.X represents leaving group.As the example of leaving group, Ke Yiju Go out halogen atom (the most not including fluorine), mesyl or p-toluenesulfonyl etc..

Three fluorene compounds (IIb) are referred to following method and synthesize: n-BuLi is used as alkali, are producing fluorenes class (I) after anion so that it is carry out coupling (J.Am.Chem.Soc., 2007,129,8458.) with alkylating agent (VIIIa).But It is, when utilizing these to use the method for n-BuLi to carry out industry manufacture, at secure context, to become present aspect all to have extremely difficult Tendency.

As the alkylating agent used in operation (ib), can enumerate diiodomethane, 1,2-ethylidene periodide, 1,3-diiodo-third Alkane, 1,4-bis-iodobutane, 1,5-bis-iodopentane, 1,6-bis-iodohexane, methylene bromide, glycol dibromide, 1,3-dibromopropane, 1,4-dibromobutane, pentamethylene bromide, 1,6-dibromo-hexane, dichloromethane, 1,2-dichloroethanes, 1,3-dichloropropane, 1, The alkyl dihalide of the straight-chain such as 4-dichloroetane, 1,5-dichloropentane, 1,6-dichloro hexane, 1-bromo-3-chloropropane (does not wraps Include fluorine atom)；The alkyl dihalide (not including fluorine atom) that 2,2-dimethyl-1,3-dichloropropane etc. comprises side chain；1,4- The aralkyl dihalide (not including fluorine atom) such as double (bromomethyl) benzene of double (bromomethyl) benzene, 1,3-；Ethylene glycol bisthioglycolate methanesulfonates, The disulfonate etc. of the glycol such as ethylene glycol bisthioglycolate tosylate, propylene glycol bis-mesylate, tetramethylene glycol bis-mesylate.

Hereinafter, by the manufacture method of three fluorenes diester (1) in the operation (ii) represented by following formula according to R¹Kind divide Do not record.

[changing 49]

In formula, R¹～R¹⁰With the R in formula (1)¹～R¹⁰Implication is identical.R_i、R_iiAnd R_iiiIt is each independently hydrogen atom, tool There is or do not have the alkyl that carbon number is 1～10 of substituent group, be 4～10 with or without the carbon number of substituent group Aryl or the aralkyl that carbon number is 6～10 with or without substituent group.

<1.8.4.1 operation (iia): autofrettage based on Michael (Michael) addition>

Three fluorenes diester represented by following formula (1a) can anti-according to represented by following operation (iia) in the presence of a base Ying Yousan fluorene compound (II) and α, beta-unsaturated esters (VI) manufactures.

[changing 50]

In formula, R³～R¹⁰With the R in formula (1)³～R¹⁰Implication is identical.R_i、R_iiAnd R_iiiRepresent independently of one another hydrogen atom, The alkyl that carbon number is 1～10 with or without substituent group, the carbon number with or without substituent group are 4～10 Aryl or with or without the aralkyl that carbon number is 6～10 of substituent group.

<1.8.4.1.1 α, beta-unsaturated esters>

As the alpha, beta-unsaturated esters of reaction reagent by represented by the logical formula (VI) in operation (iia), in logical formula (VI), R_i、R_iiAnd R_iiiRepresent alkyl that hydrogen atom, carbon number are 1～10, former with or without the carbon of substituent group independently of one another Subnumber is the aryl of 4～10 or with or without the aralkyl that carbon number is 6～10 of substituent group.Specifically, may be used To enumerate (can be that straight chain can also be as side chain) alkyl, phenyl, the 1-naphthalenes such as methyl, ethyl, n-pro-pyl, isopropyl, cyclohexyl The aryl such as base, 2-naphthyl, 2-thienyl, benzyl, 2-phenylethyl, to aralkyl such as methoxy-benzyls.

As alpha, beta-unsaturated esters (VI), acrylic acid methyl ester., ethyl acrylate, phenyl acrylate, acrylic acid can be enumerated Allyl ester, glycidyl acrylate, 2-Hydroxy ethyl acrylate, acrylic acid 4-hydroxybutyl, 1,4 cyclohexane dimethanol list The esters of acrylic acids such as acrylate, methyl methacrylate, ethyl methacrylate, phenyl methacrylate, methacrylic acid Methyl acrylic ester, the 2-ethyl propylene such as allyl ester, glycidyl methacrylate, methacrylic acid-2-hydroxy methacrylate Acid alpha-substituted unsaturation esters, methyl cinnamate, ethyl cinnamate, M Cr, the fourth such as methyl ester, 2-phenylacrylic acid methyl ester The beta substitution unsaturation esters such as olefin(e) acid ethyl ester.Wherein, it is preferably able to be introduced directly into the following 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 The carbon number of Dai Ji be 1～10 alkyl, with or without substituent group the aryl that carbon number is 4～10 or tool There is or do not has the aralkyl that carbon number is 6～10 of substituent group.), the esters of acrylic acid that is more preferably included in, methyl Esters of acrylic acid or alpha-substituted unsaturation esters, from the aspect of response speed Yu reaction selectivity, further preferred R_iiiFor Hydrogen atom or the esters of acrylic acid of methyl or methyl acrylic ester.Due to R¹⁰During for less group, industrial cost low and Distillation is refined easily, reactivity is the highest, thus particularly preferably acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, methyl Ethyl acrylate, phenyl acrylate or phenyl methacrylate.

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

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

The polymerization activity of alpha, beta-unsaturated esters (VI) is high, thus in the presence of with high concentration, have easily due to light, heat, The outside stimuluss such as soda acid and occur polymerization tendency.Now, highly exothermic owing to being attended by, thus may be abnormally dangerous. Therefore, from the aspect of safety, the consumption of alpha, beta-unsaturated esters (VI) is preferred to be less excessively used.It is commonly angled relative to former Expect that three fluorene compounds (II) are less than 10 times moles, are preferably less than 5 times moles, more preferably less than 3 times moles.About Lower limit, owing to being calculated as 2 times moles relative to raw material with theoretical amount, thus lower limit is usually more than 2 times moles.In order to accelerate reaction Carry out, not retained material or intermediate, the consumption of alpha, beta-unsaturated esters (VI) is 2.2 times relative to raw material three fluorene compound (II) More than mole, more preferably more than 2.5 times moles.

<1.8.4.1.2 alkali>

As alkali, use the alkali metal hydroxides such as Lithium hydrate, sodium hydroxide, potassium hydroxide；Calcium hydroxide, hydroxide The hydroxide of the alkaline-earth metal such as barium；The alkali-metal carbonate such as sodium carbonate, sodium bicarbonate, 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 Feldalat NM, Sodium ethylate, potassium tert-butoxide；The hydrogenated alkali metal salt such as sodium hydride, hydrofining；Three second The tertiary amines such as amine, diazabicyclo endecatylene；Tetramethylammonium hydroxide, TBAH, benzyltrimethylammonium hydroxide Deng quaternary ammonium hydroxide.They can be used alone one, it is also possible to share two or more.

At R³For methylene situation with in addition in the case of, the reactivity with three fluorene compounds (II) has bigger The tendency of difference.Therefore, it is divided into R³Situation for methylene is recorded with situation in addition.

At R³In the case of methylene, three fluorene compounds (II) the most easily carry out decomposing instead Should.Therefore, the pairs such as decomposition reaction can be suppressed anti-in the case of utilizing the organic layer 2 coating systems with water layer to react The reason answered, is preferably used water miscible inorganic base.Wherein from the standpoint of cost, reactivity, the hydrogen-oxygen of preferred as alkali The aqueous solution of the aqueous solution of compound, the most more preferably sodium hydroxide or the aqueous solution of potassium hydroxide, further preferred hydroxide The aqueous solution of sodium.

It addition, about the concentration of aqueous solution, in the case of using particularly preferred sodium hydrate aqueous solution, owing to having If concentration is low, response speed can significantly reduced tendency, thus particularly preferably use usually more than 10wt/wt%, be preferably The aqueous solution of more than 30wt/wt%, more preferably more than 40wt/wt%.

At R³In the case of beyond methylene, 2 coating systems even with organic layer with water layer also can react, but In the case of using the organic base that is dissolved in organic layer to react, due to have reaction carry out rapidly tendency and excellent Choosing uses organic base.Having the alkali alcoholate of fully alkalescence the most in the reaction, more preferably industrial cost is low Feldalat NM or Sodium ethylate.Alkali alcoholate herein can use the material of powdery, it is possible to use the liquid object such as alcoholic solution Matter.And alkali metal can be made to react with alcohol prepare.

At R³In the case of methylene, about the consumption of alkali, relative to raw material three fluorene compound (II), its upper limit does not has Limit especially, but when the consumption of alkali is too much, stirring or reacted refined load may increase, thus using as special Not preferably in the case of the sodium hydrate aqueous solution of more than the 40wt/wt% of alkali, being commonly angled relative to three fluorenes (II) is 10 times of bodies Below accumulated amount, it is preferably below below 5 times of volumes, more preferably 2 times of volumes.When alkali number is very few, response speed Significantly reduce, thus alkali is usually more than 0.1 times of volume relative to raw material three fluorene compound (II).It is preferably 0.2 times of volume Amount is above, be more preferably more than 0.5 times of volume.

At R³In the case of beyond methylene, about the consumption of alkali, relative to raw material three fluorene compound (II), its upper limit Being not particularly limited, but when the consumption of alkali is too much, stirring or reacted refined load may increase, thus are used as making In the case of the Feldalat NM of particularly preferred alkali or Sodium ethylate, be commonly angled relative to three fluorene compounds (II) be less than 5 times moles, It is preferably less than 2 times moles, more preferably less than 1 times mole, particularly preferably less than 0.5 times mole.Very few at alkali number Time, response speed significantly reduction, thus alkali is relative to raw material three fluorene compound (II) usually more than 0.005 times mole.Excellent Elect more than 0.01 times mole, more preferably more than 0.05 times mole, particularly preferably more than 0.1 times mole as.

<1.8.4.1.3 phase transfer catalyst>

In operation (iia), in the case of utilizing the organic layer 2 coating systems with water layer to react, anti-in order to improve Answer speed, phase transfer catalyst is preferably used.

As phase transfer catalyst, can enumerate tetramethyl ammonium chloride, tetrabutyl ammonium bromide, methyl tricapryl ammonium chloride, Methyl three decyl ammonium chloride, benzyltrimethylammonium chloride, tri-n-octyl methyl ammonium chloride, tetrabutylammonium iodide, acetyl group trimethyl The halogenide (not including fluorine atom) of the quaternary ammonium salt such as ammonium bromide, benzyltriethylammoinium chloride；N, N-dimethyl pyrrolidine chlorination Thing, N-ethyl-N-methyl pyrrolidine iodide, N-butyl-N-crassitude bromide, N-Benzyl-N-methyl pyrroles The halogenide (not including fluorine atom) of the season pyrrolidinium such as alkane chloride, N-ethyl-N-methyl pyrrolidine bromide；N- Butyl-N-methylmorpholine bromide, N-butyl-N-methylmorpholine iodide, N-pi-allyl-N-methylmorpholine bromide Halogenide (not including fluorine atom) Deng season alkylbenzyldimethylasaltsum saltsum；N-methyl-N-benzyl piperidinium chloride, N-methyl-N-benzyl piperazine Pyridine bromide, N, N-lupetidine iodide, N-methyl-N ethyl Piperidineacetic acid salt, N-methyl-N ethyl piperidines The halogenide (not including fluorine) of the season piperidinium salt such as iodide；Crown ether-like etc..Preferably quaternary ammonium salt, further preferred tetrabutyl bromine Change ammonium, benzyltrimethylammonium chloride or benzyltriethylammoinium chloride.

These phase transfer catalysts can be used alone one, it is also possible to share two or more.

When the consumption of phase transfer catalyst is too much relative to raw material three fluorene compound (II), there is ester hydrolysis or step step by step The tendency that the side reactions such as Ke Er (Michael) reaction are significantly carried out, and from the aspect of cost, it is commonly angled relative to three fluorenes Compound (II) is also less than 5 times moles, is preferably less than 2 times moles, more preferably less than 1 times mole.Phase transfer catalysis When the consumption of agent is very few, responds the significantly reduced tendency of speed, thus the consumption of phase transfer catalyst is relative to raw material three fluorenes Compound (II) usually more than 0.01 times mole.It is preferably more than 0.1 times mole, more preferably more than 0.5 times mole.

<1.8.4.1.4 solvent>

Operation (iia) is preferably used solvent and carries out.

Specifically, spendable solvent can be enumerated: as the acetonitrile of alkyl nitrile series solvent, propionitrile etc.；As ketone system The acetone of solvent, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) 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 propionate, 3-ethoxy-propionic acid The esters of the straight-chain such as methyl ester, methyl lactate, ethyl lactate, the ring-type esters such as 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 acetate, the third two The ether-ether classes etc. such as alcohol-1-monoethyl ether acetate；As the diethyl ether of ether series solvent, oxolane, 1,4-dioxane, methyl ring Amyl ether, t-butyl methyl ether etc.；As the 1,2-dichloroethanes of halogen series solvent, dichloromethane, chloroform, 1,1,2,2-tetra-chloroethene Alkane etc.；As the chlorobenzene of halogen system aromatic hydrocarbon, 1,2-dichloro-benzenes etc.；As amide series solvent N,N-dimethylformamide, DMAC N,N' dimethyl acetamide etc.；As the dimethyl sulfoxide of sulfoxide series solvent, sulfolane etc.；Ring penta as ring type aliphatic hydrocarbon The monocyclic aliphatic hydrocarbon such as alkane, hexamethylene, cycloheptane, cyclooctane, for the methyl cyclopentane of its derivant, ethyl cyclopentane, first Butylcyclohexane, ethyl cyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-dimethyl cyclohexane, isopropyl Hexamethylene, n-pro-pyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene, 1,2,4-3-methyl cyclohexanol Alkane, 1,3,5-trimethyl-cyclohexane etc.；The polycycle aliphatic hydrocarbons such as decahydronaphthalenes；Pentane, normal hexane, normal heptane, normal octane, The non-ring type aliphatic hydrocarbons such as isobutyltrimethylmethane., n-nonane, n-decane, n-dodecane, n-tetradecane；Toluene, right as aromatic hydrocarbon Dimethylbenzene, o-Dimethylbenzene, meta-xylene etc.；Pyridine etc. as heteroaromatic；As the methanol of alcohol series solvent, ethanol, different Propanol, n-butyl alcohol, the tert-butyl alcohol, hexanol, capryl alcohol, Hexalin etc..

At R³In the case of methylene, there is separated solvent by using with water, it is known that have and can suppress three The tendency of the side reactions such as the decomposition reaction of fluorene compound (II).Further, raw material three fluorenes chemical combination can preferably be dissolved in use In the case of the solvent of thing (II), carry out the aspect of good tendency from having reaction, raw material three fluorenes chemical combination is preferably used The solvent that dissolubility is more than 0.5 mass % of thing (II), more preferably using this dissolubility is more than 1.0 mass %, the most excellent The solvent that choosing uses this dissolubility to be 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, oxolane, Isosorbide-5-Nitrae- Dioxane or methylcyclopentyl ether.

About the consumption of solvent, the upper limit is not particularly limited, if in view of the generation effect of the goal object in each reactor Rate, then generally use and reach 20 times of volumes of raw material three fluorene compound (II), be preferably 15 times of volumes, more preferably The amount of 10 times of volumes.On the other hand, if the consumption of solvent is very few, then the dissolubility of reagent is deteriorated, stirring becomes difficulty, has simultaneously The carrying out of reaction is inclined to slowly, thus as lower limit, generally use reach raw material three fluorene compound (II) 1 times of volume, It is preferably the amount of 2 times of volumes, more preferably 4 times of volumes.

At 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 brings the tendency of considerable influence, in order to ensure this dissolubility, dielectric constant molten with certain value more than is preferably used Agent.As can preferably dissolve organic base and the solvent of three fluorene compounds (II), optimization aromatic heterocycle, alkyl nitrile series solvent, Amide series solvent, sulfoxide series solvent, particularly preferred pyridine, acetonitrile, DMF, N,N-dimethylacetamide, two Methyl sulfoxide, sulfolane.

About the consumption of solvent, the upper limit is not particularly limited, if in view of the generation effect of the goal object in each reactor Rate, then generally use reaches 20 times of volumes of raw material three fluorenes (II), is preferably 15 times of volumes, more preferably 10 times of bodies The amount of accumulated amount.On the other hand, if the consumption of solvent is very few, then the dissolubility of reagent is deteriorated, stirring becomes difficulty, has reaction simultaneously It is inclined to slowly, thus as lower limit, generally uses and reach 1 times of volume of raw material three fluorenes (II), preferably 2 times of volumes The amount of amount, more preferably 4 times of volumes.

<1.8.4.1.5 reaction formation>

When carrying out operation (iia), the form of reaction can use batch-type reaction, circulation type reaction or their combinations Form, its form is not particularly limited.

In input method reaction reagent put in reactor in the case of batch-wise, will when reaction starts In the case of alpha, beta-unsaturated esters (VI) is fed intake by disposable interpolation, owing to alpha, beta-unsaturated esters (VI) is deposited with high concentration , thus the polyreaction of side reaction is easily carried out.Thus preferably adding raw material three fluorene compound (II), phase transfer catalysis Gradually add α, beta-unsaturated esters (VI) on a small quantity after agent, solvent and alkali every time.

<1.8.4.1.6 reaction condition>

Operation (iia) if in temperature too low, then can not get sufficient response speed, otherwise if temperature is too high, then have The polyreaction tendency easy to perform of alpha, beta-unsaturated esters (VI), thus temperature treatment is critically important.Accordingly, as reaction temperature Degree, specifically, implements for 0 DEG C the most within the range having a lower limit of, preferably 10 DEG C, more preferably 15 DEG C.On the other hand, generally upper It is limited to 40 DEG C, preferably 30 DEG C, more preferably 20 DEG C implement.

About the General reactions time in operation (iia), usual lower limit is 30 minutes, is preferably 1 hour, further preferably Being 2 hours, the upper limit is not particularly limited, usually 20 hours, preferably 10 hours, more preferably 5 hours.

After termination of the reaction, following method can be used to make goal object three fluorenes diester (1a) separate out, thus carry out goal object three The separation of fluorenes diester (1a), described method is by filtering the inorganic base of byproduct metal halogenide and remaining from reactant liquor The method of solvent concentration or the method for the poor solvent of adding purpose thing is carried out after middle removing；Etc..

Additionally, after termination of the reaction, it is also possible in reactant liquor, add acid water and solubilized goal object three fluorenes diester (1a) solvent extracts.The goal object utilizing solvent extraction to go out can be by the method concentrating solvent or interpolation The methods of poor solvent etc. separate.

As the solvent that can use when extracting, if solubilized goal object three fluorenes diester (1a), the most especially Limit, but a kind in being adapted in use to halogen series solvents such as the aromatic hydrocarbon compound such as toluene, dimethylbenzene, dichloromethane, chloroform etc. Or two or more.

The three fluorenes diester (1a) herein obtained can use with the direct form with polyester or with polyestercarbonate starting monomer, Or use etc. can also be carried out with the form of the precursor of polycarbonate starting material monomer but it also may use after carrying out refining. As method for refining, common method for refining, such as recrystallization or reprecipitation method, Hydrolysis kinetics, column chromatography etc. can be used, and infinitely System.Additionally three fluorenes diester (1a) can be dissolved in suitable solvent, utilize activated carbon to process.Now can use Solvent is same with the solvent phase that can use when extracting.

<1.8.4.2 operation (iib): based on alkylating autofrettage>

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

[changing 52]

In formula, R¹～R⁹With the R in formula (1)¹～R⁹Implication is identical.X represents leaving group.As the example of leaving group, Halogen atom (the most not including fluorine), mesyl or p-toluenesulfonyl etc. can be enumerated.

The alkylated reaction of fluorenes class is widely known by the people, and such as, has report to propose 9, double (bromine hexyl) fluorenes of 9-, 9, and 9-is double Double (alkylhalide group) fluorenes (J.Org.Chem., 2010,75,2714.) of the 9,9-such as (iodine hexyl) fluorenes.According to these technological thoughts, it is possible to Three fluorene compounds (II) are synthesized three fluorenes diester (1b) as raw material.

As the alkylating agent used in operation (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 chloropropionate, 2 bromopropionic acid methyl ester, 2-iodopropionic acid methyl ester, 2-chloropropionate, 2- The chloropropionic acid tert-butyl ester, the 2 bromopropionic acid tert-butyl ester, 2 bromopropionic acid ethyl ester, 2-iodopropionic acid ethyl ester, 3-chlorobutanoate, 3-bromo-butyric acid first The halo chains such as ester, 3-iodine methyl butyrate, 3-neoprene acid ethyl ester, 3-neoprene acid ethyl ester, 3-iodine ethyl n-butyrate., the 2-iodopropionic acid tert-butyl ester Alkanoic acid Arrcostab；The halogenated-chain acid aryl esters such as phenyl chloroacetate, phenyl bromoacetate, iodoacetic acid phenyl ester；4-chloromethyl benzoic acid Methyl ester, 4-bromomethyl-benzoic acid methyl ester, 4-chloromethyl benzoic acid ethyl ester, 4-bromomethyl-benzoic acid ethyl ester, 3-chloromethyl benzoic acid The haloalkyl benzoic acid Arrcostabs etc. such as methyl ester, 3-bromomethyl-benzoic acid methyl ester.

< manufacture method of three fluorene diaryl esters of 1.8.4.3 formula (1c) (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 be by via the operation (operation synthesizing three fluorenes diester compounds (1) Or operation (iib) and the side of the ester exchange reaction (operation (iic)) with diaryl carbonate esters (11a) subsequently (iia) Method manufactures.

[changing 53]

In formula, R¹～R¹⁰With the R in formula (1)¹～R¹⁰Implication is identical.Ar¹Represent former with or without the carbon of substituent group Subnumber is the aryl of 4～10.

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

Ar¹The three fluorene diaryl ester compounds for the aryl that carbon number is 4～10 with or without substituent group (1c) can be fragrant by three fluorenes diester compounds (1) and two according to the reaction represented by operation (iic) in the presence of ester exchange catalyst Base carbonates (11a) manufactures.

<1.8.4.3.1.1 diaryl carbonate esters>

Diaryl carbonate esters as reaction reagent can enumerate diphenyl carbonate, carboxylol ester, double (chlorobenzene Base) carbonic ester, m-cresyl, carbonic acid dinaphthyl ester, double (biphenyl) esters of carbonic acid etc..The most preferably less than cost and can industry obtaining The diphenyl carbonate obtained.These diaryl carbonates can be used alone a kind, it is possible to two or more is used in mixed way.

About the consumption of diaryl carbonate esters, there is no the special upper limit relative to raw material three fluorenes diester (1), if but consumption mistake Many, then there is the tendency that reacted refined load increases, thus usually less than 20 times moles of three fluorenes diester, preferably 10 Times mole below, more preferably less than 5 times moles.

On the other hand, if the consumption of alkali is very few, then raw material three fluorenes diester (1) or three fluorenes as follows as intermediate Single aryl ester (1e) there may be residual, thus as lower limit, be commonly angled relative to raw material three fluorenes diester (1) be more than 1 times mole, It is preferably more than 1.5 times moles, more preferably more than 2 times moles.

[changing 54]

<1.8.4.3.1.2 catalyst for ester exchange reaction>

As catalyst for ester exchange reaction, can enumerate: four titanium butoxide, four isobutoxy titaniums, titanium tetramethoxide, four different Titanium propanolate, purity titanium tetraethoxide, four (2-ethyl hexyl oxy) titanium, four (octadecyl) orthotitanate, 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 compoundss such as cyclopentadienyl zirconium；Vulcanized lead, Lead oxide hydrate, 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；Hydrated ferric oxide., ferric carbonate, triacetoxyl group ferrum, trimethoxy ferrum, triple phenoxyl ferrum Deng iron compound；The zinc impregnations such as bis-acetylacetonate zinc, diacetoxy zinc, dimethoxy zinc, diethoxy zinc, two phenoxy group zinc are closed Thing；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 stannum, four phenoxy group stannum, The organo-tin compounds such as the tetrabutyl-1,3-diacetoxy distannoxane；Aluminium acetate, aluminum methoxide, aluminum ethoxide, phenoxy group aluminum Deng aluminium compound；The vfanadium compound such as vanadium dichloride, vanadium trichloride, vanadium tetrachloride, Sulfovanadic acid；The salt such as phenoxy group tetraphenylphosphonium Deng.They can be used alone one, it is also possible to share two or more.

Among these, for reasons of, the superiority that has on operation low for industrial cost, salt, lithium are preferably used Compound, zirconium compounds, organo-tin compound or titanium compound etc., wherein particularly preferably organo-tin compound or titanizing are closed Thing.

About the consumption of catalyst for ester exchange reaction, there is no the special upper limit relative to raw material three fluorenes diester (1), if but consumption Too much, then there is the tendency that reacted refined load increases, thus usually fluorenes 20 moles of below %, be preferably and 10 rub You are below %, more preferably 5 moles of below %.

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

<1.8.4.3.1.3 solvent>

Reaction dissolvent can be used in operation (iic), but the most do not use reaction dissolvent, merely with raw material three fluorenes diester (1), diaryl carbonate esters and catalyst for ester exchange reaction react.But, at raw material three fluorenes diester (1), diaryl Carbonates room temperature is solid, be difficult to stir in the case of, it is possible to use reaction dissolvent.In the situation using reaction dissolvent Under, as long as can suitably dissolve and/or disperse above-mentioned raw materials three fluorenes diester (1), diaryl carbonate esters and ester exchange The solvent of catalysts, its kind is arbitrary.

Specifically, it is possible to the solvent of use can be enumerated: as the acetonitrile of alkyl nitrile series solvent, propionitrile etc.；As ketone The acetone of series solvent, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.；As the diethyl ether of ether series solvent, oxolane, 1,4-dioxy Six rings, methylcyclopentyl ether, t-butyl methyl ether etc.；As the 1,2-dichloroethanes of halogen series solvent, dichloromethane, chloroform, 1, 1,2,2-sym-tetrachloroethane etc.；As the chlorobenzene of halogen system aromatic hydrocarbon, 1,2-dichloro-benzenes etc.；As the N of amide series solvent, N-bis- Methylformamide, DMAC N,N' dimethyl acetamide etc.；As the dimethyl sulfoxide of sulfoxide series solvent, sulfolane etc.；As ring type fat The monocyclic aliphatic hydrocarbon such as the Pentamethylene. of fat race hydrocarbon, hexamethylene, cycloheptane, cyclooctane, for methyl cyclopentane, the second of its derivant Cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-diformazan basic ring Hexane, isopropyl cyclohexane, n-pro-pyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene, 1,2,4- Trimethyl-cyclohexane, 1,3,5-trimethyl-cyclohexane etc.；The polycycle aliphatic hydrocarbons such as decahydronaphthalenes；Pentane, normal hexane, positive heptan The non-ring type aliphatic hydrocarbons such as alkane, normal octane, isobutyltrimethylmethane., n-nonane, n-decane, n-dodecane, n-tetradecane；As aromatic hydrocarbon Toluene, xylol, o-Dimethylbenzene, meta-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-tetrahydrochysene Naphthalene etc.；Pyridine etc. as heteroaromatic.

Owing to carrying out under this reaction preferably high temperature more than usually 100 DEG C, thus in above-mentioned solvent, preferably boiling point Be the chlorobenzene of the solvent of more than 100 DEG C, 1,2-dichloro-benzenes, trichloro-benzenes, toluene, xylol, o-Dimethylbenzene, meta-xylene, 1, 3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-naphthane, decahydronaphthalenes, N,N-dimethylformamide, N, N-diformazan Yl acetamide, dimethyl sulfoxide or sulfolane, for can suitably dissolve raw material three fluorenes diester (1), boiling point be 130 DEG C with Upper, the reason of the reaction that can carry out under higher temperature, particularly preferred 1,2-dichloro-benzenes, dimethylbenzene, 1，3，5-trimethyl-benzene, 1, 2,4-trimethylbenzene or 1,2,3,4-naphthane, decahydronaphthalenes.

About the consumption of solvent, the upper limit is not particularly limited, if in view of the generation effect of the goal object in each reactor Rate, then generally use reach raw material three fluorenes diester (1) 15 times of volumes, be preferably 10 times of volumes, more preferably 5 times The amount of volume.On the other hand, if the consumption of solvent is very few, then the dissolubility of reagent is deteriorated, stirring becomes difficulty, has reaction simultaneously Carrying out be inclined to slowly, thus as lower limit, generally use and reach 1 times of volume of raw material three fluorenes diester (1), be preferably 2 The amount of times volume, more preferably 4 times of volumes.

<1.8.4.3.1.4 reaction formation>

When carrying out operation (iic), the form of reaction can use batch-type reaction, circulation type reaction or their combinations Form, its form is not particularly limited.

<1.8.4.3.1.5 reaction condition>

In operation (iic), if temperature is too low, then there is the tendency that can not get sufficient response speed, thus generally exist Lower limit 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 in the upper limit, is preferably Implement for 200 DEG C, more preferably 180 DEG C.

About the General reactions time in operation (iic), usual lower limit is 1 hour, is preferably 2 hours, further preferably Being 3 hours, the upper limit is not particularly limited, usually 30 hours, preferably 20 hours, more preferably 10 hours.

In operation (iic), in order to make balance offset to product side, by-product can be under reduced pressure distilled off and enter simultaneously Row reaction.In the case of reducing pressure, pressure be usually below 20kPa, be preferably below 10kPa, more preferably 5kPa with Under implement.On the other hand, if vacuum is too high, then may continuous cropping be that the diaryl carbonate esters that reagent uses also rises China, thus in usually more than 0.1kPa, preferably more than 0.5kPa, more preferably 1.0kPa enforcement carried out above.

After termination of the reaction, poor solvent can be added in reactant liquor, make goal object three fluorene diaryl ester (1c) separate out, by This separates.

Additionally, after termination of the reaction, it is possible to the solvent of solubilized goal object three fluorene diaryl ester (Ic) is added to water In reactant liquor, extract.Utilize the goal object that solvent extraction goes out can be by the method that solvent is concentrated or add not The methods of good solvent etc. separate.

Three obtained fluorene diaryl esters (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 can be used System, column chromatography etc., and unrestrictedly.

<2 low polyfluorene diester compositions>

The low polyfluorene diester compositions of the present invention comprises three above-mentioned fluorenes diester and two fluorenes diester.By not only comprising three Fluorenes diester also comprises two fluorenes diester, has the tendency that thermostability or optical characteristics can be adjusted to desired situation easily.

<2.1 2 fluorenes diester>

The two fluorenes diester contained by low polyfluorene diester compositions of the present invention comprise 2 fluorenes with or without substituent group Unit b, the carbon atom of 9 of this fluorenes unit b be bonded directly with one another or by with or without substituent group alkylidene, Arlydene with or without substituent group or the sub-aralkyl with or without substituent group are bonded with chain.

As fluorenes unit b, it may be preferred to use as the fluorenes unit illustrated in fluorenes unit a.Low polyfluorene diester compositions institute Fluorenes unit b in the two fluorenes diester contained can be the same or different with the fluorenes unit a in three contained fluorenes diester.

Alkylidene as bonding fluorenes unit b, it may be preferred to use the Asia illustrated in the alkylidene as bonding fluorenes unit a Alkyl.The alkylidene of the bonding fluorenes unit b in two fluorenes diester contained by low polyfluorene diester compositions and three contained fluorenes two The alkylidene of the bonding fluorenes unit a in ester can be the same or different.

Similarly, as the arlydene of bonding fluorenes unit b, it may be preferred to use the arlydene institute as bonding fluorenes unit a The arlydene illustrated.The arlydene of the bonding fluorenes unit b in two fluorenes diester contained by low polyfluorene diester compositions is with contained Three fluorenes diester in the arlydene of bonding fluorenes unit a can be the same or different.

Additionally, as the sub-aralkyl of bonding fluorenes unit b, it may be preferred to use the sub-aralkyl as bonding fluorenes unit a Illustrated sub-aralkyl.The sub-aralkyl of the bonding fluorenes unit b in two fluorenes diester contained by low polyfluorene diester compositions with The sub-aralkyl of the contained bonding fluorenes unit a in three fluorenes diester can be the same or different.

The two fluorenes diester contained by low polyfluorene diester compositions of the present invention can be: is being positioned at the fluorenes unit b of two ends The carbon atom of 9 on be bonded with substituents alpha respectively³And α⁴, in this substituents alpha³And α⁴On be bonded with ester group.In this case, α³And α⁴Can be the same or different.It addition, substituents alpha³And α⁴In comprise Direct Bonding, i.e. at the carbon of 9 of fluorenes unit a Ester group can be had with Direct Bonding on atom.Alternatively base α³And α⁴, it may be preferred to use alternatively base α¹And α²Illustrated Substituent group.Similarly, as ester group, it may be preferred to use as the ester group illustrated in the ester group in three fluorenes diester.

As two fluorenes diester contained by the low polyfluorene diester compositions of the present invention, specifically, it may be preferred under use State the material represented by formula (2).

[changing 55]

R³It is each independently the alkylidene that carbon number is 1～10 with or without substituent group, has or do not have The carbon number of substituted base is the arlydene of 4～10 or with or without the Asia that carbon number is 6～10 of substituent group Aralkyl,

R⁴～R⁹It is each independently hydrogen atom, the alkyl that carbon number is 1～10 with or without substituent group, tool There is or do not have the aryl that carbon number is 4～10 of substituent group, be 1～10 with or without the carbon number of substituent group Acyl group, the acyloxy that carbon number is 1～10 with or without substituent group, the carbon number with or without substituent group Be the alkoxyl of 1～10, with or without the aryloxy group that carbon number is 1～10 of substituent group, with or without replacement The amino of base, there is the sulphur atom of substituent group, halogen atom, nitro or cyano group.Wherein, at R⁴～R⁹In, at least 2 adjacent bases Group can be mutually bonded formation ring.

R¹⁰Be carbon number be the organic substituent of 1～10.

It should be noted that formula (2) is respectively provided with the R of 2⁴～R⁹Can be the same or different respectively.Similarly, Formula (2) has the R of 2¹⁰Can be the same or different respectively.

As the R in above-mentioned formula (2)¹～R¹⁰, it may be preferred 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 low polyfluorene diester compositions of the present invention, following [I] can be enumerated Structure shown in group.

[changing 56]

[changing 57]

The physics value of the two fluorenes diester contained by low polyfluorene diester compositions of the present invention is not particularly limited, the most satisfied Physics value illustrated below.

The decomposition temperature that the two fluorenes diester of the present invention measure in a nitrogen atmosphere is preferably more than 250 DEG C, is more preferably 270 More than DEG C, more preferably more than 290 DEG C, usually less than 300 DEG C.The two fluorenes diester of the present invention are tied by the lamination of fluorenes ring Structure and make structure upright and outspoken, therefore there is decomposition temperature and meet the tendency of above-mentioned scope.Above-mentioned model is met by such decomposition temperature Enclose, have and can improve polyester, the tendency of heat stability of Merlon obtained by two fluorenes diester.Decomposition temperature such as can be led to Cross TG-DTA to be measured.

Additionally, the fusing point (m.p.) of the two fluorenes diester of the present invention is preferably more than 100 DEG C, more preferably more than 120 DEG C, enters One step is preferably more than 140 DEG C, 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 has fusing point and meets the tendency of above-mentioned scope.Meet above-mentioned scope by such fusing point, have and can improve by two Polyester that fluorenes diester obtains, the tendency of the heat stability of Merlon.Fusing point such as can be measured by TG-DTA.

Content ratio for three fluorenes diester contained by the low polyfluorene diester compositions of the present invention is not particularly limited, from Improve thermostability and then i.e. can get the aspect of desired optical characteristics with lesser amount of use and set out, relative to compositions Gross mass be preferably more than more than more than 0.1 mass %, more preferably 0.5 mass %, more preferably 1 mass %, more More preferably more than 3 mass %, more than particularly preferably 5 mass %, and usually below 30 mass %.

On the other hand, the content ratio for two fluorenes diester contained by low polyfluorene diester compositions is not particularly limited, From flexibility and the aspect of the adjustment of optical characteristics, relative to the gross mass of compositions, more than preferably 0.1 mass %, More than more preferably 0.3 mass %, more preferably more than 1 mass %, further it is preferably more than 3 mass %, especially It is preferably more than 5 mass %, and from the standpoint of improving thermostability, below preferably 50 mass %, is more preferably 40 matter Below amount below %, more preferably 30 mass %.

It addition, the content ratio for two fluorenes diester contained by low polyfluorene diester compositions and three fluorenes diester is the most special Limit, from flexibility and the aspect of the adjustment of optical characteristics, two fluorenes diester contained in compositions and three fluorenes diester Mol ratio (molal quantity of the molal quantity/tri-fluorenes diester of two fluorenes diester) is preferably more than 0.001, more preferably more than 0.003, enter One step is preferably more than 0.01, further preferably more than 0.03, particularly preferably more than 0.05, additionally from improving thermostability From the standpoint of, preferably less than 0.5, more preferably less than 0.4, more preferably less than 0.3.

About two fluorenes diester contained in low polyfluorene diester compositions, the molal quantity of three fluorenes diester, such as, can utilize The area % that calibration trace is analyzed by HPLC estimates.

<3 resin combination>

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

So, for the resin combination of the present invention, except containing three fluorenes the gathering as repetitive with divalent Outside compound, it is also possible to containing other polymer described later, additionally can also be containing additive etc..Further, the resin group of the present invention Compound can also be formed by having three fluorenes of the divalent polymer as repetitive.

Polymer contained by the resin combination of the present invention has three fluorenes of divalent as repetitive.So, by tool There are three fluorenes of divalent as repetitive, this three fluorenes can be used to obtain desired optical characteristics by a small amount of, additionally have Can be shown that the tendency of good thermostability.

It should be noted that the polymer contained by the resin combination of the present invention can also have the most further Two fluorenes of divalent are as repetitive.Sometimes three fluorenes and two fluorenes are referred to as low polyfluorene.

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

As fluorenes unit a, it may be preferred to use as the fluorenes unit illustrated in the fluorenes unit a of three fluorenes diester.

Similarly, as the alkylidene of bonding fluorenes unit a, it may be preferred to use the bonding fluorenes unit a as three fluorenes diester The alkylidene illustrated in alkylidene.It addition, as the arlydene of bonding fluorenes unit a, it may be preferred to use as three fluorenes diester The arlydene illustrated in arlydene of bonding fluorenes unit a.Additionally, as the sub-aralkyl of bonding fluorenes unit a, it may be preferred to make It is used as the sub-aralkyl illustrated in sub-aralkyl of the bonding fluorenes unit a of three fluorenes diester.

Three fluorenes of above-mentioned divalent can also be: in 3 fluorenes unit a, is positioned at the carbon atom of 9 of fluorenes unit a of two ends Upper it is bonded with substituents alpha respectively¹And α², make this substituents alpha¹And α²For divalent group.In this case, α¹And α²Can identical also Can be different.It addition, substituents alpha¹And α²In comprise Direct Bonding, i.e. the carbon atom that can also make 9 of fluorenes unit a is divalent Group.Alternatively base α¹And α², it may be preferred to use as the substituents alpha in three fluorenes diester¹And α²Illustrated substituent group.

Particularly, in the case of the carbon atom making 9 that are positioned at the fluorenes unit a of two ends is divalent group, or position is made 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 In the case of the carbon number of at least 1 is more than 2, due to fluorenes ring (fluorenes unit a) is generally perpendicularly orientated relative to main chain, because of Even and if the ratio of the low polyfluorene of the divalent in resin combination is few, it may have easily show the tendency of inverse wave length dispersibility.? In the case of the latter, from same aspect, preferably make α¹And α²Both carbon numbers are 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 α²Both carbon atoms In the case of number is 1 (that is, with or without the methylene of substituent group), (fluorenes unit a) is not big relative to main chain to fluorenes ring Cause is vertically oriented, and is orientated the most obliquely, so even the low polyfluorene of the divalent in wide range resin combination Ratio, it may have be easily formed at the tendency of the little smooth dispersibility of the difference of phase contrast in wide band.

So, the resin combination of the present invention uses spy each other by the carbon atom containing 9 had 3 fluorenes unit a The polymer of the repetitive that fixed carbon-carbon bond is formed by connecting, such that it is able to more effectively obtain the optical characteristics from fluorenes ring.

As three fluorenes of above-mentioned divalent, specifically, it may be preferred to use the material represented by following formula (11).

[changing 58]

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

It should be noted that the R in formula (11)^3aAnd R^3bCan be the same or different respectively.It addition, formula (11) is divided Not there is the R of 3⁴～R⁹Can be the same or different respectively.

As the R in above-mentioned formula (11)¹～R⁹, it may be preferred to use as the R in above-mentioned formula (1)¹～R⁹Illustrated base Group.

Polymer in the resin combination of the present invention can have two fluorenes of divalent further as repetitive.Pass through Possibly together with two fluorenes of divalent in addition to three fluorenes of divalent, have and easily thermostability or optical characteristics can be adjusted to desired feelings The tendency of condition.

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

As fluorenes unit b, it may be preferred to use as the fluorenes unit illustrated in the fluorenes unit b of two fluorenes diester.

Similarly, as the alkylidene of bonding fluorenes unit b, it may be preferred to use the bonding fluorenes unit b as two fluorenes diester The alkylidene illustrated in alkylidene.It addition, as the arlydene of bonding fluorenes unit b, it may be preferred to use as two fluorenes diester The arlydene illustrated in arlydene of bonding fluorenes unit b.Additionally, as the sub-aralkyl of bonding fluorenes unit b, it may be preferred to make It is used as the sub-aralkyl illustrated in sub-aralkyl of the bonding fluorenes unit b of two fluorenes diester.

Two fluorenes of above-mentioned divalent can also be: is bonded with respectively on the carbon atom of 9 of the fluorenes unit b being positioned at two ends Substituents alpha³And α⁴, make this substituents alpha³And α⁴For divalent group.In this case, α³And α⁴Can be the same or different.Separately Outward, substituents alpha³And α⁴In comprise Direct Bonding, i.e. the carbon atom that can also make 9 of fluorenes unit b is divalent group.As taking For base α³And α⁴, it may be preferred to use as the substituents alpha in two fluorenes diester³And α⁴Illustrated group.

Particularly, in the case of the carbon atom making 9 that are positioned at the fluorenes unit b of two ends is divalent group, or position is made 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 In the case of the carbon number of at least 1 is more than 2, due to fluorenes ring (fluorenes unit b) is generally perpendicularly orientated relative to main chain, because of Even and if the ratio of the low polyfluorene of the divalent in resin combination is few, it may have easily show the tendency of inverse wave length dispersibility.? In the case of the latter, from same aspect, preferably make α³And α⁴Both carbon numbers are more than 2.On the other hand, exist Make the α being bonded respectively on the carbon atom of 9 of fluorenes unit b of two ends³And α⁴For divalent group and make α³And α⁴Both carbon is former In the case of subnumber is 1 (that is, with or without the methylene of substituent group), (fluorenes unit b) relative to main chain is not fluorenes ring Generally perpendicularly it is orientated, and is orientated the most obliquely, so even the low polyfluorene of the divalent in wide range resin combination Ratio, it may have be easily formed at the tendency of the little smooth dispersibility of the difference of phase contrast in wide band.

As two fluorenes of above-mentioned divalent, specifically, it may be preferred to use the material represented by following formula (21).

[changing 59]

As the R in above-mentioned formula (21)¹～R⁹, it may be preferred to use as the R in above-mentioned formula (2)¹～R⁹Illustrated base Group.

It should be noted that formula (21) is respectively provided with the R of 2⁴～R⁹Can be the same or different respectively.

<3.3 polymer>

Polymer contained in the resin combination of the present invention has three fluorenes of divalent as repetitive.For example, it is possible to Enumerate the polymer that three fluorenes of divalent are formed by connecting each other by arbitrary linking group.It addition, this polymer can also be for having Two fluorenes of divalent, the copolymer of any repetitive beyond them.

<3.4 linking group>

Hereinafter enumerate the concrete structure of linking group used in above-mentioned polymer, but be not limited to these, Ke Yiju Go out the linking group shown in following [J] group

[changing 60]

[J]

(in each linking group shown in above-mentioned [J] group, Z represents the position that repetitive is connected, and Y represents and other The position that the arbitrary structures unit that the position of linking group bonding or expression make linking group bond together is connected.), can So that two or more in these linking groups are share.Additionally, in the case of linking group is asymmetrical, linking group is permissible It is attached with any direction relative to repetitive.Among them, preferably comprise thermostability and melt processable, mechanical strength The polyester of balancing good, Merlon, polyestercarbonate, the linking group shown in following [K] group.

[changing 61]

[K]

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

Linking group can be used alone a kind of group, it is possible to is share by two or more linking groups.

As the polymer that repetitive is attached through linking group, specifically, can enumerate comprise poly- Alkene, polyester, Merlon, polyamide, polyimides, polyurethane, epoxy resin, polyacrylate, polymethacrylates Or the polymer of polysulfones and they are share the polymer obtained, preferably comprise usually the polyolefin of high transparent, polyester, The polymer of Merlon, epoxy resin or polyacrylate, particularly preferably comprises thermostability and melt processable, mechanical strength The polyester of balancing good or the polymer of Merlon, particularly preferably comprise usual thermostability, chemical proofing excellent The polymer of Merlon.

In the case of making the polymer share by two or more linking groups, the combination about linking group does not has spy Do not limit, such as can enumerate share structural carbonate and ester structure as linking group polymer, share structural carbonate With carbamate structures as linking group polymer, share ester structure and the amide polymer etc. as linking group, Preferably can enumerate the polymer share structural carbonate and ester structure as linking group.Herein, two or more as share The concrete example of polymer of linking group, can enumerate polyestercarbonate, have the polyurethane of carbonic acid ester bond, polyesteramide, Polyesterimide etc., among them, preferably thermostability and melt processable, the polyestercarbonate of the balancing good of mechanical strength. In this specification, the polymer with carbonic acid ester bond is referred to as Merlon, except only there is carbonic acid ester bond as linking group Polymer outside, also comprise polyestercarbonate (there is the polymer of ester bond and carbonic acid ester bond), there is the polyurethane of carbonic acid ester bond Deng.Herein, the ratio comprising the carbonic acid ester bond in the polymer of Merlon can be arbitrary value, but in order to resin combination Give the characteristic that thermostability, the chemical proofing etc. brought by carbonic acid ester bond are excellent, be preferably more than certain proportion, carbonic acid Ester bond molar fraction in whole linking groups is preferably more than 30%, more preferably more than 50%, more preferably More than 60%, particularly preferably more than 70%, usually less than 100%.

<3.5 copolymer>

Having three fluorenes of divalent as the polymer of repetitive can be to contain arbitrary divalent organic group (its further In, do not include three fluorenes of divalent and two fluorenes of divalent) as the copolymer of repetitive.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 share with three fluorenes of divalent, from controlling in resin combination Optical characteristics required in thing and the aspect of the scope of physical property are set out, it may be preferred to use the divalent represented by following formula (3) Organic group.In this case, as arbitrary divalent organic group, can share the divalent represented by formula (3) further has Divalent organic group beyond machine group.

[changing 62]

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

In the case of polymer contains the divalent organic group represented by above-mentioned formula (3), except undertaking resin group Compound gives beyond the anisotropic function of positive refracting power, also can be by the wavelength dispersibility of phase contrast or photoelastic coefficient etc The various resin characteristics such as optics physical property and mechanical strength, thermostability, melt processable controls in the range of preferably, has Can at random control the tendency of the physical property of resin combination.

Even if it should be noted that not there is the aromatic rings vertical orientated relative to main chain or there is such fragrance Its most less resin combination of ratio in entirety of ring generally demonstrates positive refracting power anisotropy, and this is well-known 's.In the repetitive of the divalent organic group represented by above-mentioned formula (3), in addition to there is the structure of aromatic rings at side chain, All anisotropic structures of positive refracting power that demonstrates, thus it can be said that contain above-mentioned formula (3) institute of 50 moles of more than % The resin combination of the divalent organic group represented demonstrates positive refracting power anisotropy.

As it has been described above, the R in formula (3)²⁰Represent the alkylene that carbon number is 2～20 with or without substituent group Base, the arlydene that carbon number is 4～20 with or without substituent group, the carbon number with or without substituent group are The alkylidene ether of 2～100, the organic group with alicyclic structure that carbon number is 4～20 with or without substituent group Group or the organic group with heterocycle structure that carbon number is 4～20 with or without substituent group.

Hereinafter enumerate the concrete structure of " with or without the alkylidene that carbon number is 2～20 of substituent group ", but also It is not limited to these, the alkylene of the straight-chain such as ethylidene, positive propylidene, positive butylidene, positive pentylidene, positive hexylidene can be enumerated Base；1-methyl ethylidene, 2-methyl ethylidene, 1-ethylethylene residue, 2-ethylethylene residue, 1-methyl propylene, 2-methyl are sub- Propyl group, 2,2-dimethylpropylidene, 3-methyl propylene etc. comprise the alkylidene of side chain.Its carbon number is more than 2 and excellent Elect less than 12, more preferably less than 6 as.Among them, preferably there is appropriate hydrophobicity and flexibility and there is the low light of imparting The alkylidene of the straight-chain represented by formula (5) tendency of coefficient of elasticity, following.

[changing 63]

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

Hereinafter enumerate the concrete knot of " with or without the straight-chain alkylidene that carbon number is 0～18 of substituent group " Structure, but it is not limited to these, ethylidene, positive propylidene, 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.

Hereinafter enumerate the concrete structure of " with or without the arlydene that carbon number is 4～20 of substituent group ", but also It is not limited to these, can enumerate 1,2-phenylene, 1, the phenylene such as 3-phenylene, Isosorbide-5-Nitrae-phenylene；1,5-naphthylene, 2,6-are sub- The naphthylenes such as naphthyl；The heteroarylidenes such as 2,5-pyridylidene, 2,4-Asia thienyl, 2,4-furylidene.Its carbon number is preferred It is more than 4 and is less than 8, more preferably less than 6.Among them, from industrial can obtain at low cost in terms of go out Send out, preferably 1,2-phenylene, 1,3-phenylene or Isosorbide-5-Nitrae-phenylene.

As " with or without the alkylidene that carbon number is 2～20 of substituent group ", " with or without substituent group The straight-chain alkylidene that carbon number is 0～18 " with " with or without the sub-virtue that the carbon number of substituent group is 4～20 Base " substituent group that can have, can enumerate: halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine)；Carbon number It it is the alkyl (such as methyl, ethyl, isopropyl etc.) of 1～10；Carbon number is alkoxyl (the such as methoxyl group, ethoxy of 1～10 Base etc.)；Carbon number is the acyl group (such as acetyl group, benzoyl etc.) of 1～10；Carbon number is the amide groups (example of 1～10 Such as acetamido, benzamido etc.)；Nitro；Cyano group；With or without selected from halogen atom (such as fluorine atom, chlorine atom, Bromine atoms, atomic iodine), carbon number be 1～10 alkyl (such as methyl, ethyl, isopropyl etc.), carbon number be 1～10 Alkoxyl (such as methoxyl group, ethyoxyl etc.), carbon number be 1～10 acyl group (such as acetyl group, benzoyl etc.), carbon Atomic number be 1～10 amide groups (such as acetamido, benzamido etc.), nitro, 1～3 substituent group in cyano group etc. The aryl that carbon number is 6～10 (such as phenyl, naphthyl etc.) etc..The quantity of this substituent group is not particularly limited, preferably 1～ 3.In the case of substituent group is more than 2, the kind of substituent group can be the same or different.It addition, from industrial can The aspect manufactured at low cost is set out, the most unsubstituted.

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

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

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

[changing 64]

[L]

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

The substituent group can having as " with or without the sub-aralkyl that carbon number is 6～20 of substituent group ", Can enumerate: halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine)；Carbon number is alkyl (the such as first of 1～10 Base, ethyl, isopropyl etc.)；Carbon number is the alkoxyl (such as methoxyl group, ethyoxyl etc.) of 1～10；Carbon number be 1～ The acyl group (such as acetyl group, benzoyl etc.) of 10；Carbon number is amide groups (the such as acetamido, Benzoylamide of 1～10 Base etc.)；Nitro；Cyano group；With or without former selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine), carbon Subnumber be 1～10 alkyl (such as methyl, ethyl, isopropyl etc.), carbon number be 1～10 alkoxyl (such as methoxyl group, Ethyoxyl etc.), carbon number be 1～10 acyl group (such as acetyl group, benzoyl etc.), carbon number be 1～10 amide The carbon number of 1～3 substituent group in base (such as acetamido, benzamido etc.), nitro, cyano group etc. is 6～10 Aryl (such as phenyl, naphthyl etc.) etc..The quantity of this substituent group is not particularly limited, preferably 1～3.Substituent group is more than 2 In the case of, the kind of substituent group can be the same or different.It addition, from industrial can manufacture at low cost in terms of go out Send out, the most unsubstituted.

" with or without the alkylidene ether that carbon number is 2～100 of substituent group " refers to the Asia with more than 1 Alkyl and the divalent group of 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, more preferably less than 40, particularly preferably less than 30.More specifically, can enumerate: under State formula (7)

[changing 65]

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

[changing 66]

(in formula, R^2-14Represent the alkylidene that carbon number is 2～10 with or without substituent group, R^2-15Expression has Or not there is the arlydene that carbon number is 12～30 of substituent group.).

In formula (7) and formula (8), R^2-13And R^2-14Represent that the carbon number with or without substituent group is 2～10 Alkylidene.Enumerate its concrete structure below, but be not limited to these, can enumerate: ethylidene, positive propylidene, positive butylidene, just The alkylidene of the straight-chain such as pentylidene, positive hexylidene；1-methyl ethylidene, 2-methyl ethylidene, 1-ethylethylene residue, 2-ethyl Ethylidene, 1-methyl propylene, 2-methyl propylene, 2,2-dimethylpropylidene, 3-methyl propylene etc. comprise the Asia of side chain Alkyl (numerical value of the position of substitution counting from the carbon of end side herein) etc..

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

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

These R^2-13And R^2-14In, the preferably alkylidene of straight-chain, the alkylidene of straight-chain due to do not have asymmetric point because of And easily carry out the qualitative control of monomer, more preferably can import the most at low cost, flexibility and water absorption can be given Ethylidene.

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

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

[changing 67]

[M]

The substituent group can having as " with or without the arlydene that carbon number is 12～30 of substituent group ", can To enumerate: halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine)；Carbon number is alkyl (the such as first of 1～10 Base, ethyl, isopropyl etc.)；Carbon number is the alkoxyl (such as methoxyl group, ethyoxyl etc.) of 1～10；Carbon number be 1～ The acyl group (such as acetyl group, benzoyl etc.) of 10；Carbon number is amide groups (the such as acetamido, Benzoylamide of 1～10 Base etc.)；Nitro；Cyano group；With or without former selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine), carbon Subnumber be 1～10 alkyl (such as methyl, ethyl, isopropyl etc.), carbon number be 1～10 alkoxyl (such as methoxyl group, Ethyoxyl etc.), carbon number be 1～10 acyl group (such as acetyl group, benzoyl etc.), carbon number be 1～10 amide The carbon number of 1～3 substituent group in base (such as acetamido, benzamido etc.), nitro, cyano group etc. is 6～10 Aryl (such as phenyl, naphthyl etc.) etc..The quantity of this substituent group is not particularly limited, preferably 1～3.Substituent group is more than 2 In the case of, the kind of substituent group can be the same or different.It addition, from industrial can manufacture at low cost in terms of go out Send out, the most unsubstituted.

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

[changing 68]

[N]

(in above-mentioned [N] group, about being the structure of diastereomer, can be any one diastereomer, it is also possible to for Non-enantiomer mixture.)

Hereinafter enumerate the concrete structure of formula (8), but be not limited to these, can enumerate: the alkylidene shown in following [O] group Ether.

[changing 69]

[O]

(in above-mentioned [O] group, about being the structure of diastereomer, can be any one diastereomer, it is also possible to for Non-enantiomer mixture.)

Hereinafter enumerate " the organic group with alicyclic structure that carbon number is 4～20 with or without substituent group Or the organic group with heterocycle structure that carbon number is 4～20 with or without substituent group " concrete structure, but It is not limited to these, for reasons of having and can improving glass transition temperature, the tendency of photoelastic coefficient can be reduced, excellent Choosing can enumerate the Asia at any the 2 of the alicyclic structure shown in following [P] group or heterocycle structure 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 is Direct Bonding or the straight-chain of carbon number 1～5 or side chain The alkylidene of shape, 2 combine key length can be different.Preferably associative key is that reducing of glass transition temperature is few direct Bonding or methylene.

As " the organic group with alicyclic structure that carbon number is 4～20 or the tool with or without substituent group The carbon number having or not having substituent group is the organic group with heterocycle structure of 4～20 " substituent group that can have, can To enumerate: halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine)；Carbon number is alkyl (the such as first of 1～10 Base, ethyl, isopropyl etc.)；Carbon number is the alkoxyl (such as methoxyl group, ethyoxyl etc.) of 1～10；Carbon number be 1～ The acyl group (such as acetyl group, benzoyl etc.) of 10；Carbon number is amide groups (the such as acetamido, Benzoylamide of 1～10 Base etc.)；Nitro；Cyano group；With or without former selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine), carbon Subnumber be 1～10 alkyl (such as methyl, ethyl, isopropyl etc.), carbon number be 1～10 alkoxyl (such as methoxyl group, Ethyoxyl etc.), carbon number be 1～10 acyl group (such as acetyl group, benzoyl etc.), carbon number be 1～10 amide The carbon number of 1～3 substituent group in base (such as acetamido, benzamido etc.), nitro, cyano group etc. is 6～10 Aryl (such as phenyl, naphthyl etc.) etc..The quantity of this substituent group is not particularly limited, preferably 1～3.Substituent group is more than 2 In the case of, the kind of substituent group can be the same or different.It addition, from industrial can manufacture at low cost in terms of go out Send out, the most unsubstituted.

Hereinafter enumerate " the organic group with alicyclic structure that carbon number is 4～20 with or without substituent group Or the organic group with heterocycle structure that carbon number is 4～20 with or without substituent group " preferably concrete knot Structure, but be not limited to these, can enumerate: have can give high transparent and glass transition temperature, water absorption, birefringence, Formula (4) tendency of low photoelastic coefficient, following

[changing 71]

Represented group, following formula (6)

[changing 72]

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

[changing 73]

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

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

[changing 74]

[Q]

(in above-mentioned [Q] group, about being the structure of diastereomer, can be any one diastereomer, it is also possible to for Non-enantiomer mixture.)

The substituent group can having as " with or without the ring alkylidene that carbon number is 4～20 of substituent group ", Can enumerate: halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine)；Carbon number is alkyl (the such as first of 1～10 Base, ethyl, isopropyl etc.)；Carbon number is the alkoxyl (such as methoxyl group, ethyoxyl etc.) of 1～10；Carbon number be 1～ The acyl group (such as acetyl group, benzoyl etc.) of 10；Carbon number is amide groups (the such as acetamido, Benzoylamide of 1～10 Base etc.)；Nitro；Cyano group；With or without former selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine), carbon Subnumber be 1～10 alkyl (such as methyl, ethyl, isopropyl etc.), carbon number be 1～10 alkoxyl (such as methoxyl group, Ethyoxyl etc.), carbon number be 1～10 acyl group (such as acetyl group, benzoyl etc.), carbon number be 1～10 amide The carbon number of 1～3 substituent group in base (such as acetamido, benzamido etc.), nitro, cyano group etc. is 6～10 Aryl (such as phenyl, naphthyl etc.) etc..The quantity of this substituent group is not particularly limited, preferably 1～3.Substituent group is more than 2 In the case of, the kind of substituent group can be the same or different.It addition, from industrial can manufacture at low cost in terms of go out Send out, the most unsubstituted.

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

[changing 75]

[R]

(in above-mentioned [R] group, about being the structure of diastereomer, can be any one diastereomer, it is also possible to for Non-enantiomer mixture.).Among these, from the industrial aspect that can obtain at low cost, the most following [R-2] group Shown in the organic group with alicyclic structure.

[changing 76]

[R-2]

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

[changing 77]

[S]

(in above-mentioned [S] group, about being the structure of diastereomer, can be any one diastereomer.)

The substituent group can having as " with or without the acetal ring that carbon number is 2～20 of substituent group ", Can enumerate: halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine)；Carbon number is alkyl (the such as first of 1～10 Base, ethyl, isopropyl etc.)；Carbon number is the alkoxyl (such as methoxyl group, ethyoxyl etc.) of 1～10；Carbon number be 1～ The acyl group (such as acetyl group, benzoyl etc.) of 10；Carbon number is amide groups (the such as acetamido, Benzoylamide of 1～10 Base etc.)；Nitro；Cyano group；With or without former selected from halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine), carbon Subnumber be 1～10 alkyl (such as methyl, ethyl, isopropyl etc.), carbon number be 1～10 alkoxyl (such as methoxyl group, Ethyoxyl etc.), carbon number be 1～10 acyl group (such as acetyl group, benzoyl etc.), carbon number be 1～10 amide The carbon number of 1～3 substituent group in base (such as acetamido, benzamido etc.), nitro, cyano group etc. is 6～10 Aryl (such as phenyl, naphthyl etc.) etc..The quantity of this substituent group is not particularly limited, preferably 1～3.Substituent group is more than 2 In the case of, the kind of substituent group can be the same or different.It addition, from industrial can manufacture at low cost in terms of go out Send out, the most unsubstituted.

The preferred group in divalent organic group represented by formula (3) is the alkylidene with or without substituent group, tool There is or do not has the alkylidene ether of substituent group, with or without the organic group with alicyclic structure of substituent group or tool Have or do not have the organic group with heterocycle structure of substituent group, these preferred group do not have in main chain aromatic rings or A large amount of part-structures contained beyond aromatic rings in main chain, thus have and be capable of in blooming required low photoelasticity The tendency of coefficient.More preferably at least one in following radicals:

There is the tendency that can give high transparent and glass transition temperature, water absorption, birefringence, low photoelastic coefficient Following formula (4),

[changing 78]

Or there is hydrophobicity and the flexibility of appropriateness, there is the following formula (5) of the tendency that can give low photoelastic coefficient

[changing 79]

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

[changing 80]

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

[changing 81]

(in formula, R^2-13Representing the alkylidene that carbon number is 2～10 with or without substituent group, p is 1～40 Integer.) or there is the following formula (8) that can give high transparent with the tendency of glass transition temperature

[changing 82]

(in formula, R^2-14Represent the alkylidene that carbon number is 2～10 with or without substituent group, R^2-15Expression has Or not there is the arlydene that carbon number is 12～30 of substituent group.) or have and can give high transparent and glass transition Temperature, the following formula (9) of birefringent tendency

[changing 83]

(in formula, R^2-16Represent the base with acetal ring that carbon number is 2～20 with or without substituent group Group.).Group represented by further preferred above-mentioned formula (4), the group represented by above-mentioned formula (4) is by giving high transparency Property can give inclining of the physical property excellent as phase retardation film with glass transition temperature, water absorption, low photoelastic coefficient and having To.

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

Divalent organic group represented by formula (3) is share two or more in the case of, limit the most especially about a combination thereof Fixed.Such as, for giving high transparent and glass transition temperature, birefringent purpose, represented by the most above-mentioned formula (4) Organic group represented by organic group or above-mentioned formula (9), for the purpose of imparting flexibility, the most above-mentioned formula (5) institute Organic group represented by the organic group represented or above-mentioned formula (7), on the other hand, for giving high transparent and glass Changing the purpose of the flexibility of transition temperature, appropriateness, the organic group represented by the most above-mentioned formula (6), among them, according to institute The combination of the purpose required selects the combination of corresponding organic group.In particular, it is preferred that it is above-mentioned for being equivalent to The repetitive that the ISB (isosorbide) of the organic group represented by formula (4) originates is with to be equivalent to above-mentioned formula (6) represented The combination of repetitive originated of the CHDM (1,4 cyclohexane dimethanol) of organic group or be equivalent to above-mentioned formula (9) The repetitive that the SPG (the spiroglycol) of represented organic group originates is organic be equivalent to represented by above-mentioned formula (6) The combination of the repetitive in the CHDM source of group.

<3.7 copolymerization composition>

So, three fluorenes of divalent, two fluorenes of divalent and the divalent organic group represented by formula (3) are at least contained using In the case of the copolymer of repetitive, as long as can show in the range of optics physical property described later, can be above-mentioned Copolymer contains the divalent organic group represented by three fluorenes of divalent, two fluorenes of divalent, formula (3) with any quality.

About the summation of content ratio of two fluorenes of three fluorenes and the divalent of divalent, in order to show inverse wave length dispersibility and guarantee Melt processable, mechanical strength, relative to the quality that above-mentioned copolymer is overall, more than preferably 5 mass %, be more preferably 10 matter More than amount more than %, more preferably 12 mass %, more than particularly preferably 15 mass %, and preferably 90 mass % with Under, below more preferably 80 mass %, more preferably below 70 mass %, below particularly preferably 60 mass %.

It addition, from obtaining the aspect of desired optical characteristics by lesser amount of use, containing of three fluorenes of divalent The proportional Functionality, quality and appealing design overall relative to copolymer elects more than more than 1 mass %, more preferably 3 mass %, further preferably as Be more than more than 5 mass %, particularly preferably 10 mass %, and below preferably 50 mass %, more preferably 40 mass % Below, more preferably below 30 mass %.

It addition, from give positive refracting power anisotropic from the standpoint of, the divalent organic group represented by formula (3) excellent The Functionality, quality and appealing design selecting content ratio overall relative to above-mentioned copolymer elect as more than more than 10 mass %, more preferably 20 mass %, More preferably more than 30 mass %, more than particularly preferably 40 mass %, and below preferably 95 mass %, more preferably It is below below below 90 mass %, more preferably 88 mass %, particularly preferably 85 mass %, most preferably 80 matter Amount below %.

<3.8 polymer are blended>

The resin combination of the present invention contains three fluorenes with divalent as the polymer of repetitive.It addition, the present invention Resin combination is in addition to containing this polymer, it is also possible to contain other composition further.

In the resin combination of the present invention, expect to show by other effect of being brought is blended, it is also possible to containing arbitrarily Polymer as other composition.That is, except have three fluorenes of divalent as the polymer of repetitive in addition to, it is also possible to coexist There is arbitrary polymer.

Coexisting described in herein refers to there is polymer of more than two kinds in resin combination, and this method coexisted does not limits, Can enumerate carry out mixing with the state of solution or melted state by polymer of more than two kinds method, containing more than a kind Polymer solution in or fused solution in carry out the method etc. be polymerized.

For example, it is possible to be blended, there is the polymer as repetitive of the divalent organic group represented by formula (3), it is possible to So that the polymer with arbitrary repetitive is blended.It should be noted that have the divalent organic group represented by formula (3) Polymer as repetitive can have the divalent organic group beyond formula (3) further as repetitive, it is also possible to There is the two or more divalent organic groups represented by formula (3) as repetitive.Herein, as represented by formula (3) Divalent organic group, it is possible to use the group shown in preference in the copolymer.

Particularly from the aspect suitably used as phase retardation film, preferably coexist and demonstrate positive refracting power anisotropy Polymer or the blend of oligomer or copolymer；Good for optical property, have and can carry out melted masking or molten The reason of the tendency of liquid cast masking, more preferably coexist thermoplastic resin.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., wherein preferred polyester or Merlon can be enumerated.

More specifically, can enumerate: the olefin polymer such as polyethylene, polypropylene；Have and derive from bisphenol-A or bis-phenol The Merlon of the construction unit of Z, isosorbide etc.；Polyethylene terephthalate, polybutylene terephthalate (PBT), poly- Naphthalate, polycyclic hexane Dimethylenecyclohexacompound dicarboxylic ester, poly terephthalic acid-1,4 cyclohexane dimethanol ester etc. are poly- Esters etc., can share the polymer of more than two kinds among them.

In the case of the resin combination of the present invention is carried out film molding, owing to preferred film is optically transparent, thus excellent Choosing carries out the polymer that is blended and three fluorenes with divalent have as the refractive index close of the polymer of repetitive or select The combination of the compatibility.

From showing inverse wave length dispersibility and guaranteeing the aspect of melt processable, mechanical strength, resin combination In three fluorenes of divalent and the summation of content ratio of two fluorenes of the divalent Functionality, quality and appealing design overall relative to resin combination elect 5 matter as More than amount more than %, more preferably 10 mass %, more preferably more than 12 mass %, particularly preferably 15 mass % with More than upper, most preferably 20 mass %, and below preferably 90 mass %, below more preferably 80 mass %, the most excellent Elect below below 70 mass %, particularly preferably 60 mass % as.Additionally from same aspect, 2 represented by formula (3) The ratio that preferably comprises of the organic group of the valency Functionality, quality and appealing design overall relative to resin combination elects more than 10 mass %, more preferably as It is more than more than more than 20 mass %, more preferably 30 mass %, particularly preferably 40 mass %, and preferably 95 matter Below amount below %, more preferably 90 mass %, more preferably below 88 mass %, particularly preferably 85 mass % with Under, below most preferably 80 mass %.

It addition, the resin combination of the present invention can be containing the two or more divalent organic groups represented by above-mentioned formula (3) Group, such as, is being applied in combination repetitive that ISB (isosorbide) originates and the weight that CHDM (1,4-CHDM) originates In the case of multiple unit, it is not particularly limited about its content ratio, from high glass-transition temperature and birefringence, water absorption rate Aspect is set out, and the repetitive in ISB source is preferably more than 20 mass %, more excellent relative to resin combination with molar fraction Elect below more than more than 30 mass %, more preferably 40 mass %, and preferably 95 mass %, more preferably 90 matter as Below amount below %, more preferably 80 mass %.

It addition, in the case of the repetitive of the repetitive and CHDM source that are applied in combination ISB source, contain about it Proportional be not particularly limited, from the aspect of flexibility, the repetitive in CHDM source relative to resin combination to rub Your mark meter is preferably more than more than more than 5 mass %, more preferably 10 mass %, more preferably 15 mass %, and It is preferably below below below 60 mass %, more preferably 50 mass %, more preferably 40 mass %.

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

It addition, in the case of the repetitive of the repetitive and CHDM source that are applied in combination SPG source, contain about it Proportional be not particularly limited, from the aspect of flexibility, the repetitive in CHDM source relative to resin combination to rub Your mark meter is preferably more than more than more than 5 mass %, more preferably 10 mass %, more preferably 15 mass %, and It is preferably below below below 60 mass %, more preferably 50 mass %, more preferably 40 mass %.

<3.10 physics value>

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

<3.20 Abbe number>

In the resin combination of the present invention, in the feelings being assumed to be the wide band zero birefraction materials 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, and usually more than 15.

In the resin combination of the present invention, come from the 740cm of fluorenes ring orientation^-1Absorb in draw direction and vertical direction Strength ratio is preferably more than 1.2, more preferably more than 1.3, more preferably more than 1.4, and usually less than 2.0.Will In the case of the resin combination of the present invention is used as inverse wave length dispersion membrane purposes, at the 740cm coming from fluorenes ring orientation^-1Absorption exist During the strength ratio height of draw direction and vertical direction, even if the repetitive with fluorenes ring contained in this resin combination Ratio reduces, it may have demonstrate the tendency of inverse wave length dispersibility.It should be noted that above-mentioned strength ratio can be by the following method It is measured.

First made stretched film by the resin combination of the present invention, implement polarisation ATR and analyze.In this analysis result, source 1245cm in carbonyl orientation^-1Absorb strength ratio (2 color ratios: the intensity of draw direction/hang down in draw direction and vertical direction Nogata to intensity) be more than 1.2, confirm main chain draw direction be orientated.Then calculate and come from fluorenes ring orientation 740cm^-1Absorb in the strength ratio of draw direction Yu vertical direction.

<3.22 main chains and fluorenes angulation>

About the resin combination of the present invention, the specific conformation (configuration) of three fluorenes of divalent is not with gauche conformation for stablizing structure In the case of as, main chain and the fluorenes ring angulation at transoid conformation is more than 50 °, is preferably more than 60 °, more preferably When more than 70 °, it is contemplated that inverse wave length dispersibility can be shown.

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

For AM1 method, software uses the PC Spartan Pro 1.0.5 that Wavefunction society of the U.S. manufactures (32 versions of Windows (registered trade mark)).It should be noted that the input value focusing on decision content etc. relevant to computational accuracy is complete Portion uses the default value of this software.

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

Use AM1 method, for 2 side chains present in each monomer both for transoid conformation and both be two kinds The energy difference of the conformer of gauche conformation calculates.Additionally, for transoid 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 is as main chain direction, using the plane of 3,6,9 carbon atoms through fluorenes as fluorenes plane.This Time, although the straight line in the fluorenes plane intersected with main chain direction is unlimited existence, but the fluorenes minimum with the angle in main chain direction Straight line in plane is well-determined.Using this 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 formula (3) as repetition The method of unit, from the transparency of obtained resin combination, the aspect of uniformity, the most following method:

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

2. three fluorenes diester compounds are utilized following formula (21) the institute table with the organic group represented by above-mentioned formula (3) After the dihydroxy compounds shown carries out ester exchange, with following formula (21) institute of the organic group having represented by above-mentioned formula (3) The dihydroxy compounds represented carries out copolymerization, the method imported by two steps；

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

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

HO-R²⁰-OH (21)

HOCOR²⁰-COOH (28)

In formula (21) and formula (28), R²⁰R with above-mentioned formula (3)²⁰Identical.

Herein, the divalent organic group represented by above-mentioned formula (3) can use the group of single kind, it is possible to by two kinds Above different organic group is applied in combination.Being applied in combination two or more different organic group can be two or more not by use The same dihydroxy compounds represented by above-mentioned formula (21) and/or the dicarboxylic acid compound represented by above-mentioned formula (28) reach Become.

<3.24 phase contrasts ratio>

The resin combination of the present invention, in the case of being assumed to be phase retardation film purposes, preferably measures at wavelength 450nm Phase contrast (Re450) with wavelength 550nm at mensuration the ratio of phase contrast (Re550), i.e. phase contrast ratio meet following formula (20)。

Re450/Re550≤1.0(20)

Herein, " the phase contrast ratio of the resin combination of the present invention meets above-mentioned formula (20) " refers to, is being shaped to stretched film Time, at following condition determination, the phase contrast (Re450) measured at wavelength 450nm and the phase contrast measured at wavelength 550nm (Re550) ratio meets above-mentioned formula (20).

Phase contrast ratio measures as follows.Utilize hot press that resin combination is suppressed, make film.This film is cut Become the size of regulation, carry out free end simple tension, make stretched film.(prince measures machine society to use measuring difference of phases device Manufacture KOBRA-WPR), for this stretched film phase contrast (Re450) at wavelength 450nm and the phase contrast at wavelength 550nm (Re550) it is measured.For draw direction, in the case of phase contrast ratio (Re450/Re550) meets above-mentioned formula (20), this tree Oil/fat composition demonstrates the wavelength dispersibility useful as phase retardation film.

In the case of the resin combination of present invention inverse wave length dispersion membrane purposes in being assumed to phase retardation film, phase contrast Than (Re450/Re550) the upper limit preferably less than 1.0, more preferably less than 1.0, more preferably less than 0.95, more enter one Step is preferably less than 0.93, particularly preferably less than 0.91.Additionally, the lower limit of phase contrast ratio (Re450/Re550) be preferably 0 with Upper, more preferably more than 0.50, further preferably more than 0.50, be further preferably more than 0.70, particularly preferably 0.75 Above, most preferably more than 0.80.

As long as in the value of phase contrast ratio (Re450/Re550) is above-mentioned scope, then wavelength is the longest, phase place more can be shown Difference, can obtain preferable phase difference characteristics under each wavelength of visibility region.Such as, as making to shake in mutually perpendicular direction The phase place of dynamic polarized light carries out the 1/4 λ plate that 1/4 wavelength (90 °) changes, and can use by the basis with such wavelength dispersibility The phase retardation film that invention resin combination obtains, by itself and polarizing plate sticking, thus makes circular polarizing disk etc., it is possible to realize entirely There is under portion's wavelength circular polarizing disk and the image display device of the black excellence preventing external light reflection function.On the other hand, The value of phase contrast ratio (Re450/Re550) be above-mentioned extraneous in the case of, the decolouring (color け) caused by wavelength becomes big, tool There is the tendency producing coloring problem in circular polarizing disk or image display device.

" invention 3 "

Hereinafter, to low polyfluorene, the low polyfluorene compositions comprising this low polyfluorene of the present invention 3 and use this low polyfluorene to obtain To resin combination be described in detail.

It should be noted that (formula) formula (1) set forth below～(5), (4-1), (2a), (2b), (2c-1), (2c- 2), (2d), (7)～(9), (11), (A), (A-1), (B) are for illustrating each structure in the present invention 3.

The Oligofluorenylene compounds A1 of 1 reactive functional groups<1 have>

The low polyfluorene (hereinafter sometimes called " low polyfluorene A1 ") with 1 reactive functional groups of the present invention comprises tool There is or do not has the carbon atom of 9 of fluorenes unit a of more than 2 of substituent group 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 are with chain bonding Oligomeric fluorene structural units a become, and,

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

[changing 84]

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

So, by making reactive functional groups be ad hoc structure, thus industrially it is obtained in that, furthermore, it is possible to be suitable for The raw material of monomer as the resin combination of optical applications.

<1.1 alkylidenes, arlydene, sub-aralkyl>

Identical with the group of explanation in the item at<1.1 alkylidenes, arlydene, the sub-aralkyl>of above-mentioned " invention 2 ".

Identical with the substituent group of explanation in the item of<substituent group that 1.2 fluorenes unit a can have>of above-mentioned " invention 2 ".

<1.3 reactive functional groups>

Low polyfluorene 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 represented.Reactive functional groups refers not only to be used directly for the group of polyreaction, also refers to through conversion React and can be used in the group of polyreaction.

[changing 85]

Hereinafter enumerate above-mentioned R^a～R^cIn " with or without the alkyl that carbon number is 1～10 of substituent group " concrete Structure, but it is not limited to these, methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, positive decyl etc. can be enumerated straight The alkyl of chain；Isopropyl, 2-methyl-propyl, 2,2-dimethyl propyl, 2-ethylhexyl etc. comprise the alkyl of side chain；Ring third Base, cyclopenta, cyclohexyl, the isothrausmatic alkyl of ring octyl group.

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

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

Hereinafter enumerate above-mentioned R^a～R^cIn " with or without the aryl that carbon number is 4～10 of substituent group " concrete Structure, but it is not limited to these, the aryl such as phenyl, 1-naphthyl, 2-naphthyl can be enumerated；2-pyridine radicals, 2-thienyl, 2-furan The heteroaryls such as base.

Be preferably less than 8 with or without the carbon number in the aryl that carbon number is 4～10 of substituent group, more excellent Elect less than 7, and preferably more than 4, more preferably more than 5 as.If in the range of Gai, the importing with reactive functional groups be held Easy tendency.

As the concrete example of the aryl being replaced, can enumerate 2-aminomethyl phenyl, 4-aminomethyl phenyl, 4-chlorphenyl, 3,5- 3,5-dimethylphenyl, 4-benzoylphenyl, 4-methoxyphenyl, 4-nitrobenzophenone, 4-cyano-phenyl, 3-trifluoromethyl, 3,4-Dimethoxyphenyl, 3,4-methylene dihydroxyphenyl, 2,3,4,5,6-pentafluorophenyl group, 4-methylfuran base etc..

Hereinafter enumerate above-mentioned R^a～R^cIn the tool of " with or without the aralkyl that carbon number is 6～10 of substituent group " Body structure, but be not limited to these, can enumerate benzyl, 2-phenylethyl, to methoxy-benzyl etc..

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

The substituent group can having as this aralkyl, can enumerate halogen atom (such as fluorine atom, chlorine atom, bromine atoms, Atomic iodine)；Carbon number is the alkyl (such as methyl, ethyl, isopropyl etc.) of 1～10；Carbon number is the alkoxyl of 1～10 (such as methoxyl group, ethyoxyl etc.)；Carbon number is the acyl group (such as acetyl group, benzoyl etc.) of 1～10；Carbon number is The amide groups (such as acetamido, benzamido etc.) of 1～10；Nitro；Cyano group etc..The quantity of this substituent group limits the most especially Fixed, preferably 1～3.In the case of substituent group is more than 2, the kind of substituent group can be the same or different.It addition, from The industrial aspect that can manufacture at low cost is set out, the most unsubstituted.

As the concrete example of the aralkyl being replaced, can enumerate benzyl, 2-phenylethyl, to methoxy-benzyl etc..

Among these, readily it is inclined to owing to having the importing of reactive functional groups, thus preferably R^aAnd R^bFor hydrogen atom Following formula (A-1).Additionally, from industrial can obtain raw material at low cost from the standpoint of, R^cIt is preferably hydrogen atom or first Base, more preferably hydrogen atom.

[changing 86]

It addition, the concrete structure of " ester group " is not particularly limited in X, such as can enumerate end group is that carbon number is The ester group of the organic substituent of 1～10.

Among these, it is the alkyl of 1～6 from the industrial aspect that can obtain at low cost, preferably carbon number. In this case, being easily subject to the aspect of hydrolysis, easily generation carboxylic acid from synthesis, carbon number is preferably more than 2, separately Outward, from by removing the low-boiling point alcohol of generation the ester exchange with dihydroxy compounds it is thus possible to be efficiently synthesized polyester and gather From the standpoint of ester carbonic ester, preferably less than 4, more preferably less than 2.Particularly preferred substituent group is ethyl.

On the other hand, in the case of the aryl that carbon number is 6～8, ester exchange reaction is easily carried out, thereby through inciting somebody to action Aryl ester compound and dihydroxy compounds, carbonic diester add in input reactor in the lump such that it is able to go out with one-step synthesis As the polyestercarbonate of preferred polymers, thus it is preferred.Particularly, particularly preferably molecular weight is little, at polyester carbonic acid The phenyl that can remove as phenol distillation after Lipase absobed.It addition, in the case of aryl, in terms of the reactivity when polymerization Set out, described later diaryl carbonate esters is preferably used as carbonic diester, from can easily remove the aspect of by-product, The more preferably aryl of the aryl in ester group and diaryl carbonate apoplexy due to endogenous wind is identical.

It addition, ester group can be converted to, by carrying out reduction, the alcohol that the raw material as Merlon or polyester is useful.

In X, the concrete structure of " amide groups " is not particularly limited, such as, can enumerate: have 2 hydrogen on (i) nitrogen-atoms former The primary amide base of son；(ii) there is on nitrogen-atoms the secondary amide base of hydrogen atom and organic substituent that carbon number is 1～10； (iii) there is on nitrogen-atoms the teritary amide base of the organic substituent that 2 carbon numbers are 1～10 independently of one another.Former as carbon Subnumber is the organic substituent of 1～10, it may be preferred to use as the organic substituent that the carbon number in " ester group " is 1～10 Illustrated group.

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

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

<1.4 concrete structure>

As low polyfluorene A1 of the present invention, specifically, it may be preferred to use the material represented by following formula (1).

[changing 87]

In formula (1),

R⁴～R⁹It is each independently hydrogen atom, the alkyl that carbon number is 1～10 with or without substituent group, tool There is or do not have the aryl that carbon number is 4～10 of substituent group, be 1～10 with or without the carbon number of substituent group Acyl group, the acyloxy that carbon number is 1～10 with or without substituent group, the carbon number with or without substituent group Be the alkoxyl of 1～10, with or without the aryloxy group that carbon number is 1～10 of substituent group, with or without replacement The amino of base, the vinyl that carbon number is 1～10, former with or without the carbon of substituent group with or without substituent group Subnumber is the acetenyl of 1～10, has the sulphur atom of substituent group, has the silicon atom of substituent group, halogen atom, nitro or cyanogen Base.Wherein, at R⁴～R⁹In, at least 2 adjacent groups can be mutually bonded formation ring.

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

N represents the integer value of 1～5.

In above-mentioned formula (1), as R³And R⁴～R⁹, it may be preferred to use illustrated in this group of above-mentioned " invention 1 " Group.

The concrete example of low polyfluorene A1 of 1 reactive functional groups<1.5 have>

As the concrete example of low polyfluorene A1 of the present invention, the structure shown in following [E] group can be enumerated.

[changing 88]

[changing 89]

The physical property of low polyfluorene A1 of 1 reactive functional groups<1.6 have>

The physics value of low polyfluorene A1 of the present invention is not particularly limited, and preferably meets physics value illustrated below.

Chlorine content ratio in low polyfluorene A1 of the present invention is preferably below 100 mass ppm in terms of Cl reduced mass.Enter one Step is preferably below 10 mass ppm.In the case of the content ratio of chlorine component is many, obtaining using low polyfluorene A1 as raw material Monomer also can contain chlorine component in a large number, catalysqt deactivation used in polyreaction, polymerization can be made to cannot be carried out to desired Molecular weight, or reaction in destabilization, have productivity ratio be deteriorated probability.And also have in obtained polymer Chlorine component remaining, may make the heat stability of polymer reduce.

In low polyfluorene A1 of the present invention, may be containing sodium or the potassium isometric preiodic type periodic chart deriving from following operation The group II metals such as the 1st race's metal or calcium, this operation carries out crosslinking instead for making formaldehydes and fluorenes class have an effect in the presence of a base The operation answered；The content ratio of these metals is preferably below below 500 mass ppm, more preferably 200 mass ppm, further It is preferably below below 50 mass ppm, particularly preferably 10 mass ppm.If metal ingredient is many, then using low polyfluorene A1 as former Also can contain metal ingredient in a large number in the monomer expected and obtain, add man-hour in polyreaction or resin, polymer may become easy Coloring.Additionally, contained metal ingredient demonstrates catalyst action or catalysqt deactivation effect, it is also possible to make polymerization in not Stabilisation.

In low polyfluorene A1, the lowest polyfluorene list aryl ester of the present invention, may be containing being brought by following operation 12nd races such as group II metal, zinc, cadmium such as the transition metal such as titanium, copper, ferrum, sodium, potassium isometric preiodic type periodic chart the 1st race, magnesium, calcium 14th race's metal such as metal or stannum, this operation is for make diaryl carbonates esters make in the presence of catalyst for ester exchange reaction It is used for carrying out the operation of ester exchange；The content ratio of these metals is preferably below 500 mass ppm, more preferably 200 mass Below below ppm, more preferably 50 mass ppm, below particularly preferably 10 mass ppm.If metal ingredient is many, then with The monomer that low polyfluorene obtains as raw material also can contain metal ingredient in a large number, add man-hour in polyreaction or resin, polymerization Thing may become easy coloring.Additionally, contained metal ingredient demonstrates catalyst action or catalysqt deactivation effect, it is also possible to Can make polymerization is destabilization.

The tone of the tetrahydrofuran solution of 10 mass % of low polyfluorene A1 of the present invention is preferably less than 50.Further preferably It is less than 10.The absorption edge of low polyfluorene A1 extends close to the region of visible ray, has and is exposing because of polymerization or resin processing The character easily coloured when high temperature.The polymer good in order to obtain tone, in preferred polymeric reaction, monomer used to the greatest extent may be used Can colour few.From this viewpoint, low polyfluorene A1 preferably as raw material monomer colours few as far as possible.Owing to tone becomes with concentration Ratio, thus can be under variable concentrations, be measured and be standardized as the value that 10 mass % concentration obtain.Herein, low The tone (APHA value) of polyfluorene A1 can be measured: according to JIS-K0071-1 (1998), by Kishida Chemical society system Make color standard liquid (1000 degree) dilution, made diluent and low polyfluorene A1 are encased in the color comparison tube of internal diameter 20mm also Compare, thus measure this tone.

Low polyfluorene A1 of the present invention 5% weightless temperature in thermogravimetric measures is preferably more than 230 DEG C, is more preferably 250 More than DEG C.The most particularly preferably more than 270 DEG C.Fluorenes is the structure very rich in electronics, is bonded in the substituent group on fluorenes ring Reactive high, easily produce thermal decomposition.If using the monomer that heat decomposition temperature is low in the polymerization, then can produce when polymerization Heat is decomposed, polymerization carries out may colouring less than desired molecular weight or obtained polymer, thus preferably as The heat decomposition temperature of low polyfluorene A1 of raw material monomer is the highest.

The manufacture method of low polyfluorene A1 of 1 reactive functional groups<1.7 have>

Manufacture method for low polyfluorene A1 of the present invention is not particularly limited, such as, can enumerate following method: at alkali In the presence of make low polyfluorene represented by following formula (3) and the olefine reaction with electron-withdrawing group represented by following formula (4), Thus manufacture low polyfluorene A1 represented by following formula (1).

[changing 90]

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

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

N represents the integer value of 1～5.

In above-mentioned formula (3) and (4), as R³～R⁹、R^a～R^c, X and n, it may be preferred to use in above-mentioned formula (1) as R³ ～R⁹、R^a～R^c, situation illustrated in X and n.

The alkene of electron-withdrawing group<1.7.1 have>

It addition, as the alkene with electron-withdrawing group represented by above-mentioned formula (4), can enumerate acrylic acid methyl ester., Ethyl acrylate, phenyl acrylate, allyl acrylate, glycidyl acrylate, 2-Hydroxy ethyl acrylate, acrylic acid The esters of acrylic acids such as 4-hydroxybutyl, 1,4 cyclohexane dimethanol mono acrylic ester；Methyl methacrylate, methacrylic acid second Ester, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, methacrylic acid-2-hydroxy methacrylate Deng methyl acrylic ester；The alpha-substituted unsaturation esters such as 2-ethyl methyl acrylate, 2-phenylacrylic acid methyl ester；Cinnamic acid first The beta substitution unsaturation esters such as ester, ethyl cinnamate, M Cr, butenoic acid ethyl；Beta-nitrostyrene equiconjugate nitro Olefines；The 'alpha ', ' bela '-unsaturated nitrile classes such as acrylonitrile；The alpha, beta-unsaturated aldehyde classes such as acrylic aldehyde, methacrolein, crotonic aldehyde.Wherein, excellent Choosing can be introduced directly into the esters of unsaturated carboxylic acids represented by following formula (4-1) of reactive functional groups.

[changing 91]

(in formula, R^cWith the R in formula (4)^cIdentical, R⁹Represent the organic substituent that carbon number is 1～10.).Herein, make For R⁹The organic substituent that carbon number is 1～10, it may be preferred to using is 1～10 as the carbon number in " ester group " Group illustrated in organic substituent.

In the unsaturated carboxylic acid represented by formula (4-1), more preferably esters of acrylic acid, methyl acrylic ester or α- Replace unsaturated esters, from response speed and the aspect of reaction selectivity, further preferred R^cFor hydrogen atom or methyl Esters of acrylic acid or methyl acrylic ester.R⁹Time less, industrial low cost and distillation refine easily, reactivity is the highest, because of And particularly preferably acrylic acid methyl ester., 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-hydroxyl In the case of butyl ester, 1,4-CHDM mono acrylic ester etc. have the esters of hydroxy alkyl, can be obtained by a step Polyestercarbonate, the raw material of polyester, thus particularly preferably.

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

It is not particularly limited for having the consumption of the alkene of electron-withdrawing group, singly adds adult from optionally obtaining From the standpoint of, more than preferably 0.1 equivalent, more than more preferably 0.3 equivalent, more preferably more than 0.5 equivalent, the most excellent Elect below below more than 0.7 equivalent, and preferably 2.0 equivalents, more preferably 1.8 equivalents, more preferably 1.5 equivalent as Below, it is particularly preferably below 1.2 equivalents.

<1.7.2 alkali>

At R³For methylene situation with in addition in the case of, there is the reactivity of low polyfluorene represented by formula (3) There is the tendency of larger difference.Therefore, it is divided into R³Situation for methylene is recorded with situation in addition.

At R³In the case of methylene, the low polyfluorene represented by formula (3) is the most easily carried out point Solve reaction.Therefore, decomposition reaction etc. can be suppressed in the case of utilizing the organic layer 2 coating systems with water layer to react The reason of side reaction, is preferably used water miscible inorganic base.Wherein from the standpoint of cost, reactivity, preferred as alkali Hydroxide, the most particularly preferably sodium hydroxide or potassium hydroxide.

Additionally, about the concentration of aqueous solution, in the case of using particularly preferred sodium hydrate aqueous solution, if due to dense Spending low, response speed can significantly reduce, thus particularly preferably use usually more than 5wt/wt%, be preferably 10wt/wt% with Aqueous solution upper, more preferably more than 25wt/wt%.

At R³In the case of beyond methylene, 2 coating systems even with organic layer with water layer also can react, but In the case of using the organic base being dissolved in organic layer to react, owing to reaction carries out being preferably used organic rapidly Alkali.There is the alkali alcoholate of fully alkalescence the most in the reaction, Feldalat NM that more preferably industrial cost is low or second Sodium alkoxide.Alkali alcoholate herein can use the material of powdery, it is possible to use the liquids such as alcoholic solution.And it is permissible Make alkali metal react with alcohol to prepare.

At R³In the case of methylene, about the consumption of alkali, relative to the low polyfluorene represented by starting materials of formulae (3), on it Limit is not particularly limited, but when the consumption of alkali is too much, stirring or reacted refined load may increase, thus is using In the case of sodium hydrate aqueous solution as more than the 25wt/wt% of particularly preferred alkali, it is commonly angled relative to formula (3) represented Low polyfluorene be below 20 times of volumes, be preferably below 10 times of volumes, more preferably below 5 times of volumes.At alkali When measuring very few, response speed significantly reduces, thus alkali is usually 0.2 times of volume relative to the low polyfluorene represented by starting materials of formulae (3) More than amount.It is preferably more than more than 0.5 times of volume, more preferably 1 times of volume.

At R³In the case of beyond methylene, about the consumption of alkali, relative to the low polyfluorene represented by starting materials of formulae (3), Its upper limit is not particularly limited, but when the consumption of alkali is too much, stirring or reacted refined load may increase, thus In the case of using the Feldalat NM as particularly preferred alkali or Sodium ethylate, being commonly angled relative to the low polyfluorene represented by formula (3) is 5 Times mole following, be preferably less than 2 times moles, more preferably less than 1 times mole, be particularly preferably less than 0.5 times mole. When alkali number is very few, response speed significantly reduction, thus alkali is relative to the low polyfluorene represented by starting materials of formulae (3) usually More than 0.005 times mole.It is preferably more than 0.01 times mole, more preferably more than 0.05 times mole, particularly preferably 0.1 times to rub More than Er.

<1.7.3 phase transfer catalyst>

In the case of utilizing the organic layer 2 coating systems with water layer to react, in order to improve response speed, it is preferably used Phase transfer catalyst.

As phase transfer catalyst, can enumerate tetramethyl ammonium chloride, tetrabutyl ammonium bromide, methyl tricapryl ammonium chloride, Methyl three decyl ammonium chloride, benzyltrimethylammonium chloride, tri-n-octyl methyl ammonium chloride, tetrabutylammonium iodide, acetyl group trimethyl The halogenide (not including fluorine) of the quaternary ammonium salt such as ammonium bromide, benzyltriethylammoinium chloride；N, N-dimethyl pyrrolidine chloride, N- Ethyl-N-methyl pyrrolidine iodide, N-butyl-N-crassitude bromide, N-Benzyl-N-methyl pyrrolidine chlorine The halogenide (not including fluorine) of the season pyrrolidinium such as compound, N-ethyl-N-methyl pyrrolidine bromide；N-butyl-N-first The season morpholine such as base morpholine bromide, N-butyl-N-methylmorpholine iodide, N-pi-allyl-N-methylmorpholine bromide The halogenide (not including fluorine) of salt；N-methyl-N-benzyl piperidinium chloride, N-methyl-N-benzyl piperidinium bromide, N, The seasons such as N-lupetidine iodide, N-methyl-N ethyl Piperidineacetic acid salt, N-methyl-N ethyl piperidines iodide The halogenide (not including fluorine) of piperidinium salt；Crown ether-like etc..Preferably quaternary ammonium salt, further preferred benzyltrimethylammonium chloride or Person's benzyltriethylammoinium chloride.They can be used alone one, it is also possible to share two or more.

When the consumption of phase transfer catalyst is too much relative to the low polyfluorene represented by starting materials of formulae (3), have ester hydrolysis or The tendency that the side reaction such as michael reaction is significantly carried out step by step, and from the aspect of cost, it is commonly angled relative to formula (3) institute table The low polyfluorene shown also is less than 5 times moles, is preferably less than 2 times moles, more preferably less than 1 times mole.Phase transfer is urged When the consumption of agent is very few, responds the significantly reduced tendency of speed, thus the consumption of phase transfer catalyst is low relative to raw material Polyfluorene is usually more than 0.01 times mole.It is preferably more than 0.1 times mole, more preferably more than 0.5 times mole.

<1.7.4 solvent>

The reaction of the alkene with electron-withdrawing group represented by above-mentioned formula (4) is preferably used solvent and carries out.

At R³In the case of methylene, there is separated solvent by using with water, it is known that having can suppressed FCM (3) tendency of the side reactions such as the decomposition reaction of the low polyfluorene represented by.Further, starting materials of formulae can preferably be dissolved in use (3), in the case of the solvent of the low polyfluorene represented by, carry out the aspect of good tendency from having reaction, be preferably used former The solvent that dissolubility is more than 0.5 mass % of the low polyfluorene represented by material formula (3), more preferably using this dissolubility is 1.0 matter Amount more than %, the solvent particularly preferably using this dissolubility to be 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-dichloro Benzene, oxolane, 1,4-dioxane or methylcyclopentyl ether.

On the other hand, at R³In the case of the group beyond methylene, it is known that have represented by organic base and formula (3) Response speed is brought the tendency of considerable influence by the dissolubility of low polyfluorene, in order to ensure this dissolubility, is preferably used and has necessarily It is worth the solvent of above dielectric constant.As the solvent of the low polyfluorene can preferably dissolved represented by organic base and formula (3), preferably Heteroaromatic, alkyl nitrile series solvent, amide series solvent, sulfoxide series solvent, particularly preferred pyridine, acetonitrile, N, N-dimethyl methyl Amide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, sulfolane.

Above-mentioned solvent can be used alone one, it is also possible to two or more is used in mixed way.

About the consumption of solvent, the upper limit is not particularly limited, if in view of the generation effect of the goal object in each reactor Rate, then generally use and reach 20 times of volumes of the low polyfluorene represented by starting materials of formulae (3), be preferably 15 times of volumes, further It is preferably the amount of 10 times of volumes.On the other hand, if the consumption of solvent is very few, then the dissolubility of reagent is deteriorated, stirring becomes difficulty, with The carrying out of Shi Fanying is slow, thus as lower limit, generally use reach the low polyfluorene represented by starting materials of formulae (3) 1 times of volume, It is preferably the amount of 2 times of volumes, more preferably 4 times of volumes.

<1.7.5 reaction formation>

The form of reaction can be with the form using batch-type reaction, circulation type reacts or they combine, to its form It is not particularly limited.

In input method reaction reagent put in reactor in the case of batch-wise, will when reaction starts Have the alkene of electron-withdrawing group by disposable add feed intake in the case of, owing to having the alkene of electron-withdrawing group Hydrocarbon exists with high concentration, thus the polyreaction of side reaction is easily carried out.Thus it is preferably low add represented by starting materials of formulae (3) After polyfluorene, phase transfer catalyst, solvent and alkali, the most a small amount of gradually interpolation has the alkene of electron-withdrawing group.

<1.7.6 reaction condition>

If temperature is too low, then can not get sufficient response speed, otherwise if temperature is too high, then there is electron-withdrawing group Alkene has the tendency easily carrying out polyreaction, thus temperature treatment is particularly important.Accordingly, as reaction temperature, tool Say body, implement for 0 DEG C the most within the range having a lower limit of, preferably 10 DEG C, more preferably 15 DEG C.On the other hand, in the upper limit it is generally Implement for 40 DEG C, preferably 30 DEG C, more preferably 20 DEG C.

About the General reactions time, usual lower limit is 2 hours, is preferably 4 hours, more preferably 6 hours, and the upper limit does not has It is particularly limited to, usually 30 hours, preferably 20 hours, more preferably 10 hours.

After termination of the reaction, following method can be used to make low polyfluorene A1 represented by the above-mentioned formula of goal object (1) separate out, thus Carrying out the separation of low polyfluorene A1 represented by the above-mentioned formula of goal object (1), described method is by filtering byproduct metal halogenation The inorganic base of thing and remaining carries out the method for solvent concentration or the bad molten of adding purpose thing after removing from reactant liquor The method of agent；Etc..

Additionally, after termination of the reaction, it is also possible in reactant liquor, add acid water and solubilized goal object above-mentioned formula (1) institute The solvent of low polyfluorene A1 represented extracts.The goal object utilizing solvent extraction to go out can be by the side concentrating solvent The method etc. of method or interpolation poor solvent separates.

As the solvent that can use when extracting, if low polyfluorene A1 represented by the above-mentioned formula of solubilized goal object (1) , it is not particularly limited, but is adapted in use to the halogen systems such as the aromatic hydrocarbon compound such as toluene, dimethylbenzene, dichloromethane, chloroform One kind or two or more in solvent etc..

In the case of in low polyfluorene A1 represented by formula (1) herein obtained, X is ester group, it is possible to polyester or polyester carbonic acid The form of the precursor of ester starting monomer uses but it also may use after carrying out refining.As method for refining, can use common Method for refining, such as recrystallization or reprecipitation method, Hydrolysis kinetics, column chromatography etc., and unrestrictedly.Additionally low polyfluorene A1 can be dissolved In suitable solvent, activated carbon is utilized to process.The solvent that now can use and the solvent phase that can use when extracting With.

In the case of in low polyfluorene A1 represented by formula (1) herein obtained, X is carboxyl, it is possible to directly with polyester or polyester The form use etc. of the precursor of carbonate source monomer.In addition can be converted into, by esterification, the low polyfluorene that X is ester group.

In the case of in low polyfluorene A1 represented by formula (1) herein obtained, X is nitro or cyano group, can be by utilizing hydrogen The hydride reduction hydrogenating or utilizing the reducing agents such as lithium aluminium hydride to carry out that the methods such as the palladium carbon under atmosphere are carried out manufactures has ammonia The low polyfluorene of base.It addition, in the case of X is cyano group, No. 3280169 description of U.S. Patent No. and U.S. Patent No. can be passed through The low polyfluorene that the method migration of No. 3324084 description etc. becomes X to be ester group.

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

The low polyfluorene (hereinafter sometimes called " low polyfluorene A2 ") with 2 different reactive functional groups of the present invention It is that the carbon atom of 9 of the fluorenes unit a comprising with or without substituent group more than 2 is 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 The low polyfluorene of oligomeric fluorene structural units a of shape bonding, this low polyfluorene is characterised by,

The carbon atom of 9 of fluorenes unit a of any one end of this oligomeric fluorene structural units a has following formula (A) reactive functional groups represented by, has and this 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 bonding alkylidene of fluorenes unit a, arlydene and sub-aralkyl, the most preferably can use at < 1.1 alkylenes Base, arlydene, sub-aralkyl > in illustrated group.

Similarly, the substituent group can having as fluorenes unit a, preferably can use < 1.2 fluorenes unit a can have Substituent group > in illustrated group.

Similarly, as the R in formula (A)^a～R^cAnd X, the most preferably can use institute in<1.3 reactive functional groups> The group illustrated.

<2.1 arbitrary reactive functional groups>

As it has been described above, on low polyfluorene A2 of the present invention has on the carbon atom of 9 of the fluorenes unit a of any one end State the reactive functional groups represented by formula (A), the carbon atom of 9 of the fluorenes unit a of another end has and this reaction The arbitrary reactive functional groups that property functional group is different.

It is not particularly limited about 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.

So, by 1 low polyfluorene there are 2 different reactive functional groups, thus have can be easily to resin Give the tendency of the specific physical property from two kinds of reactive functional groups.

Hereinafter enumerate the concrete structure of above-mentioned arbitrary reactive functional groups, but be not limited to these, hydroxyl can be enumerated Methyl, 2-hydroxyethyl, 3-hydroxypropyl, hydroxybutyl, 2,2-dimethyl-3-hydroxypropyl, 2-methoxy-2-methyl Propylidene, 4-hydroxy phenyl, 4-hydroxy-3-methyl phenyl, 4-(2-hydroxyl-oxethyl) phenyl, (4-(hydroxymethyl) hexamethylene- 1-yl) hydroxyl such as methyl；Methoxycarbonyl, ethoxy carbonyl, phenyloxycarbonyl, ethoxy carbonyl methyl, 2-(ethyoxyl carbonyl 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 group；2-hydroxyl Base oxethyl carbonyl, 2-(2-hydroxyl-oxethyl) carbonylethyl, 2-methyl-2-(2-hydroxyl-oxethyl) carbonylethyl, 2-(2-hydroxyl Base oxethyl) carbonyl propyl group, 2-(4-hydroxybutoxy) carbonylethyl, 2-methyl-2-(4-hydroxybutoxy) carbonylethyl, 2- [[4-(hydroxymethyl) hexamethylene-1-base] methoxyl group] carbonylethyl, 2-methyl-2-[[4-(hydroxymethyl) hexamethylene-1-base] Methoxyl group] the hydroxyl ester group such as carbonylethyl；The carboxyls such as carboxyl, carboxymethyl group, 2-carboxy ethyl, 2-methyl-2-carboxy ethyl；Ammonia The amino such as ylmethyl, 2-amino-ethyl, 3-aminopropyl；Acryloyloxymethyl, methacryloxymethyl, 2-(propylene Acyloxy) ethyl, 2-(methacryloxy) ethyl, 3-(acryloxy) propyl group, 3-(methacryloxy) propyl group Deng acryloyl group；The epoxy radicals etc. such as 2,3-glycidyl, 2,3-glycidyl oxy methyl, 2-(2,3-glycidoxy) ethyl.

It should be noted that low polyfluorene A2 of the present invention can be will have low polyfluorene the gathering as repetitive of divalent The raw material of compound uses, and reactive functional groups is preferably only at 2, at the polymerizing condition for manufacturing various resin combination Under, the substituent group played a role as polymerisation reactivity group is preferably not included in interior.

Among these, about the preferred compositions of the reactive functional groups represented by formula (A) Yu another reactive functional groups, Owing to polyester can be manufactured by a kind of Oligofluorenylene compounds, can enumerate: formula (A) is that ester group, another reactive functional groups are The combination of hydroxyl；Formula (A) be carboxyl, another reactive functional groups be the combination of hydroxyl；And formula (A) be ester group, another Reactive functional groups is the combination of hydroxyl ester group.It addition, ester group, hydroxyl, carboxyl and the hydroxyl ester group in this section and previous paragraphs The ester group of the concrete structure as reactive functional groups of the middle illustration that falls, hydroxyl, carboxyl and hydroxyl ester group implication are identical.

<2.2 concrete structure>

As low polyfluorene A2 of the present invention, specifically, it may be preferred to use the material represented by following formula (2).

[changing 93]

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

Or for choosing freely with or without substituent group the alkylidene that carbon number is 1～10, with or without The carbon number of substituent group is the arlydene of 4～10 and with or without the sub-aralkyl that carbon number is 6～10 of substituent group The group of more than 2 in the group of basis set one-tenth by oxygen atom, with or without substituent group sulphur atom, with or without The group that the nitrogen-atoms of substituent group or carbonyl are formed by connecting.

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

N represents the integer value of 1～5.

In above-mentioned formula (2), as R³, it may be preferred to use as the R in above-mentioned formula (1)³Illustrated group.

Additionally, as R⁴～R⁹, it may be preferred to use as the R in above-mentioned formula (1)⁴～R⁹Illustrated group.

It addition, as R^a～R^cAnd X, it may be preferred to use as the R in above-mentioned formula (A)^a～R^cWith the group illustrated in X.

As R¹⁰, in<the low polyfluorenes of 4.1 divalents>described later, it may be preferred to use alternatively base α¹And α²Illustrated Group.

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

It addition, the concrete structure of " amino " is not particularly limited in A, such as, can enumerate: there are on (i) nitrogen-atoms 2 The primary amino radical of hydrogen atom；(ii) there is on nitrogen-atoms the secondary amino group of hydrogen atom and organic substituent that carbon number is 1～10； (iii) there is on nitrogen-atoms the tertiary amino of the organic substituent that 2 carbon numbers are 1～10 independently of one another.As carbon atom Number is the organic substituent of 1～10, it may be preferred to using as the carbon number in " ester group " of the X of above-mentioned formula (A) is 1～10 The group illustrated in organic substituent.

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

The concrete example of low polyfluorene A2 of 2 different reactive functional groups<2.3 have>

As the concrete example of low polyfluorene A2 of the present invention, the structure shown in following [F] group can be enumerated.

[changing 94]

[changing 95]

The physical property of low polyfluorene A2 of 2 different reactive functional groups<2.4 have>

Identical with the situation of explanation in the item of above-mentioned physical property of low polyfluorene A1 of 1 reactive functional groups<1.6 have>.

The manufacture method of low polyfluorene A2 of 2 different reactive functional groups<2.5 have>

Manufacture method for low polyfluorene A2 of the present invention is not particularly limited, such as, can enumerate following method: make State the low polyfluorene represented by formula (1) to react with having electrophilic compound, manufacture low polyfluorene A2 represented by above-mentioned formula (2).

[changing 96]

Hereinafter, by the manufacture method of low polyfluorene A2 represented by above-mentioned formula (2) according to the kind with electrophilic compound Class is divided into autofrettage A, autofrettage B, autofrettage C, autofrettage D are recorded.

<2.5.1 autofrettage A: the manufacture method of addition based on formaldehydes>

Have hydroxymethyl as the low polyfluorene represented by the following formula (2a) of reactive functional groups can in the presence of a base, Manufacture by low polyfluorene A1 represented by following formula (1) and formaldehydes according to the reaction represented by autofrettage A.

[changing 97]

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

<2.5.1.1 formaldehydes>

As long as the formaldehydes used in autofrettage A is that the material that can supply formaldehyde in reaction system limits the most especially Fixed, the formaldehyde of gaseous state, formalin, the paraformaldehyde of oxymethylene polymerization, trioxane etc. can be enumerated.These it In, when using paraformaldehyde, industrial cost low and due to for powder thus operability easily, can accurate weighing, thus special The most preferred.

About the consumption of formaldehydes, relative to low polyfluorene A1 of raw material, its upper limit is not particularly limited, if but consumption is too much, Then there is the tendency that reacted refined load increases, thus be commonly angled relative to low polyfluorene A1 and be less than 10 times moles, be preferably 5 Times mole below, more preferably less than 3 times moles.About lower limit, rub owing to being calculated as 1 times relative to raw material with theoretical amount You, thus lower limit is usually more than 1 times mole.In order to accelerate reaction and carry out, not retained material or intermediate, thus formaldehydes phase Polyfluorene A1 low for raw material is somewhat excessively used does not has any problem yet.Now the preferable amount of formaldehydes is oligomeric relative to raw material Fluorenes A1 is more than 1.1 times moles, more preferably more than 1.2 times moles.

<2.5.1.2 alkali>

As alkali, use the alkali metal hydroxides such as Lithium hydrate, sodium hydroxide, potassium hydroxide；Calcium hydroxide, hydroxide The hydroxide of the alkaline-earth metal such as barium；The alkali-metal carbonate such as sodium carbonate, sodium bicarbonate, 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 Feldalat NM, Sodium ethylate, potassium tert-butoxide；The hydrogenated alkali metal salt such as sodium hydride, hydrofining；Three second The tertiary amines such as amine, diazabicyclo endecatylene；The quaternary ammonium hydroxide such as Tetramethylammonium hydroxide, TBAH etc..They Can be used alone one, it is also possible to share two or more.

Among them, having the alkali alcoholate of fully alkalescence the most in the reaction, more preferably industrial cost is low Feldalat NM or Sodium ethylate.Alkali alcoholate herein can use the material of powdery, it is possible to use the liquid object such as alcoholic solution Matter.And alkali metal can be made to react with alcohol prepare.

The consumption of alkali does not has the special upper limit, when consumption is too much, has the tendency that reacted refined load increases, thus Being less than 1 times mole, preferably less than 0.5 times mole, more preferably less than 0.2 times mole relative to low polyfluorene A1 is Good.On the other hand, when the consumption of alkali is very few, reaction is carried out slowly, thus as lower limit, being commonly angled relative to low polyfluorene A1 of raw material is More than 0.01 times mole, preferably more than 0.05 times mole.

<2.5.1.3 solvent>

Autofrettage A is preferably used solvent and carries out.

Specifically, spendable solvent can be enumerated: as the acetonitrile of alkyl nitrile series solvent, propionitrile etc.；As ketone system The acetone of solvent, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) 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 propionate, 3-ethoxy-propionic acid The esters of the straight-chain such as methyl ester, methyl lactate, ethyl lactate, the ring-type esters such as 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 acetate, the third two The ether-ether classes etc. such as alcohol-1-monoethyl ether acetate；As the diethyl ether of ether series solvent, oxolane, 1,4-dioxane, methyl ring Amyl ether, t-butyl methyl ether etc.；As the 1,2-dichloroethanes of halogen series solvent, dichloromethane, chloroform, 1,1,2,2-tetra-chloroethene Alkane etc.；As the chlorobenzene of halogen system aromatic hydrocarbon, 1,2-dichloro-benzenes etc.；As amide series solvent N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone etc.；As the dimethyl sulfoxide of sulfoxide series solvent, sulfolane etc.；As ring The monocyclic aliphatic hydrocarbon such as the Pentamethylene. of formula aliphatic hydrocarbon, hexamethylene, cycloheptane, cyclooctane；Methyl ring penta for its derivant Alkane, ethyl cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-bis- Hexahydrotoluene, isopropyl cyclohexane, n-pro-pyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene, 1,2,4-trimethyl-cyclohexane, 1,3,5-trimethyl-cyclohexane etc.；The polycycle aliphatic hydrocarbons such as decahydronaphthalenes；Pentane, just oneself The non-ring type aliphatic hydrocarbons such as alkane, normal heptane, normal octane, isobutyltrimethylmethane., n-nonane, n-decane, n-dodecane, n-tetradecane；As The toluene of aromatic hydrocarbon, xylol, o-Dimethylbenzene, meta-xylene etc.；As the methanol of alcohol series solvent, ethanol, isopropanol, just Butanol, the tert-butyl alcohol, hexanol, capryl alcohol, Hexalin etc..

Wherein, the dissolubility for the anion generated by low polyfluorene A1 is high, have reaction carries out the former of good tendency The amide series solvent of cause, preferably polar solvent or sulfoxide series solvent, particularly preferred DMF.

These solvents can be used alone one, it is also possible to two or more is used in mixed way.About the consumption of solvent, the upper limit does not has There is restriction especially, if in view of the formation efficiency of the goal object in each reactor, then generally use and reach low polyfluorene A1 of raw material 10 times of volumes, be preferably the amount of 7 times of volumes, more preferably 4 times of volumes.On the other hand, if the consumption of solvent Very few, then stirring becomes difficulty, and the carrying out with reaction is inclined to slowly, thus as lower limit, it is low that usual use reaches raw material 1 times of volume of polyfluorene A1, it is preferably the amount of 2 times of volumes, more preferably 3 times of volumes.

<2.5.1.4 reaction formation>

When carrying out autofrettage A, the form of reaction can use batch-type reaction, circulation type reaction or their combination and The form become, is not particularly limited its form.

In input method reaction reagent put in reactor in the case of batch-type, when reaction starts by alkali In the case of being fed intake by disposable interpolation, easily carry out due to known decomposition reaction, thus preferably adding raw material After low polyfluorene A1, formaldehydes and solvent several times, each a small amount of method adding alkali.

<2.5.1.5 reaction condition>

If the temperature of autofrettage A is too low, then can not get sufficient response speed, on the contrary if temperature is too high, then understand have into The tendency of row decomposition reaction, preferably carries out temperature treatment.Therefore, use as optimum solvent DMF and In the case of Sodium ethylate as optimal alkali ,-50 DEG C the most within the range having a lower limit of, the upper limit is 30 DEG C and implements.Specifically, at R³ In the case of methylene, in the upper limit preferably 20 DEG C of reaction temperature, implement under conditions of more preferably 10 DEG C.Another Aspect, implements under conditions of lower limit is preferably-20 DEG C, more preferably more than 0 DEG C.At R³In the case of ethylidene, Implement under conditions of the upper limit of reaction temperature is preferably 25 DEG C, more preferably 20 DEG C.On the other hand, lower limit be preferably 0 DEG C, Implement under conditions of more preferably more than 10 DEG C.

After termination of the reaction, reactant liquor can be added in the acid waters such as dilute hydrochloric acid, or the acid waters such as dilute hydrochloric acid are added It is added in reactant liquor, makes the low polyfluorene represented by goal object formula (2a) separate out, thus separate.

Additionally, after termination of the reaction, it is possible to the solvent of the low polyfluorene represented by solubilized goal object formula (2a) is added with water It is added in reactant liquor, extracts.Utilize the goal object that solvent extraction goes out can be by by the method for solvent concentration or add not The methods of good solvent etc. separate.

The obtained low polyfluorene represented by formula (2a) can be directly used in polymerization as polymer raw material, it is possible to is carrying out It is polymerized after Jing Zhi.As method for refining, can use common method for refining, such as recrystallization or reprecipitation method, Hydrolysis kinetics, Column chromatography etc., and unrestrictedly.

The existence of metal ingredient in the polymerization more to come into question, and can make long period type periodic chart the 1st race and the 2nd race Metal content ratio in monomer be below below 500 mass ppm, more preferably 200 mass ppm, more preferably 50 Below quality ppm, below particularly preferably 10 mass ppm.In order to remove metal ingredient, separatory operation is the most highly effective , but the low polyfluorene represented by goal object formula (2a) has and is only dissolved in DMF or oxolane is contour Tendency in polar solvent, thus mostly the separatory operation utilizing 2 coating systems to carry out is extremely difficult.On the other hand, for instead Precipitate after should stopping, even if carrying out washing, the common refinement treatment such as the hot suspension washing that utilizes any solvent to carry out, also Being difficult to fully remove be mixed into metal ingredient, in precipitate, possible remaining has the metal ingredient of hundreds of quality ppm order of magnitude. As the good method for refining for removing metal ingredient, the reaction precipitate containing impurity is dissolved in N, N-dimethyl formyl Add after in the solvent that the dissolubility such as amine, oxolane is higher and make its method separated out as easy and effective nothing to water Machine salt remove method and preferred.

<2.5.2 autofrettage B: the manufacture method of additive reaction based on the alkene with electron-withdrawing group>

Low polyfluorene represented by following formula (2b) can be in the presence of a base, according to the reaction represented by autofrettage B by following Low polyfluorene A1 and the alkene (4-2) with electron withdraw group different from above-mentioned formula (4) represented by formula (1) manufacture.

[changing 98]

In formula (2b), R³～R⁹、R^a～R^c, X with n identical with above-mentioned formula (1).It addition, R^a2～R^c2It is each independently hydrogen former Son, the alkyl that carbon number is 1～10 with or without substituent group, the carbon number with or without substituent group are 4 ～the aryl of 10 or the aralkyl that carbon number is 6～10 with or without substituent group, Xa is ester group, amide groups, carboxylic Base, cyano group or nitro.Wherein, R^a～R^cWith X and R^a2～R^c2With in Xa, the most any 1 is different.

As R^a2～R^c2And Xa, preferably can use 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, need to make the most any 1 difference.Particularly, from easily, resin is given from differential responses The aspect of the specific physical property of property functional group is set out, and in preferred formula (2b), X from Xa is different.

Low polyfluorene represented by formula (2b) can be according to the method system of low polyfluorene A1 manufactured represented by above-mentioned formula (1) Make.At this point it is possible to carry out separating, refining after manufacturing low polyfluorene A1, manufacture afterwards；Formula (3) can also be made represented Low polyfluorene and formula (4) represented by the olefine reaction with electron-withdrawing group after, then make having represented by formula (4-2) The alkene of electron-withdrawing group reacts.

< 2.5.3 autofrettage C: alkylation based on low polyfluorene A1, the system of the low polyfluorene represented by formula (2c) of hydrolysis Make method) >

Low polyfluorene represented by following formula (2c) can be manufactured by following method, and described method is: through by low The alkylated reaction of polyfluorene A1 and alkylating agent represented by formula (8) carrys out the leaving group that has represented by synthesis type (2c-1) The operation (operation (ia)) of low polyfluorene and the method for ensuing hydrolysis (operation (iia))；Alternatively, it is also possible to pass through Following method manufactures, and described method is: through anti-with the alkylation of the alkylating agent represented by formula (9) by low polyfluorene A1 The operation (operation (ib)) of the low polyfluorene with blocking group represented by synthesis type (2c-2) and ensuing hydrolysis should be come The method of reaction (operation (iib))；Etc..

[changing 99]

In formula, R³～R⁹、R^a～R^c, X with n identical with above-mentioned formula (1).R¹⁰R with above-mentioned formula (2)¹⁰Identical.

It 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, and such as, has report to propose 9, double (bromine hexyl) fluorenes of 9-, 9, and 9-is double Double (alkylhalide group) fluorenes (J.Org.Chem., 2010,75,2714.) of the 9,9-such as (iodine hexyl) fluorenes.According to these technological thoughts, it is possible to Low polyfluorene A is synthesized as raw material the low polyfluorene with leaving group.Additionally, about the hydrolysis of halogen, it is known to many cases report Accuse (Bull.Korean Chem.Soc., 2008,29.2491.), thus can oligomeric by represented by this route synthesis type (2c) Fluorenes.

As the alkylating agent used in operation (ia), can enumerate: diiodomethane, 1,2-ethylidene periodide, 1,3-diiodo- Propane, 1,4-bis-iodobutane, 1,5-bis-iodopentane, 1,6-bis-iodohexane, methylene bromide, glycol dibromide, 1,3-dibromo third Alkane, 1,4-dibromobutane, pentamethylene bromide, 1,6-dibromo-hexane, dichloromethane, 1,2-dichloroethanes, 1,3-dichloropropane, The alkyl dihalide of the straight-chain such as 1,4-dichloroetane, 1,5-dichloropentane, 1,6-dichloro hexane, 1-bromo-3-chloropropane is (no Including fluorine atom)；The alkyl dihalide (not including fluorine atom) that 2,2-dimethyl-1,3-dichloropropane etc. comprises side chain；1, The aralkyl dihalide (not including fluorine atom) such as double (bromomethyl) benzene of 4-, double (bromomethyl) benzene of 1,3-；Ethylene glycol bisthioglycolate methanesulfonic acid The disulfonate of the glycol such as ester, ethylene glycol bisthioglycolate tosylate, propylene glycol bis-mesylate, tetramethylene glycol bis-mesylate Deng.

As the alkylating agent used in operation (ib), 3-bromopropyl alcohol, 2-bromopropyl alcohol, 3-chloro-2,2-diformazan can be enumerated The protective etc. of the haloalkyl alcohol such as base-1-propanol.

<2.5.4. autofrettage D: the autofrettage of the low polyfluorene represented by alkylating formula (2d) based on low polyfluorene A1)>

Low polyfluorene represented by formula (2d) can be by the alkylation of the alkylating agent represented by low polyfluorene A1 and formula (10) Reaction manufactures.

[changing 100]

In formula (10), Xb and R¹⁰Identical with above-mentioned formula (8).R²¹With R⁹Identical.

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

R¹⁰For the formula (2d) beyond Direct Bonding low polyfluorene can by the presence of a base, according to<2.5.3 autofrettage C> The middle method identical as the method described in operation (ia) or (iib) is to the alkylating agent represented by low polyfluorene A1 and formula (10) It is alkylated reaction to manufacture.

As in autofrettage D use alkylating agent, 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 ester, 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 alkane acid alkyl esters such as the bromo-propionic acid tert-butyl ester, iodopropionic acid methyl ester, iodopropionic acid ethyl ester, the iodopropionic acid tert-butyl ester；4-chloromethylbenzene Methyl formate, 4-bromomethyl-benzoic acid methyl ester, 4-chloromethyl benzoic acid ethyl ester, 4-bromomethyl-benzoic acid ethyl ester, 3-chloromethylbenzene The haloalkyl benzoic acid Arrcostabs etc. such as methyl formate, 3-bromomethyl-benzoic acid methyl ester.

<3 low polyfluorene compositions>

The low polyfluorene compositions of the present invention comprises low polyfluorene A1 (having the Oligofluorenylene compounds of 1 reactive functional groups) And/or they (are referred to as by low polyfluorene A2 (having the Oligofluorenylene compounds of 2 different reactive functional groups) sometimes below " low polyfluorene A ") and with this low polyfluorene A, there is described later low polyfluorene B of different chemical structures.Particularly, from controlling the poly-of resin The aspect of sum velocity or molecular weight etc. is set out, and preferably comprises low polyfluorene A1, on the other hand, from obtain easily resulting from 2 kinds with The aspect of the resin characteristics etc. of upper reactive functional groups is set out, and preferably comprises low polyfluorene A2.

<3.1 low polyfluorene B>

Above-mentioned low polyfluorene B comprises the carbon atom of 9 of the fluorenes unit b of more than 2 with or without substituent group each other By the alkylidene with or without substituent group, the arlydene with or without substituent group or with or without taking Oligomeric fluorene structural units that the sub-aralkyl of Dai Ji is bonded with chain (the most oligomeric fluorene structural units b),

[changing 101]

In formula (B), R^d～R^fBe each independently hydrogen atom, carbon number with or without substituent group is 1～10 Alkyl, the aryl that carbon number is 4～10 with or without substituent group or the carbon atom with or without substituent group Number is the aralkyl of 6～10, X¹For ester group, amide groups, carboxyl, cyano group or nitro.* it is former with the carbon of 9 of fluorenes unit b The associative key that son combines.

As the bonding alkylidene of fluorenes unit b, arlydene and sub-aralkyl, the most preferably can use at < 1.1 alkylenes Base, arlydene, sub-aralkyl > in illustrated group.It addition, bonding fluorenes unit b group with low polyfluorene is bonded fluorenes unit a Group can be the same or different.From the aspect that can manufacture simultaneously, the most identical.

Similarly, as the R in formula (B)^d～R^fAnd X¹, the most preferably can use and make in<1.3 reactive functional groups> For R^a～R^cWith the group illustrated in X.It addition, the R in formula (B)^d～R^fAnd X¹R with the formula (A) in low polyfluorene^a～R^cCan with X With identical can also be different.From the aspect that can manufacture simultaneously, the most identical.

As low polyfluorene B of the present invention, specifically, it may be preferred to use the material represented by following formula (7).

[changing 102]

In formula (7), R¹³It is each independently Direct Bonding, the Asia that carbon number is 1～4 with or without substituent group Alkyl,

R¹⁴～R¹⁹Be each independently hydrogen atom, with or without substituent group the alkyl that carbon number is 1～10, The aryl that carbon number is 4～10 with or without substituent group, the carbon number with or without substituent group are 1～10 Acyl group, the acyloxy that carbon number is 1～10 with or without substituent group, the carbon atom with or without substituent group Number is the alkoxyl of 1～10, with or without the aryloxy group that carbon number is 1～10 of substituent group, with or without taking The amino of Dai Ji, the vinyl that carbon number is 1～10 with or without substituent group, the carbon with or without substituent group Atomic number be 1～10 acetenyl, have substituent group sulphur atom, have the silicon atom of substituent group, halogen atom, nitro or Cyano group.Wherein, at R¹⁴～R¹⁹In, at least 2 adjacent groups can be mutually bonded formation ring.

R^d～R^fIt is each independently hydrogen atom, the alkyl that carbon number is 1～10 with or without substituent group, tool Have or do not have substituent group the aryl that carbon number is 4～10 or with or without the carbon number of substituent group be 6～ The aralkyl of 10,

X¹For ester group, amide groups, carboxyl, cyano group or nitro.

N represents the integer value of 1～5.

As the R in formula (7)¹³, preferably can use as the R in formula (1)³Illustrated group.Similarly, as formula (7) R in¹⁴～R¹⁹, preferably can use as the R in formula (1)⁴～R⁹Illustrated group.It addition, as in formula (7) R^d～R^f, preferably can use as the R in formula (1)^a～R^cIllustrated group.Additionally, as the X in formula (7)¹, preferably may be used To use as the group illustrated in the X in formula (1).As the n in formula (7), preferably can use as the n institute in formula (1) The group illustrated.

As the concrete example of low polyfluorene B of the present invention, the structure shown in following [G] group can be enumerated.

[changing 103]

[changing 104]

[changing 105]

<3.4 content>

About the content of above-mentioned low polyfluorene A in the low polyfluorene compositions of the present invention, it is not particularly limited, from controlling polymerization The aspect of the molecular weight of thing is set out, and more than preferably 0.1 mass %, more than more preferably 0.5 mass %, is further preferably More than 1 mass %, and below preferably 60 mass %, below more preferably 50 mass %, be further preferably 40 matter Amount below %.

About the content of above-mentioned low polyfluorene B in the low polyfluorene compositions of the present invention, it is not particularly limited, from improving polymerization The aspect of the degree of polymerization of thing is set out, and more than preferably 5 mass %, more than more preferably 10 mass %, is further preferably 15 More than quality %.Additionally, it is preferred that be below below 60 mass %, more preferably 50 mass %, further preferably 40 matter Amount below %.

It addition, about low polyfluorene A contained by low polyfluorene compositions and the content ratio of low polyfluorene B, be not particularly limited, From the aspect of the molecular weight controlling polymer, low polyfluorene A contained in compositions is (oligomeric with the mol ratio of low polyfluorene B The molal quantity of the molal quantity of fluorenes A/low polyfluorene B) be preferably more than 0.001, more preferably more than 0.005, more preferably More than 0.01, and from improving the aspect of the degree of polymerization of polymer, preferably less than 0.05, more preferably less than 0.03, More preferably less than 0.02.

Low polyfluorene A contained in low polyfluorene compositions, the molal quantity of low polyfluorene B such as can also utilize calibration trace by The area % that HPLC analyzes estimates.

<4 resin combination>

The low polyfluorene of the present invention can be used to manufacture resin combination.

In the case of using low polyfluorene A as low polyfluorene, for example, it is possible to it is shown to obtain being had following formula (5) by end The resin combination that formed of the polymer of structure or containing the resin combination of this polymer.

[changing 106]

In formula (5), R³It is each independently Direct Bonding, the Asia that carbon number is 1～4 with or without substituent group Alkyl,

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

N represents the integer value of 1～5.

* it is the associative key being combined with linking group.

As the R in formula (5)³～R⁹、R^a～R^cAnd n, can be suitable for using as the R in formula (1)³～R⁹、R^a～R^cAnd n Illustrated situation.

The polymer of the resin combination of the present invention preferably has the low polyfluorene of divalent as repetitive.

In the case of Gai, the resin combination of the present invention be except containing the low polyfluorene polymerization as repetitive with divalent Beyond thing, it is also possible to containing other polymer described later, additionally can be containing additive etc..

About obtaining there is the low polyfluorene of divalent as the method for the polymer of repetitive, it is not particularly limited, such as, exists In the case of using Oligofluorenylene compounds A2 as low polyfluorene, can obtain having from reactive functional groups is two or more Linking group and there is the low polyfluorene polymer as repetitive of divalent.Further, by using low polyfluorene B, it is also possible to To the low polyfluorene polymer as repetitive with divalent.

The low polyfluorene of divalent comprises the fluorenes unit of more than 2 with or without substituent group, and 9 of this fluorenes unit Carbon atom each other by the alkylidene with or without substituent group, the arlydene with or without substituent group or tool The sub-aralkyl having or not having substituent group is bonded with chain.

As fluorenes unit, it may be preferred to use as the fluorenes unit illustrated in the fluorenes unit a of low polyfluorene A, as low polyfluorene B The fluorenes unit illustrated in fluorenes unit b.

Similarly, as the alkylidene of bonding fluorenes unit, it may be preferred to use the bonding fluorenes unit a's as low polyfluorene A Group illustrated in alkylidene, as the group illustrated in the alkylidene of the bonding fluorenes unit b of low polyfluorene B.

It addition, as the arlydene of bonding fluorenes unit, it may be preferred to use the Asia of the bonding fluorenes unit a as low polyfluorene A Group illustrated in aryl, as the group illustrated in the arlydene of the bonding fluorenes unit b of low polyfluorene B.

Additionally, as the sub-aralkyl of bonding fluorenes unit, it may be preferred to use the bonding fluorenes unit a's as low polyfluorene A Sub-group illustrated in aralkyl, as the group illustrated in the sub-aralkyl of the bonding fluorenes unit b of low polyfluorene B.

The low polyfluorene of above-mentioned divalent can also be: in the fluorenes unit more than 2, at 9 of the fluorenes unit being positioned at two ends Carbon atom on be bonded with substituents alpha respectively¹And α², make this substituents alpha¹And α²For divalent group.In this case, α¹And α²Can With identical can also be different.It addition, substituents alpha¹And α²In comprise Direct Bonding, i.e. the carbon that can also make 9 of fluorenes unit is former Son is divalent group.

Alternatively base α¹And α²It is not particularly limited, Direct Bonding, former with or without the carbon of substituent group can be enumerated Subnumber is the alkylidene of 1～10, with or without the arlydene that carbon number is 4～10 of substituent group or have or not The carbon number with substituent group is the sub-aralkyl of 6～10；Or choosing is freely with or without the carbon number of substituent group Be the alkylidene of 1～10, with or without the arlydene that carbon number is 4～10 of substituent group with or without replacement The carbon number of base be 6～10 sub-aralkyl composition group in more than 2 group pass through 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.

Hereinafter enumerate and " select the free alkylidene that carbon number is 1～10 with or without substituent group, have or do not have The carbon number of substituted base is the arlydene of 4～10 and with or without the sub-virtue that the carbon number of substituent group is 6～10 Alkyl composition group in more than 2 group pass through oxygen atom, with or without substituent group sulphur atom, have or do not have The group that the nitrogen-atoms of substituted base or carbonyl are formed by connecting " concrete structure, but be not limited to these, can enumerate following Divalent group shown in [H] group.

[changing 107]

[H]

Among these, preferably while the transparency that can keep resin combination and stability give flexibility, The group that the group of more than 2 in alkylidene, arlydene or sub-aralkyl is formed by connecting by oxygen atom, more preferably may be used Oxygen is passed through giving the alkylidene shown in following [I] group of the glass transition temperature improving resin combination while flexibility The group that atom is formed by connecting.

[changing 108]

[I]

Among these, in substituent group_α ¹And α²In at least 1 be Direct Bonding or substituents alpha¹And α²In at least 1 In the case of individual carbon number is more than 2, owing to fluorenes ring (fluorenes unit) is generally perpendicularly orientated relative to main chain, even if thus The ratio of the low polyfluorene of the divalent in resin combination is few, it may have easily show the tendency of inverse wave length dispersibility.The latter's In the case of, from same aspect, preferably make α¹And α²Both carbon numbers are more than 2.On the other hand, substituent group is made α¹And α²In the case of both carbon numbers are 1 (that is, with or without the methylene of substituent group), fluorenes ring (fluorenes unit) phase It not generally perpendicularly to be orientated for main chain, but be orientated the most obliquely, so even at wide range resin combination In the ratio of low polyfluorene of divalent, it may have be easily formed at the tendency of the little smooth dispersibility of the difference of phase contrast in wide band.

It may further be preferable that have the low photoelasticity system being capable of required by blooming owing to not there is aromatic rings Number tendency, Direct Bonding, methylene, ethylidene, positive propylidene, positive butylidene, methylmethylene, 1-methyl ethylidene, 2-methyl ethylidene, 2,2-dimethylpropylidene, 2-methoxy-2-methyl propylene or the alicyclic ring shown in 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.)

Further it is preferably Direct Bonding, methylene, ethylidene, positive propylidene, positive butylidene, methylmethylene, 1- Methyl ethylidene, 2-methyl ethylidene or 2,2-dimethylpropylidene.Particularly preferably methylene, ethylidene or positive sub-third Base.

On the other hand, for the mechanical strength of film obtained by improving, the purpose of reliability under high temperature, it is preferably able to carry The glass transition temperature of high resin compositions, carbon number be 4～10 arlydene or choosing freely with or without The carbon number of substituent group is the alkylidene of 1～10 and with or without the arlydene that carbon number is 4～10 of substituent group The group that is formed by connecting by oxygen atom of more than 2 groups in the group of composition, more preferably Isosorbide-5-Nitrae-phenylene, 1,5-Asia naphthalene Divalent group shown in base, 2,6-naphthylene or following [H2] group.

[changing 110]

[H2]

It addition, in the case of being applied to have the phase retardation film of inverse wave length dispersibility, suitably select substituents alpha¹And α²It is Important.Such as, due to the group that carbon number is 1 with methylene as representative, to have unforeseeable inverse wave length dispersibility low Tendency, thus α¹And α²Be preferably Direct Bonding or its at least any one be carbon number be the group of more than 2.

It is further preferred that be capable of owing to not there is aromatic rings the low photoelastic coefficient required by blooming, straight Connect bonding, ethylidene, positive propylidene, positive butylidene, methylmethylene, 1-methyl ethylidene, 2-methyl ethylidene, 2,2-diformazan Ester ring type alkylidene shown in base propylidene, 2-methoxy-2-methyl propylene or above-mentioned [J] group；Or can increase The glass transition temperature of high resin compositions, 1,4-phenylene, the free carbon number with or without substituent group of choosing Be 1～10 alkylidene and with or without substituent group the arlydene that carbon number is 4～10 form group in 2 with On the group that is formed by connecting by oxygen atom of group.

Most preferably ethylidene or positive propylidene.Owing to having inclining of glass transition temperature reduction when chain length is longer To, thus the shortest chain-like groups, such as preferably carbon number is the group of less than 3.Further, due to molecular structure Reduce, it is thus possible to the concentration (fluorenes ratio) of the fluorenes ring in raising repetitive such that it is able to efficiency shows institute's phase well The optics physical property hoped.

So, the resin combination of the present invention is by being led to each other by the carbon atom of 9 of the fluorenes unit b with more than 2 The polymer crossing the repetitive that specific carbon-carbon bond is formed by connecting is formed, or containing this polymer, thus have can be more Effectively obtain the tendency of optical characteristics from fluorenes ring.

As the low polyfluorene of above-mentioned divalent, specifically, it may be preferred to use the material represented by following formula (11).

[changing 111]

In formula (11), R¹～R³It is each independently Direct Bonding or the carbon number with or without substituent group is The alkylidene of 1～4.

N represents the integer value of 1～5.

As the R in above-mentioned formula (11)¹And R², substituents alpha can be preferably used as respectively¹And α²Illustrated group.

It addition, as the R in above-mentioned formula (11)³～R⁹And n, the R in above-mentioned formula (1) can be preferably used as respectively³~ R⁹With the situation illustrated in n.

<4.2 polymer>

Polymer contained in the resin combination of the present invention has the low polyfluorene of divalent as repetitive.Such as, may be used To enumerate the polymer that the low polyfluorene of divalent is formed by connecting each other by arbitrary linking group.It addition, this polymer can also be There is the copolymer of any repetitive beyond the low polyfluorene of divalent.

<4.3 linking group>

Identical with the linking group of explanation in the item of<3.4 linking group>of above-mentioned " invention 2 ".

<4.4 copolymer>

Having the low polyfluorene of divalent can also be for comprising arbitrary divalent organic group further as the polymer of repetitive Group's (the most not including the low polyfluorene of divalent) is as the copolymer of repetitive.In this case, repetitive the most preferably passes through Above-mentioned linking group is connected.

In the copolymer, as the arbitrary divalent organic group that can share with the low polyfluorene of divalent, " invent with above-mentioned In the item of<3.5 copolymer>2 ", the group of explanation is identical.

<4.5 copolymerization composition>

Identical with the copolymerization composition of explanation in the item at<the 3.7 copolymerization composition>of above-mentioned " invention 2 ".

Identical with the composition of explanation in the item of<compositions of 3.9 resin combinations>of above-mentioned " invention 2 ".

" invention 4 "

Hereinafter, to the low polyfluorene diester of the present invention 4 and the manufacturer of the resin combination employing this low polyfluorene diester Method is described in detail.

It should be noted that (formula) formula (1) set forth below, (1a), (1b), (1a-I), (1a-II), (10e), (I) ～(V), (IIa), (IIb), (VI-1) are for illustrating each structure in the present invention 4.

<1 low polyfluorene diester A>

The low polyfluorene diester (hereinafter sometimes called " low polyfluorene diester A ") of the present invention comprises with or without replacement The fluorenes unit of more than 2 of base, the carbon atom of 9 of this fluorenes unit is 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 low polyfluorene diester of the present invention, specifically, it may be preferred to use the material represented by following formula (1).

[changing 112]

In formula, R¹～R³It is each independently Direct Bonding or the carbon number with or without substituent group is 1～4 Alkylidene.

R¹⁰Be carbon number be the organic substituent of 1～10.

N represents the integer value of 1～5.

In above-mentioned formula (1), as R¹And R², the R of above-mentioned " invention 1 " can be preferably used in respectively¹And R²This group Group illustrated in.

Similarly, as R³, it may be preferred to use the R in above-mentioned " invention 1 "³This group in illustrated group.

As R⁴～R⁹, it may be preferred to use the R in above-mentioned " invention 1 "⁴～R⁹This group in illustrated group.

It addition, as R¹⁰, it may be preferred to use in<1.3 ester group>of above-mentioned " invention 2 " as organic substituent institute example The group shown.

Owing to can reducing the heat stability of low polyfluorene diester A, causing coloring, thus the content of above-mentioned metal is preferably 400 Below quality ppm, below more preferably 200 mass ppm, more preferably 100 mass ppm be preferably 50 further below Below quality ppm, below particularly preferably below 10ppm, most preferably 5 mass ppm.

The kind of above-mentioned metal is not particularly limited, due to the gold used as catalyst when low polyfluorene diester manufactures Belong to and being likely mixed into, thus be thought of as selected from long period type periodic chart the 1st race, the 2nd race, the 12nd race, the 14th race and transition metal In at least one metal.Specifically, as the 1st race's metal, lithium, sodium, potassium, caesium can be enumerated, as group II metal, can To enumerate magnesium, calcium, barium, as the 12nd race's metal, zinc, cadmium can be enumerated, as the 13rd race's metal, aluminum can be enumerated, as 14 race's metals, can enumerate stannum, lead, as transition metal, can enumerate ferrum, copper, titanium, zirconium, manganese, cobalt, vanadium.The present invention's is oligomeric Catalyst remaining etc. when fluorenes diester is owing to manufacturing, usually contains metal.

In the low polyfluorene diester of the present invention, may be containing the sodium brought by following operation, potassium isometric preiodic type cycle The metal of the 2nd races such as the metal of Biao 1 race, calcium, this operation carries out hydroxyl first for making formaldehydes have an effect in the presence of a base The operation of base.Additionally, it is possible to can be containing transition metal, sodium, the isometric preiodic types of potassium such as the titanium brought by following operation, copper, ferrum The metal of the 14th races such as the metal of the 2nd race, zinc, the cadmiums etc. such as periodic chart the 1st race, magnesium, calcium the 12nd metal of race, stannum, this operation is Diaryl carbonates esters is made to have an effect and carry out the operation of ester exchange in the presence of catalyst for ester exchange reaction.

Among these, from the reactive aspect of catalyst for ester exchange reaction, preferably transition metal, it is more preferably Titanium or zirconium, more preferably titanium.

As the algoscopy of the content of metal, such as, can enumerate ICP-QMS method.

As the method making amount of metal be above-mentioned scope, such as, can enumerate common method for refining, such as recrystallization, sink again Filter operation, the column chromatographies etc. such as shallow lake method, Hydrolysis kinetics, filter filtration.It addition, the ester-interchange method manufacture present invention's is low utilizing In the case of polyfluorene diester A, the carboxylic acid composition reducing the moisture in raw material or impurity in advance is critically important.

Manufacture method about the low polyfluorene of the present invention is not particularly limited, such as can be by the manufacture shown in following formula The method such as method A or autofrettage B manufactures.

[changing 113]

Herein, in each structural formula, R¹～R³It is each independently Direct Bonding or with or without substituent group Carbon number is the alkylidene of 1～4.

N represents the integer value of 1～5.

R¹⁰Be carbon number be the organic substituent of 1～10.

<1.3.1 autofrettage A>

Autofrettage A is following method: using fluorenes class (I) as raw material, is converted to 9-hydroxymethyl fluorenes class (IV), passes through afterwards Dehydration synthesis alkene body (V), makes alkene body (V) react with fluorenyl anion, manufactures R³Low polyfluorene chemical combination for methylene Thing (II).It should be noted that unsubstituted 9-hydroxymethyl fluorenes can be bought as reagent.Also can low polyfluorene that thus place obtains Compound (II) imports ester group according to operation described later (ii) and makes low polyfluorene diester (1).

The most known have 9-hydroxymethyl fluorenes is converted into 9-methylene-9H-fluorenes after synthesized by anionic polymerisation low The method (J.Am.Chem.Soc., 123,2001,9182-9183.) of the mixture of polyfluorene.It is referred to these methods, manufactures Oligofluorenylene compounds (II).

<1.3.2 autofrettage B>

Autofrettage B is following method: carry out synthesis of oligonucleotides fluorenes by the cross-linking reaction (operation (i)) carrying out raw material fluorenes class (I) Compound (II), manufactures low polyfluorene diester (1) thereafter by importing ester group (operation (ii)).

[changing 114]

Above-mentioned various in, R¹～R¹⁰With the R in formula (1)¹～R¹⁰Implication is identical.

Below autofrettage B is divided into autofrettage and operation (ii) the low polyfluorene diester of operation (i) Oligofluorenylene compounds (II) (1) autofrettage is recorded.

[changing 115]

Above-mentioned various in, R³～R⁹With n and the R in above-mentioned formula (1)³～R⁹Implication is identical.

Below the manufacture method of the Oligofluorenylene compounds (II) in operation (i) is divided into n and R³Situation record.

< 1.3.3.1n=1, R³Situation for Direct Bonding: 9,9 ': 9 ', 9 " manufacture method of-three difluorenes >

9, the synthetic method of 9 '-difluorene is known to be had multiple, can carry out synthesizing 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 purchased as reagent Enter.

< 1.3.3.2n=2, R³Situation for Direct Bonding: 9,9 ': 9 ', 9 " manufacture method of-three difluorenes >

< 1.3.3.3 operation (ia): R³The manufacture method of situation for methylene >

The methylene-crosslinked Oligofluorenylene compounds that has represented by following formula (IIa) can be by fluorenes class (I) and formaldehydes Reaction the most represented manufactures.

[changing 116]

Above-mentioned various in, R⁴～R⁹With n and the R in above-mentioned formula (1)⁴～R⁹Implication is identical.

<1.3.3.3.1 formaldehydes>

(definition of theoretical amount)

In the case of being manufactured as the Oligofluorenylene compounds (IIa) of target, formaldehydes is relative to the reason of raw material fluorenes class (I) Stoichiometric (mol ratio) is represented by n/ (n+1).

(the preferably more than reason of theoretical amount)

In the case of the formaldehydes that fluorenes class (I) uses more than theoretical amount, there is can generate with as target low Polyfluorene compound (IIa) compares the tendency of the Oligofluorenylene compounds that fluorenes cross-links further.Fluorenes due to Oligofluorenylene compounds Number of rings more increases dissolubility and more can reduce, thus there are the low polyfluorene chemical combination of more than 4 fluorenes ring crosslinkings in goal object In the case of thing, it is known that there is the tendency that refined load increases.Therefore it is usually preferred to the consumption of formaldehydes is goal theory amount Less than n/ (n+1) times mole.

(not the most being significantly less than the reason of theoretical amount)

If it addition, the consumption of formaldehydes is significantly less than theoretical amount n/ (n+1), then with the Oligofluorenylene compounds as target (IIa) compare the few Oligofluorenylene compounds of the number of crosslinks of fluorenes ring and be main product or raw material fluorenes class (I) unreacted has residual, It will be appreciated that have the tendency that yield is greatly reduced.

Thus, about the optimum amount of formaldehydes, specifically, in the case of n=1, relative to fluorenes class (I) usually More than 0.1 times mole, preferably more than 0.3 times mole, more preferably more than 0.38 times mole, and usually 0.5 times Below mole, it is preferably less than 0.46 times mole, more preferably less than 0.42 times mole.

Additionally, in the case of n=2, usually more than 0.5 times mole, be preferably more than 0.55 times mole, the most excellent Elect more than 0.6 times mole as, and usually less than 0.66 times mole, be preferably less than 0.65 times mole, more preferably Less than 0.63 times mole.It follows that according to the consumption of formaldehydes, the structure of main product and the ratio of product have the biggest change Change, by using under conditions of limiting formaldehydes consumption, it is possible to obtain the Oligofluorenylene compounds of target n number with high yield (IIa)。

<1.3.3.3.2 alkali>

In the case of utilizing homogeneous system to react, among them, there is the alkali of fully alkalescence the most in the reaction Feldalat NM that the alkoxide of metal, more preferably industrial cost are low and Sodium ethylate.Alkali alcoholate herein can use powdery Material, it is possible to use the liquids such as alcoholic solution.And alkali metal can be made to react with alcohol prepare.

On the other hand, in the case of utilizing two coating systems to react, among them, have the most in the reaction fully The aqueous solution of alkali metal hydroxide of alkalescence, sodium hydroxide that more preferably industrial cost is low, the aqueous solution of potassium hydroxide.

It addition, about the concentration of aqueous solution, in the case of using particularly preferred sodium hydrate aqueous solution, when concentration is low Response speed significantly reduces, thus particularly preferably use usually more than 10wt/wt%, be preferably more than 25wt/wt%, more excellent Elect the aqueous solution of more than 40wt/wt% as.

In the case of utilizing homogeneous system to react, the consumption of alkali there is no the special upper limit relative to raw material fluorenes class (I), but If consumption is too much, then stirring or reacted refined load increase, thus usually less than 10 times moles of fluorenes class (I), preferred It it is less than 5 times moles, more preferably less than 1 times mole.On the other hand, if the consumption of alkali is very few, then the carrying out reacted is slow Slow, thus as lower limit, be commonly angled relative to raw material fluorenes class (I) and be more than 0.01 times mole, be preferably more than 0.1 times mole, enter One step is preferably more than 0.2 times mole.

On the other hand, in the case of utilizing two coating systems to react, the consumption of alkali there is no spy relative to raw material fluorenes class (I) The other upper limit, if but consumption is too much, then and stirring or reacted refined load increase, thus 10 times moles of usually fluorenes class (I) Below, it is preferably less than 5 times moles, more preferably less than 2 times moles.On the other hand, if the consumption of alkali is very few, then react Carry out slow, thus as lower limit, be commonly angled relative to raw material fluorenes class (I) and be more than 0.1 times mole, be preferably 0.3 times mole Above, more preferably more than 0.4 times mole.

<1.3.3.3.3 solvent>

Operation (ia) is preferably used solvent and carries out.As the concrete example of the solvent that can use, can enumerate: as alkyl The acetonitrile of nitrile series solvent, propionitrile etc.；As the diethyl ether of ether series solvent, oxolane, 1,4-dioxane, methylcyclopentyl Ether, t-butyl methyl ether etc.；As the 1,2-dichloroethanes of halogen series solvent, dichloromethane, chloroform, 1,1,2,2-sym-tetrachloroethane Deng；As the chlorobenzene of halogen system aromatic hydrocarbon, 1,2-dichloro-benzenes etc.；As N,N-dimethylformamide, the N of amide series solvent, N-dimethyl acetylamide, N-Methyl pyrrolidone etc.；As the dimethyl sulfoxide of sulfoxide series solvent, sulfolane etc.；As ring type The monocyclic aliphatic hydrocarbon such as the Pentamethylene. of aliphatic hydrocarbon, hexamethylene, cycloheptane, cyclooctane, for its derivant methyl cyclopentane, Ethyl cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-dimethyl Hexamethylene, isopropyl cyclohexane, n-pro-pyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene, 1,2, 4-trimethyl-cyclohexane, 1,3,5-trimethyl-cyclohexanes etc., the polycycle aliphatic hydrocarbon such as decahydronaphthalenes；Pentane, normal hexane, just The non-ring type aliphatic hydrocarbons such as heptane, normal octane, isobutyltrimethylmethane., n-nonane, n-decane, n-dodecane, n-tetradecane；As aromatic series The toluene of hydrocarbon, xylol, o-Dimethylbenzene, meta-xylene etc.；As the methanol of alcohol series solvent, ethanol, isopropanol, n-butyl alcohol, The tert-butyl alcohol, hexanol, capryl alcohol, Hexalin etc..

In the reaction of homogeneous system, the dissolubility of the anion owing to being generated by fluorenes class (I) is high, have reaction carries out good Good tendency, thus the preferably amide series solvent of polar solvent or sulfoxide series solvent.Wherein, particularly preferably N, N-bis- Methylformamide.This is because, the dissolubility that Oligofluorenylene compounds (IIa) is in DMF is low, in goal object Separate out rapidly after generation, suppress the carrying out of its above reaction, there is the tendency that the selectivity of goal object increases.

In the reaction of two coating systems, form 2 layers with alkaline aqueous solution, fluorenes class (I) dissolubility of the anion generated Height, has reaction and carries out good tendency, thus the preferably ether series solvent of polar solvent or halogen series solvent.Wherein special You Xuanwei oxolane.This is because, the dissolubility that Oligofluorenylene compounds (IIa) is in oxolane is low, raw in goal object Separate out rapidly after one-tenth, suppress the carrying out of its above reaction, there is the tendency that the selectivity of goal object increases.

About the consumption of solvent, generally use and reach 10 times of volumes of raw material fluorenes class (I), be preferably 7 times of volumes, enter One step is preferably the amount of 4 times of volumes.On the other hand, if the consumption of solvent is very few, then stirring becomes difficult, has entering of reaction simultaneously Row is inclined to slowly, thus as lower limit, generally use reach raw material fluorenes class (I) 1 times of volume, be preferably 2 times of volumes, The more preferably amount of 3 times of volumes.

<1.3.3.3.4 reaction formation>

<1.3.3.3.5 reaction condition>

For operation (ia), in order to suppress the life of the compound of fluorenes ring crosslinking compared with Oligofluorenylene compounds (IIa) Become, react the most at low temperatures.On the other hand, if temperature is too low, then sufficient response speed may be can not get.

Accordingly, as concrete reaction temperature, generally it is 40 DEG C in the upper limit, is preferably the temperature of 30 DEG C, more preferably 20 DEG C Under implement.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 and implement.

About the General reactions time in operation (ia), usual lower limit is 30 minutes, is preferably 60 minutes, further preferably Be 2 hours, the upper limit without particular limitation of, but usually 20 hours, be preferably 10 hours, more preferably 5 hours.

After termination of the reaction, reactant liquor can be added in the acid waters such as dilute hydrochloric acid, or the acid waters such as dilute hydrochloric acid are added It is added in reactant liquor, makes goal object Oligofluorenylene compounds (IIa) separate out, thus separate.

Additionally, after termination of the reaction, it is possible to the solvent of solubilized goal object Oligofluorenylene compounds (IIa) is added to water In reactant liquor, extract.Utilize the goal object that solvent extraction goes out can be by by the method for solvent concentration or add bad molten The methods of agent etc. separate.But, owing to Oligofluorenylene compounds (IIa) at room temperature has dissolubility in a solvent very Low tendency, thus generally preferably contact the method making it separate out with acid water.

Obtained Oligofluorenylene compounds (IIa) also can use directly as the raw material of operation (ii), it is possible to is carrying out essence After system in operation (ii).As method for refining, common method for refining, such as recrystallization, reprecipitation method, extraction essence can be used System, column chromatography etc., and unrestrictedly.

< 1.3.3.4 operation (ib): R³Manufacture method for the situation beyond Direct Bonding >

Oligofluorenylene compounds represented by following formula (IIb) can be using fluorenes class (I) as raw material, at alkylating agent (VIIIa) and manufacture according to the reaction represented by following formula (ib) in the presence of alkali.

[changing 117]

Oligofluorenylene compounds structural formula (IIb) in above-mentioned formula represents.

In above-mentioned formula, R³、R⁴～R⁹With n and the R in above-mentioned formula (1)³、R⁴～R⁹Identical with n implication.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), use n-BuLi is as alkali, in the anion producing fluorenes class (I) After so that it is it is widely known by the people with the method for alkylating agent (VIIIa) coupling, it is known to R³Situation or R for ethylidene³For Asia The autofrettage of propyl group etc. (Organometallics, 2008,27,3924；J.Molec.Cat.A:Chem., 2004,214, 187.).Additionally, also utilize in addition to alkylidene report example that xylylene carries out cross-linking (J.Am.Chem.Soc., 2007,129,8458.).But, when utilizing these to use the method for n-BuLi to carry out industry manufacture, at secure context, one-tenth Present aspect all has extremely difficult tendency.

As the alkylating agent used in operation (ib), can enumerate: diiodomethane, 1,2-ethylidene periodide, 1,3-diiodo- Propane, 1,4-bis-iodobutane, 1,5-bis-iodopentane, 1,6-bis-iodohexane, methylene bromide, glycol dibromide, 1,3-dibromo third Alkane, 1,4-dibromobutane, pentamethylene bromide, 1,6-dibromo-hexane, dichloromethane, 1,2-dichloroethanes, 1,3-dichloropropane, The alkyl dihalide of the straight-chain such as 1,4-dichloroetane, 1,5-dichloropentane, 1,6-dichloro hexane, 1-bromo-3-chloropropane is (no Including fluorine atom)；The alkyl dihalide (not including fluorine atom) that 2,2-dimethyl-1,3-dichloropropane etc. comprises side chain；1, The aralkyl dihalide (not including fluorine atom) such as double (bromomethyl) benzene of 4-, double (bromomethyl) benzene of 1,3-；Ethylene glycol bisthioglycolate methanesulfonic acid The disulfonate of the glycol such as ester, ethylene glycol bisthioglycolate tosylate, propylene glycol bis-mesylate, tetramethylene glycol bis-mesylate Deng.

Below, the manufacture method of the low polyfluorene diester (1) in the operation (ii) represented by following formula is pressed R¹And R²Kind divide Do not record.

[changing 118]

Above-mentioned various in, R¹～R⁹With n and the R in above-mentioned formula (1)¹～R⁹Identical with n implication.R_i、R_iiAnd R_iiiRepresent hydrogen Atom, the alkyl that carbon number is 1～10 with or without substituent group, the carbon number with or without substituent group are The aryl of 4～10 or the aralkyl that carbon number is 6～10 with or without substituent group.

<1.3.4.1 operation (iia): in formula (1), autofrettage based on Michael (Michael) addition>

Low polyfluorene diester represented by following formula (1a) can be in the presence of a base according to represented by following operation (iia) Reaction is by Oligofluorenylene compounds (II) and α, and beta-unsaturated esters (VI) manufactures.

[changing 119]

In above-mentioned formula, R³～R¹⁰With n and the R in above-mentioned formula (1)³～R¹⁰Identical with n implication.R_i、R_iiAnd R_iiiThe most independent Ground represents hydrogen atom, the alkyl that carbon number is 1～10 with or without substituent group, the carbon with or without substituent group Atomic number is the aryl of 4～10 or with or without the aralkyl that carbon number is 6～10 of substituent group.

<1.3.4.1.1 α, beta-unsaturated esters>

As alpha, beta-unsaturated esters (VI), acrylic acid methyl ester., ethyl acrylate, phenyl acrylate, acrylic acid can be enumerated Allyl ester, glycidyl acrylate, 2-Hydroxy ethyl acrylate, acrylic acid-4-hydroxybutyl, 1,4 cyclohexane dimethanol The esters of acrylic acids such as mono acrylic ester, methyl methacrylate, ethyl methacrylate, phenyl methacrylate, metering system Methyl acrylic ester, the 2-ethyls third such as allyl propionate, glycidyl methacrylate, methacrylic acid-2-hydroxy methacrylate The alpha-substituted unsaturation esters such as e pioic acid methyl ester, 2-phenylacrylic acid methyl ester, methyl cinnamate, ethyl cinnamate, M Cr, The beta substitution unsaturation esters such as butenoic acid ethyl.Wherein, it is preferably able to be introduced directly into the following 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 The carbon number of Dai Ji be 1～10 alkyl, with or without substituent group the aryl that carbon number is 4～10 or tool There is or do not has the aralkyl that carbon number is 6～10 of substituent group.), the esters of acrylic acid that is more preferably included in, methyl Esters of acrylic acid or alpha-substituted unsaturation esters, from the aspect of response speed Yu reaction selectivity, further preferred R_iiiFor Hydrogen atom or the esters of acrylic acid of methyl or methyl acrylic ester.Due to R¹⁰During for less group, industrial cost low and Distillation is refined easily, reactivity is the highest, thus further preferably acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, Ethyl methacrylate, phenyl acrylate or phenyl methacrylate.Among these, owing to being difficult to by hydrolysis, being difficult to life One-tenth by-product carboxylic acid, thus particularly preferably ethyl acrylate, ethyl methacrylate.

On the other hand, about the organic substituent of ester group, for 2-Hydroxy ethyl acrylate, acrylic acid-4-hydroxybutyl, In the case of 1,4-CHDM mono acrylic ester etc. has the esters of hydroxy alkyl, polyester carbon can be obtained by a step Acid esters, the raw material of polyester, thus particularly preferably.

The polymerization activity of alpha, beta-unsaturated esters (VI) is high, thus in the presence of with high concentration, have easily due to light, heat, The outside stimuluss such as soda acid and occur polymerization tendency.Now, highly exothermic owing to being attended by, thus may be abnormally dangerous. Therefore, from the aspect of safety, the consumption of alpha, beta-unsaturated esters (VI) is preferred to be less excessively used.It is commonly angled relative to former Material Oligofluorenylene compounds (II) is less than 10 times moles, is preferably less than 5 times moles, more preferably less than 3 times moles.Close In lower limit, owing to being calculated as 2 times moles relative to raw material with theoretical amount, thus lower limit is usually more than 2 times moles.Anti-in order to accelerate Should carry out, not retained material or intermediate, the consumption of alpha, beta-unsaturated esters (VI) relative to raw material Oligofluorenylene compounds (II) is More than 2.2 times moles, more preferably more than 2.5 times moles.

<1.3.4.1.2 alkali>

At R³For methylene situation with in addition in the case of, the reactivity with Oligofluorenylene compounds (II) has relatively The tendency of big difference.Therefore, it is divided into R³Situation for methylene is recorded with situation in addition.

At R³In the case of methylene, Oligofluorenylene compounds (II) the most easily carries out decomposing instead Should.Therefore, the pairs such as decomposition reaction can be suppressed anti-in the case of utilizing the organic layer 2 coating systems with water layer to react The reason answered, is preferably used water miscible inorganic base.Wherein from the standpoint of cost, reactivity, the hydrogen-oxygen of preferred as alkali The aqueous solution of the aqueous solution of compound, the most more preferably sodium hydroxide or the aqueous solution of potassium hydroxide.

It addition, about the concentration of aqueous solution, in the case of using particularly preferred sodium hydrate aqueous solution, if concentration is low Then response speed can significantly reduce, thus use is usually more than 10wt/wt%, preferably more than 30wt/wt%, is more preferably The aqueous solution of more than 40wt/wt%.

At R³In the case of methylene, about the consumption of alkali, relative to raw material Oligofluorenylene compounds (II), its upper limit does not has There is restriction especially, but when the consumption of alkali is too much, stirring or reacted refined load may increase, thus using conduct In the case of the sodium hydrate aqueous solution of more than the 40wt/wt% of particularly preferred alkali, being commonly angled relative to low polyfluorene (II) is 10 Below times volume, it is preferably below below 5 times of volumes, more 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 relative to raw material Oligofluorenylene compounds (II).It is preferably 0.2 More than times volume, more than more preferably 0.5 times of volume.

At R³In the case of beyond methylene, about the consumption of alkali, relative to raw material Oligofluorenylene compounds (II), on it Limit is not particularly limited, but when the consumption of alkali is too much, stirring or reacted refined load may increase, thus is using In the case of the Feldalat NM of particularly preferred alkali or Sodium ethylate, it is commonly angled relative to Oligofluorenylene compounds (II) and is 5 times moles Below, less than 2 times moles, more preferably less than 1 times mole, particularly preferably less than 0.5 times mole it are preferably.At alkali number Time very few, response speed significantly reduction, thus alkali is relative to the low polyfluorene of raw material (II) usually more than 0.005 times mole.Excellent Elect more than 0.01 times mole, more preferably more than 0.05 times mole, particularly preferably more than 0.1 times mole as.

<1.3.4.1.3 phase transfer catalyst>

As phase transfer catalyst, can enumerate tetramethyl ammonium chloride, tetrabutyl ammonium bromide, methyl tricapryl ammonium chloride, Methyl three decyl ammonium chloride, benzyltrimethylammonium chloride, tri-n-octyl methyl ammonium chloride, tetrabutylammonium iodide, acetyl group trimethyl The halogenide (not including fluorine) of the quaternary ammonium salt such as ammonium bromide, benzyltriethylammoinium chloride；N, N-dimethyl pyrrolidine chloride, N- Ethyl-N-methyl pyrrolidine iodide, N-butyl-N-crassitude bromide, N-Benzyl-N-methyl pyrrolidine chlorine The halogenide (not including fluorine) of the season pyrrolidinium such as compound, N-ethyl-N-methyl pyrrolidine bromide；N-butyl-N-first The season morpholine such as base morpholine bromide, N-butyl-N-methylmorpholine iodide, N-pi-allyl-N-methylmorpholine bromide The halogenide (not including fluorine) of salt；N-methyl-N-benzyl piperidinium chloride, N-methyl-N-benzyl piperidinium bromide, N, The seasons such as N-lupetidine iodide, N-methyl-N ethyl Piperidineacetic acid salt, N-methyl-N ethyl piperidines iodide The halogenide (not including fluorine) of piperidinium salt；Crown ether-like etc..Preferably quaternary ammonium salt, further preferred tetrabutyl ammonium bromide, benzyl three Ammonio methacrylate or benzyltriethylammoinium chloride.

The consumption of phase transfer catalyst relative to raw material Oligofluorenylene compounds (II) too much time, there is ester hydrolysis or step by step The tendency that the side reactions such as michael reaction are significantly carried out, and from the aspect of cost, it is commonly angled relative to Oligofluorenylene compounds (II) also it is less than 5 times moles, is preferably less than 2 times moles, more preferably less than 1 times mole.Phase transfer catalyst When consumption is very few, responds the significantly reduced tendency of speed, thus the consumption of phase transfer catalyst is relative to the low polyfluorene of raw material Compound (II) usually more than 0.01 times mole.It is preferably more than 0.1 times mole, more preferably more than 0.5 times mole.

<1.3.4.1.4 solvent>

Operation (iia) is preferably used solvent and carries out.

At R³In the case of methylene, there is separated solvent by using with water, it is known that have and can suppress low The tendency of the side reactions such as the decomposition reaction of polyfluorene compound (II).Further, the low polyfluorene of raw material can preferably be dissolved in use In the case of the solvent of compound (II), for reasons of there is reaction and carry out good tendency, raw material low polyfluorene is preferably used The solvent that dissolubility is more than 0.5 mass % of compound (II), more preferably using this dissolubility is more than 1.0 mass %, spy Solvent that this dissolubility be 1.5 mass % more than is not preferably used.In particular, it is preferred that halogen system aliphatic hydrocarbon, halogen system virtue Fragrant race hydrocarbon, aromatic hydrocarbon or ether series solvent, particularly preferred dichloromethane, chlorobenzene, chloroform, 1,2-dichloro-benzenes, oxolane, 1,4-dioxane or methylcyclopentyl ether.

About the consumption of solvent, the upper limit is not particularly limited, if in view of the generation effect of the goal object in each reactor Rate, then generally use and reach 20 times of volumes of raw material Oligofluorenylene compounds (II), be preferably 15 times of volumes, further preferably It it is the amount of 10 times of volumes.On the other hand, if the consumption of solvent is very few, then the dissolubility of reagent is deteriorated, stirring becomes difficulty, the most anti- The carrying out answered is slow, thus reaches 1 times of volume of raw material Oligofluorenylene compounds (II) as lower limit, generally use, be preferably 2 The amount of times volume, more preferably 4 times of volumes.

At R³In the case of beyond methylene, it is known that there is the dissolubility of organic base and Oligofluorenylene compounds (II) to instead Answer speed to bring the tendency of considerable influence, in order to ensure this dissolubility, the dielectric constant with certain value more than is preferably used Solvent.As can preferably dissolve organic base and the solvent of Oligofluorenylene compounds (II), optimization aromatic heterocycle, alkyl nitrile are molten Agent, amide series solvent, sulfoxide series solvent, particularly preferred pyridine, acetonitrile, DMF, N,N-dimethylacetamide, Dimethyl sulfoxide, sulfolane.

About the consumption of solvent, the upper limit is not particularly limited, if in view of the generation effect of the goal object in each reactor Rate, then generally use reach the low polyfluorene of raw material (II) 20 times of volumes, be preferably 15 times of volumes, more preferably 10 times The amount of volume.On the other hand, if the consumption of solvent is very few, then the dissolubility of reagent is deteriorated, stirring becomes difficulty, has reaction simultaneously Carrying out be inclined to slowly, thus as lower limit, generally use and reach 1 times of volume of the low polyfluorene of raw material (II), be preferably 2 times The amount of volume, more preferably 4 times of volumes.

<1.3.4.1.5 reaction formation>

<1.3.4.1.6 reaction condition>

Operation (iia) if in temperature too low, then can not get sufficient response speed, otherwise if temperature is too high, then there is α, The polyreaction of beta-unsaturated esters (VI) is easily carried out, is easily generated the low polyfluorene represented by following formula (1a-I) by hydrolysis Monoesters monocarboxylic acid and the tendency of the low polyfluorene dicarboxylic acids represented by (1a-II), thus preferably carry out temperature treatment.Accordingly, as Reaction temperature, specifically, implements for 0 DEG C the most within the range having a lower limit of, preferably 10 DEG C, more preferably 15 DEG C.On the other hand, logical Often it is 40 DEG C, preferably 30 DEG C, more preferably 20 DEG C in the upper limit to implement.

[changing 121]

In above-mentioned formula, n, R³～R¹⁰、R_i、R_iiAnd R_iiiWith n, the R in above-mentioned formula (1a)³～R¹⁰、R_i、R_iiAnd R_iiiImplication phase With.

About the General reactions time in operation (iia), usual lower limit is 30 minutes, is preferably 1 hour, further preferably Being 2 hours, if the response time is long, then the low polyfluorene diester (1a) generated is likely to occur hydrolysis and generates carboxylic acid, thus generally It is 10 hours, is preferably 5 hours, more preferably 2 hours.

After termination of the reaction, following method can be used to make goal object low polyfluorene diester (1a) separate out, thus carry out goal object The separation of low polyfluorene diester (1a), described method is by filtering the inorganic base of byproduct metal halogenide and remaining from instead Answer and carry out the method for solvent concentration or the method for the poor solvent of adding purpose thing after liquid removes；Etc..

Additionally, after termination of the reaction, it is also possible in reactant liquor, add acid water and solubilized goal object low polyfluorene diester (1a) solvent extracts.The goal object utilizing solvent extraction to go out can be by the method concentrating solvent or interpolation The methods of poor solvent etc. separate.

As the solvent that can use when extracting, as long as solubilized goal object low polyfluorene diester (1a), there is no spy Do not limit, but be adapted in use to 1 in halogen series solvents such as the aromatic hydrocarbon compound such as toluene, dimethylbenzene, dichloromethane, chloroform etc. Plant or two or more.

The low polyfluorene diester (1a) herein obtained can make with the direct form with polyester or with polyestercarbonate starting monomer With, or use etc. can also be carried out with the form of the precursor of polycarbonate starting material monomer but it also may make after carrying out refining With.Particularly, as impurity containing carboxylic acid compositions such as low polyfluorene monoesters monocarboxylic acid (1a-I) and low polyfluorene dicarboxylic acids (1a-II) In the case of, when the manufacture of oligomeric fluorene diaryl ester (2), not only can cause to become the catalyst poison of catalyst for ester exchange reaction, Tenor contained by oligomeric fluorene diaryl ester (2) also can increase, it is known that the reduction with heat stability is relevant, the most preferably enters Row purification operations.As method for refining, common method for refining, such as recrystallization, reprecipitation method, Hydrolysis kinetics, post color can be used Spectrum etc., and unrestrictedly.In Hydrolysis kinetics, by using the aqueous solution of alkalescence, such that it is able to by carboxylic acid composition with the shape of carboxylate Formula removes in water layer, thus preferably.More preferably use sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide etc. The aqueous solution of inorganic base, is the most preferably difficult to the water-soluble of the weak base such as the sodium bicarbonate of hydrolysis, sodium carbonate, potassium carbonate Liquid.It addition, also can low polyfluorene diester (1a) be dissolved in suitable solvent, activated carbon is utilized to process.Now can make Solvent and the solvent phase that can use when extracting with.

The low polyfluorene diester (1a) herein obtained can be directly as polyester or polyestercarbonate starting monomer or conduct The precursor of polycarbonate starting material monomer carries out use etc..

<1.3.4.2 operation (iib): manufacture method based on alkylated reaction>

Low polyfluorene diester (1b) can be by through Oligofluorenylene compounds (II) and alkylating agent (VIIIb) and (VIIIc) The method of alkylated reaction manufacture.

[changing 122]

In above-mentioned formula, R¹～R¹⁰With n and the R in above-mentioned formula (1)¹～R¹⁰Identical with n implication.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, and such as, has report to propose 9, double (bromine hexyl) fluorenes of 9-, 9, and 9-is double Double (alkylhalide group) fluorenes (J.Org.Chem., 2010,75,2714.) of the 9,9-such as (iodine hexyl) fluorenes.According to these technological thoughts, it is possible to Oligofluorenylene compounds (II) is carried out synthesis of oligonucleotides fluorenes diester (1b) as raw material.

As the alkylating agent used in operation (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 ester, 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 alkane acid alkyl esters such as ethyl ester, neoprene acid ethyl ester, iodine ethyl n-butyrate., the iodopropionic acid tert-butyl ester；Phenyl chloroacetate, bromoacetic acid benzene The halogenated-chain acid aryl esters such as ester, iodoacetic acid phenyl ester；4-chloromethyl benzoic acid methyl ester, 4-bromomethyl-benzoic acid methyl ester, 4-chloromethane The alkyl halides such as yl benzoic acid ethyl ester, 4-bromomethyl-benzoic acid ethyl ester, 3-chloromethyl benzoic acid methyl ester, 3-bromomethyl-benzoic acid methyl ester Yl benzoic acid Arrcostab etc..

It should be noted that after the reaction terminating of operation (iib), preferably low to goal object polyfluorene diester (1b) is carried out point From refined.The method made as separation and purification, preferably can use in<separation and purification of 1.3.4.1.7 goal object> The method recorded.

< manufacture method (low polyfluorene two based on the ester exchange reaction virtue of the oligomeric fluorene diaryl ester of 1.3.4.3 formula (2) The autofrettage of base ester compounds (2)) >

Oligomeric fluorene diaryl ester compounds (2) can be by through low polyfluorene diester compound (1) and diaryl carbonate The method of the ester exchange reaction operation (operation (iic)) of class (11a) manufactures.

[changing 123]

In above-mentioned formula, R¹～R¹⁰With n and the R in above-mentioned formula (1)¹～R¹⁰Identical with n implication.Ar¹Represent and have or do not have The carbon number of substituted base is the aryl of 4～10.

< manufacture method (the low polyfluorene two based on ester exchange reaction of the oligomeric fluorene diaryl ester of 1.3.4.3.1 formula (2) The autofrettage of aryl ester compound (2)) >

Ar¹Oligomeric fluorene diaryl ester compounds for the aryl that carbon number is 4～10 with or without substituent group (2) can in the presence of ester exchange catalyst according to the reaction represented by operation (iic) by low polyfluorene diester compound (1), two virtue Base carbonates (11a) manufactures.

<1.3.4.3.1.1 low polyfluorene diester compound (1)>

When the content of the carboxylic acid of low polyfluorene diester compound (1) is many, carboxylic acid becomes the catalyst of catalyst for ester exchange reaction Poison, has and needs a large amount of tendency using catalyst for ester exchange reaction.Therefore, if the content of carboxylic acid is many, then there is low polyfluorene two The tendency that tenor contained by aryl ester compound (2) increases.From the metal reduced contained by oligomeric fluorene diaryl ester (2) The aspect of amount is set out, and the content of the carboxylic acid in low polyfluorene diester compound (1) is preferably below 5 mass %, more preferably 3 matter Below amount below %, more preferably 2 mass %, below further preferably 1 mass %.It addition, carboxylic acid content is the fewest The most preferred, if wanting to be 0 mass %, likely raising with significant cost to prevent that impurity is mixed into etc. or producing effect Rate reduces.The content maintaining productivity ratio and accessible carboxylic acid is usually more than 0.1 mass %.

As the carboxylic acid contained by low polyfluorene diester compound (1), such as, can enumerate low polyfluorene monoesters monocarboxylic acid, oligomeric Fluorenes dicarboxylic acids.

Low polyfluorene monoesters monocarboxylic acid contained by low polyfluorene diester compound (1), low polyfluorene dicarboxylic acids molal quantity such as The area % that calibration trace can be utilized to be analyzed by HPLC estimates.

<1.3.4.3.1.2 diaryl carbonate esters>

Diaryl carbonate esters as reaction reagent can enumerate diphenyl carbonate, carboxylol ester, double (chlorobenzene Base) carbonic ester, m-cresyl, carbonic acid dinaphthyl ester, double (biphenyl) esters of carbonic acid etc..The most preferably less than cost and can industry obtaining The diphenyl carbonate obtained.

These diaryl carbonates can be used alone a kind, it is possible to two or more is used in mixed way.

About the consumption of diaryl carbonate esters, there is no the special upper limit relative to raw material low polyfluorene diester (1), if but consumption Too much, then there is the tendency that reacted refined load increases, thus less than 20 times moles of the lowest polyfluorene diester, preferred It it is less than 10 times moles, more preferably less than 5 times moles.

On the other hand, if the consumption of arylcarbonic acid esters is very few, then raw material low polyfluorene diester (1) or as intermediate as Low polyfluorene list aryl ester (10e) shown in lower there may be residual, thus as lower limit, is commonly angled relative to raw material low polyfluorene diester (1) it is more than 1 times mole, is preferably more than 1.5 times moles, more preferably more than 2 times moles.

[changing 124]

<1.3.4.3.1.3 catalyst for ester exchange reaction>

As catalyst for ester exchange reaction, can enumerate: four titanium butoxide, four isobutoxy titaniums, titanium tetramethoxide, four different Titanium propanolate, purity titanium tetraethoxide, four (2-ethyl hexyl oxy) titanium, four (stearic epoxide) titanium, four phenoxide titaniums, titanium acetylacetone (IV), the titanium compound 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 epoxide 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 oxide hydrate, 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 compound such as copper, copper chloride；The ferrum such as hydrated ferric oxide., ferric carbonate, triacetoxyl group ferrum, trimethoxy ferrum, triple phenoxyl ferrum Compound；The zinc compounds such as bis-acetylacetonate zinc, diacetoxy zinc, dimethoxy zinc, diethoxy zinc, two phenoxy group zinc；Two Normal-butyl stannum oxide, diphenyl tin oxide, di-n-octyl tin oxide, dimethoxy di-n-butyl tin, di-n-butyl tin two propylene Acid esters, di-n-butyl tin dimethylacrylate, di-n-butyl tin dilaurate, tetramethoxy stannum, four phenoxy group stannum, four fourths The organo-tin compounds such as base-1,3-diacetoxy distannoxane；The aluminum such as aluminium acetate, aluminum methoxide, aluminum ethoxide, phenoxy group aluminum Compound；The vfanadium compound such as vanadium dichloride, vanadium trichloride, vanadium tetrachloride, Sulfovanadic acid；The salt etc. such as phenoxy group tetraphenylphosphonium. They can be used alone one, it is also possible to share two or more.

About the consumption of catalyst for ester exchange reaction, there is no the special upper limit relative to raw material low polyfluorene diester (1), if but using Too much, the most reacted refined load increases amount, thus usually fluorenes 20 moles of below %, be preferably 10 moles of below %, More preferably 5 moles of below %.

On the other hand, when the consumption of catalyst for ester exchange reaction is very few, the response time may be long, thus under conduct Limit, be commonly angled relative to raw material low polyfluorene diester be 0.1 mole of more than %, be preferably 0.5 mole of more than %, more preferably 1 Mole more than %.

<1.3.4.3.1.4 solvent>

Reaction dissolvent can be used in operation (iic), but the most do not use reaction dissolvent, merely with the low polyfluorene of raw material two Ester (1), diaryl carbonate esters and catalyst for ester exchange reaction react.But, raw material low polyfluorene diester (1), two Arylcarbonic acid esters room temperature is solid, be difficult to stir in the case of, it is possible to use reaction dissolvent.In the feelings using reaction dissolvent Under condition, as long as can suitably dissolve and/or disperse above-mentioned raw materials low polyfluorene diester (1), diaryl carbonate esters and ester The solvent of exchange reaction catalyst, its kind is arbitrary.

Specifically, it is possible to the solvent of use can be enumerated: as the acetonitrile of alkyl nitrile series solvent, propionitrile etc.；As ketone The acetone of series solvent, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.；As the diethyl ether of ether series solvent, oxolane, 1,4-dioxy Six rings, methylcyclopentyl ether, t-butyl methyl ether etc.；As the 1,2-dichloroethanes of halogen series solvent, dichloromethane, chloroform, 1, 1,2,2-sym-tetrachloroethane etc.；As the chlorobenzene of halogen system aromatic hydrocarbon, 1,2-dichloro-benzenes etc.；As the N of amide series solvent, N-bis- Methylformamide, DMAC N,N' dimethyl acetamide etc.；As the dimethyl sulfoxide of sulfoxide series solvent, sulfolane etc.；As ring type fat The monocyclic aliphatic hydrocarbon such as the Pentamethylene. of fat race hydrocarbon, hexamethylene, cycloheptane, cyclooctane；Methyl cyclopentane, second for its derivant Cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-diformazan basic ring Hexane, isopropyl cyclohexane, n-pro-pyl hexamethylene, t-butylcyclohexane, n-butyl cyclohexane, isobutyl group hexamethylene, 1,2,4- Trimethyl-cyclohexane, 1,3,5-trimethyl-cyclohexane etc.；The polycycle aliphatic hydrocarbons such as decahydronaphthalenes；Pentane, normal hexane, positive heptan The non-ring type aliphatic hydrocarbons such as alkane, normal octane, isobutyltrimethylmethane., n-nonane, n-decane, n-dodecane, n-tetradecane；As aromatic hydrocarbon Toluene, xylol, o-Dimethylbenzene, meta-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-tetrahydrochysene Naphthalene etc.；Pyridine etc. as heteroaromatic.

Owing to carrying out under this reaction preferably high temperature more than usually 100 DEG C, thus in above-mentioned solvent, preferably boiling point Be the chlorobenzene of the solvent of more than 100 DEG C, 1,2-dichloro-benzenes, trichloro-benzenes, toluene, xylol, o-Dimethylbenzene, meta-xylene, 1, 3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-naphthane, decahydronaphthalenes, N,N-dimethylformamide, N, N-diformazan Yl acetamide, dimethyl sulfoxide or sulfolane, for can suitably dissolve raw material low polyfluorene diester (10b), boiling point is 130 More than DEG C, the reason of the reaction that can carry out under higher temperature, particularly preferred 1,2-dichloro-benzenes, dimethylbenzene, 1,3,5-trimethyls Benzene, 1,2,4-trimethylbenzene or 1,2,3,4-naphthane, decahydronaphthalenes.

About the consumption of solvent, the upper limit is not particularly limited, if in view of the generation effect of the goal object in each reactor Rate, then generally use reach raw material low polyfluorene diester (1) 15 times of volumes, be preferably 10 times of volumes, more preferably 5 The amount of times volume.On the other hand, if the consumption of solvent is very few, then the dissolubility of reagent is deteriorated, stirring becomes difficulty, simultaneous reactions Carry out slowly, thus as lower limit, generally use and reach 1 times of volume with the densitometer of raw material low polyfluorene diester (1), be preferably The amount of 2 times of volumes, more preferably 4 times of volumes.

<1.3.4.3.1.5 reaction formation>

<1.3.4.3.1.6 reaction condition>

After termination of the reaction, poor solvent can be added in reactant liquor, make goal object oligomeric fluorene diaryl ester (2) separate out, Thus separate.

Additionally, after termination of the reaction, it is possible to the solvent of oligomeric for solubilized goal object fluorene diaryl ester (2) is added to water In reactant liquor, extract.The goal object utilizing solvent extraction to go out can be by utilizing the side of poor solubility produced by temperature difference The method etc. of method, the method concentrating solvent or interpolation poor solvent separates.

Obtained oligomeric fluorene diaryl ester (2) also can be as the polycarbonate starting material containing polyestercarbonate or polyester Raw material is directly used in polymerization.As method for refining, common method for refining, such as recrystallization, reprecipitation method, extraction essence can be used System, column chromatography etc., and unrestrictedly.

When utilizing the method for refining such as recrystallization, reprecipitation method to carry out refined, permissible as the concrete spendable solvent of good solvent Enumerate the acetonitrile as alkyl nitrile series solvent, propionitrile etc.；As the acetone of ketone series solvent, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) Deng；As the diethyl ether of ether series solvent, oxolane, 1,4-dioxane, methylcyclopentyl ether, t-butyl methyl ether etc.；As The 1,2-dichloroethanes of halogen series solvent, dichloromethane, chloroform, 1,1,2,2-sym-tetrachloroethane etc.；As halogen system aromatic hydrocarbon Chlorobenzene, 1,2-dichloro-benzenes etc.；As the N,N-dimethylformamide of amide series solvent, DMAC N,N' dimethyl acetamide etc.；As The dimethyl sulfoxide of sulfoxide series solvent, sulfolane etc.；As the toluene of aromatic hydrocarbon, xylol, o-Dimethylbenzene, a diformazan Benzene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-naphthane etc.；Pyridine etc. as heteroaromatic.

Oligomeric fluorene diaryl ester (2) is big for the poor solubility of temperature, thus the methyl that preferred boiling point is more than 100 DEG C is different Butyl ketone, 1,4-dioxane, methylcyclopentyl ether, t-butyl methyl ether, 1,1,2,2-sym-tetrachloroethane, chlorobenzene, 1,2-dichloro-benzenes, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, sulfolane, toluene, xylol, o-Dimethylbenzene, Dimethylbenzene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-naphthane, pyridine.Among these, more preferably at ester In the presence of exchange catalysts the most stable, for non-halogen system, the toluene of aromatic hydrocarbon that carrying capacity of environment is little, to diformazan Benzene, o-Dimethylbenzene, meta-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene.

These good solvents can be used alone one, it is also possible to two or more is used in mixed way.

About the consumption of solvent, the upper limit is not particularly limited, if in view of the refined effect of the goal object in each reactor Rate, then generally use reaches 15 times of quality of oligomeric fluorene diaryl ester (2), is preferably 10 times of quality, more preferably 5 times of matter The amount of amount.On the other hand, if the consumption of solvent is very few, then the dissolubility of reagent is deteriorated, stirring becomes difficulty, and the carrying out of simultaneous reactions is delayed Slowly, thus as lower limit, generally use reaches 0.3 times of quality with the densitometer of oligomeric fluorene diaryl ester (2), is preferably 0.5 times The amount of quality, more preferably 1 times of quality.

When utilizing the method for refining such as recrystallization, reprecipitation method to carry out refined, it is possible to use the poor solubility that temperature produces, only Use good solvent to carry out crystallize, but in order to improve the response rate, poor solvent is preferably used.Tool as spendable poor solvent Style, can enumerate the monocyclic aliphatic hydrocarbon such as the Pentamethylene. as ring type aliphatic hydrocarbon, hexamethylene, cycloheptane, cyclooctane；For The methyl cyclopentane of its derivant, ethyl cyclopentane, hexahydrotoluene, ethyl cyclohexane, 1,2-dimethyl cyclohexane, 1,3-bis- Hexahydrotoluene, 1,4-dimethyl cyclohexane, isopropyl cyclohexane, n-pro-pyl hexamethylene, t-butylcyclohexane, normal-butyl hexamethylene Alkane, isobutyl group hexamethylene, 1,2,4-trimethyl-cyclohexane, 1,3,5-trimethyl-cyclohexane etc.；The polycycle fat such as decahydronaphthalenes Race's hydrocarbon；Pentane, normal hexane, normal heptane, normal octane, isobutyltrimethylmethane., n-nonane, n-decane, n-dodecane, n-tetradecane etc. are acyclic Formula aliphatic hydrocarbon；As the methanol of alcohol series solvent, ethanol, isopropanol, n-butyl alcohol, the tert-butyl alcohol, hexanol, capryl alcohol, Hexalin etc..

Owing to highly polar impurity can be removed, thus, as the preferred methanol of poor solvent, ethanol, isopropanol, positive fourth The short methanol of the alcohol series solvents, more preferably carbochain such as alcohol, the tert-butyl alcohol, hexanol, capryl alcohol, Hexalin, ethanol.

Oligomeric fluorene diaryl ester (2) exists and stablizes shape and the crystal polymorphism of metastable setting.Utilize good solvent, pass through When the poor solubility that temperature produces makes crystallization, crisp with the crystallization that metastable setting separates out, have when becoming stable shape mutually Micronized tendency.Micronized crystallization when industrially using as resin raw material, poor fluidity, it is possible to cause and feed intake Bad.On the other hand, using as the toluene of good solvent, xylol, o-Dimethylbenzene, meta-xylene, 1，3，5-trimethyl-benzene, Aromatic hydrocarbons such as 1,2,4-trimethylbenzene, 1,2,3,4-naphthane and as the methanol of poor solvent, ethanol, isopropanol, positive fourth When the alcohol series solvents such as alcohol, the tert-butyl alcohol, hexanol, capryl alcohol, Hexalin are combined, due to from initially obtaining the crystallization of stable shape, There is not micronization, thus preferably.

When the aromatic hydrocarbon as good solvent and the alcohol series solvent as poor solvent are combined, if alcohol series solvent Interpolation temperature low, then the crystallization of metastable setting before alcohol series solvent adds, has the tendency of its ratio increase.Therefore, The interpolation temperature of alcohol series solvent is usually more than 20 DEG C, preferably more than 30 DEG C, more preferably more than 40 DEG C, is particularly preferably 50 More than DEG C.

In the crystallization of the metastable setting of oligomeric fluorene diaryl ester (2), if utilizing powder X-ray diffraction determinator (XRD) be analyzed, in 2 θ=5.6 °, 8.5 °, 11.0 °, 12.5 °, 12.9 °, 14.9 °, 16.3 °, 19.1 ° (θ=± 0.2 °) Observe distinctive peak.Owing to the crystallization of metastable setting is crisp, easily cause phase transfer, thereby through continuously stirred in crystallize And there is micronization, cause the discharge from reactor bad or filterability is deteriorated.It addition, the crystallization of metastable setting is to impact The most weak, in order to avoid powder fluidity, to reduce feeding intake of causing bad, preferably without the peak of these angle of incidence in crystallization.

If the amount of good solvent used in the crystallize of oligomeric fluorene diaryl ester (2) is very few, then it is difficult to dissolve low polyfluorene two virtue Base ester (2), purification efficiency also reduces, thus the lower limit of the amount of good solvent is relative to oligomeric fluorene diaryl ester (2) usually 0.3 times The amount of the amount of the amount of quality, preferably 0.5 times of quality, more preferably 0.7 times of quality, further preferably 0.9 times of quality Amount.It addition, if the amount of good solvent is too much, the loss in filtrate of the most oligomeric fluorene diaryl ester (2) increases, and yield rate reduces, because of And, the upper limit of the amount of good solvent is usually the amount of 5 times of quality relative to oligomeric fluorene diaryl ester (2), is preferably 4 times of quality The amount of the amount of amount, more preferably 3 times of quality, further preferably 2 times of quality.

If the amount of poor solvent used in the crystallize of oligomeric fluorene diaryl ester (2) is very few, the most oligomeric fluorene diaryl ester (2) Loss in filtrate increases, and yield rate reduces, thus, the lower limit of the amount of poor solvent is relative to oligomeric fluorene diaryl ester (2) The usually amount of the amount of the amount of 2 times of quality, preferably 3 times of quality, more preferably 3.5 times of quality, further preferably 4 times of matter The amount of amount.It addition, if the amount of poor solvent is too much, then purification efficiency also reduces, and still efficiency reduces, and productivity ratio reduces, because of And, the upper limit of the amount of poor solvent is usually the amount of 10 times of quality relative to oligomeric fluorene diaryl ester (2), is preferably 9 times of quality Amount, the amount of more preferably 8 times of quality, be further preferably the amount of 7 times of quality.

In order to from initially obtaining the crystallization of stable shape, if disposably adding substantial amounts of poor solvent, then dissolubility drastically under Fall, crystallization once separated out, and therefore crystal size is difficult to increase.For oligomeric fluorene diaryl ester (2), if specific good molten The specific poor solvent of a small amount of interpolation in agent, then have the tendency that dissolubility rises.To be the worst by utilizing this character Solvent is added separately or supplies specific poor solvent intermittently, has the tendency that can increase crystal size further.Make For specific good solvent, preferably toluene, xylol, o-Dimethylbenzene, meta-xylene, 1，3，5-trimethyl-benzene, 1,2,4-front threes Aromatic hydrocarbon, more preferably industrial cost are low for base benzene, 1,2,3,4-naphthanes etc., be readily available toluene, xylol, adjacent diformazan Benzene, meta-xylene.As specific poor solvent, preferably methanol, ethanol, isopropanol, n-butyl alcohol, the tert-butyl alcohol, hexanol, capryl alcohol, The alcohol series solvents such as Hexalin, more preferably industrial cost are low, be readily available isopropanol, methanol, ethanol.Particularly preferable as specific Good solvent o-Dimethylbenzene, as the combination of methanol of specific poor solvent.

Specific poor solvent is divided into 2 times in the case of being added, if the specific poor solvent initially added Ratio is too high, then poor solvent impact strengthen, do not observe dissolubility improve effect, thus usually 40 mass % with Under, be preferably below 30 mass %, below more preferably 20 mass %.On the other hand, if that initially adds is specific bad molten The ratio of agent is too low, then do not observe poor solvent additive effect, thus usually more than 5 mass %, be preferably 10 mass % Above, it is more preferably more than 15 mass %.

Specific poor solvent is divided into 2 times in the case of being added, needs by specific good solvent with specific The combination of poor solvent adjusts optimal interpolation temperature, in the case of particularly preferred o-Dimethylbenzene with methanol, if methanol Interpolation temperature low, then adding the crystallization of metastable setting before methanol, there is the tendency that its ratio increases.Therefore, initially The interpolation temperature of methanol added be usually more than 45 DEG C, be preferably more than 50 DEG C, be more preferably more than 55 DEG C, the most excellent Elect more than 60 DEG C as.The lower limit of the temperature of the methanol added subsequently is usually more than 0 DEG C, preferably more than 5 DEG C, is more preferably 10 More than DEG C.On the other hand, the upper limit of the temperature of the methanol added subsequently be usually less than 42 DEG C, be preferably less than 40 DEG C, more excellent Elect less than 38 DEG C as.

The grain diameter of oligomeric fluorene diaryl ester (2) significantly changes according to the difference of crystallize condition.If the particle diameter of granule Too small, then in the filter progress of crystallization, it is susceptible to the blocking of filter cloth, filtration time is elongated, or liquid holdup raises, and has The tendency that the purity of oligomeric fluorene diaryl ester (2) reduces.It addition, when using as resin raw material, powder fluidity is deteriorated, and has May cause feed intake bad.Therefore, the lower limit of the mean diameter of the granule of oligomeric fluorene diaryl ester (2) be usually more than 50 μm, It is preferably more than more than more than more than 70 μm, more preferably 90 μm, further preferably 130 μm, particularly preferably 170 μm. If the mean diameter of the granule of oligomeric fluorene diaryl ester (2) is excessive, when using as resin raw material, it is possible to blocking is filtered Device.Therefore, the upper limit of the mean diameter of the granule of oligomeric fluorene diaryl ester (2) is usually below 2cm, is preferably below 1cm, more It is preferably below 0.5cm, further preferably below 0.3cm.

The grain diameter of oligomeric fluorene diaryl ester (2) significantly changes according to crystallize condition.If the particle diameter of granule is too small, then Being susceptible to the blocking of filter cloth in the filter progress of crystallization, filtration time is elongated, or liquid holdup raises, and has low polyfluorene two The tendency that the purity of aryl ester (2) reduces.It addition, when using as resin raw material, powder fluidity is deteriorated, it is possible to cause Feed intake bad.Therefore, the accumulation % that particle diameter is more than 50 μm of the granule of oligomeric fluorene diaryl ester (2) is usually more than 50 μm and is More than 50%, be preferably more than 60%, more preferably more than 70%, be further preferably more than 80%, particularly preferably More than 90%.

The primary crystallization obtained by crystallize or the particle diameter of the agglutinator of primary crystallization coagulation according to reactor or are stirred The various conditions such as the material mixing the shape of oar, mixing speed, reactor and change.If in general becoming large-sized, then shearing force Increase, thus the most crushed, and particle diameter has the tendency diminished.But, by according to above-mentioned crystallize condition, such as even with 1m³Above reactor, it is also possible to obtain the oligomeric fluorene diaryl ester (2) of preferable particle size.

Operate by crystallize is repeated, the content of metal can be reduced.Now, recrystallization temperature is the lowest, 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 of particularly preferred catalyst for ester exchange reaction Ti compound is used as catalyst, low polyfluorene two The removing difficulty of the Ti in aryl ester (2), the remaining of Ti becomes problem sometimes.In this case, the most after termination of the reaction Reactant liquor or the oligomeric fluorene diaryl ester (2) separated once is dissolved in the solution in above-mentioned solvent again Add water, make Ti its inactivation, be changing into insoluble titanium residue, in filter progress, remove titanium residue afterwards.Now, exist In the case of adding water in reactant liquor after reaction terminating, the titanium level of residue carrying out refining is many, and filter progress causes big bearing Lotus, thus there is the tendency that filterability is deteriorated.It is therefore preferable that add poor solvent for the time being in reaction terminating liquid, by major part Ti compound remove, make oligomeric fluorene diaryl ester (2) re-dissolved after separation afterwards, with water inactivate after, carry out to filterer Sequence.

The particle diameter of titanium residue is the least, if aperture is greatly, cannot completely remove titanium residue, it is possible to be mixed in goods.Cause This, the aperture of the filter material used in filter progress is usually below 10 μm, is preferably below below 5 μm, more preferably 1 μm.Separately On the one hand, if the aperture of filter material is too small, then the rate of filtration reduces, it is possible to cause the delay of activity time.Accordingly, as filtration The aperture of filter material used in operation, usually more than 0.01 μm, is preferably more than more than 0.05 μm, more preferably 0.1 μm.Separately Outward, when the filtering surface of the filter material used in filter progress is plane, titanium residue is piled up in filtering surface so that it is blocking, therefore to Shorten filtration time, need the filter area of excess.On the other hand, if the filter material of use is shaped as filter bag in filter progress Such cylindrical shape closing bottom surface, then titanium residue can be piled up in bottom surface, can also filter from side, therefore can reduce stifled The danger of plug, therefore preferably.It addition, about the material of filter material used in filter progress, from low cost, industrial it is readily available Aspect is set out, preferably polypropylene system, cotton system and polyester system, from the aspect that thermostability is high, preferably polyester system, cotton system and Cotton system that Teflon system, more preferably low cost, thermostability are the highest and the filter material of polyester.As filter progress, can enumerate Sucking filtration, centrifugal filtration, pressure filtration.Wherein, pressure filtration because of the rate of filtration fast and preferred.In order to improve the rate of filtration, pressurization The pressure filtered is usually more than 0.11MPa, is preferably more than 0.15Mpa, more preferably more than 0.20MPa.Pressure filtration Higher limit additionally depends on equipment, in order to avoid equipment being caused big load, usually below 5.0MPa, be preferably 3.0MPa with Under, more preferably below 1.0MPa.

Filter progress can use filtration adjuvant.As filtration adjuvant, kieselguhr, cellulose powder, sulfur can be enumerated Acid magnesium, sodium sulfate, silica gel, activated alumina, activated carbon, active hargil, perlite, glass fibre, bead etc..

Among these, preferably filter area is big, loss caused by absorption is few kieselguhr, cellulose powder, perlite.

<2 low polyfluorene diester B>

The low polyfluorene diester (hereinafter sometimes called " low polyfluorene diester B ") of the present invention comprises with or without replacement The fluorenes unit of more than 2 of base,

The content ratio of carboxylic acid is below 5 mass %.

As alkylidene, arlydene, sub-aralkyl, preferably can use at<1.1 alkylidenes, arlydene, sub-aralkyl> Group illustrated in.

Similarly, as fluorenes unit, preferably can use in<substituent group that 1.2 fluorenes unit can have>illustrated Fluorenes unit.

The low polyfluorene diester B of the present invention can be: is bonded respectively on the carbon atom of 9 of the fluorenes unit being positioned at two ends Substituted base α¹And α², in this substituents alpha¹And α²On be bonded with ester group.In this case, α¹And α²Can identical can not also With.It addition, substituents alpha¹And α²In comprise Direct Bonding, i.e. can have ester group with Direct Bonding on the carbon atom of 9 of fluorenes unit.

As ester group, ester group illustrated in<1.3 ester group>of above-mentioned " invention 2 " preferably can be used.Particularly, by In having the tendency that the patience for hydrolysis raises, thus the preferably alkyl of straight-chain, more preferably methyl or ethyl.

Alternatively base α¹And α², preferably can use < 1.4 substituents alpha in above-mentioned " invention 2 "¹And α²Illustrated in > Group.

It addition, as the concrete structure of low polyfluorene diester B, it may be preferred to use the structure shown in above-mentioned formula (1).Separately Outward, as concrete example, the structure shown in above-mentioned [H] group can be enumerated.

As it has been described above, in the low polyfluorene diester of the present invention, the content ratio of carboxylic acid is below 10 mass %.By so making The content of carboxylic acid is prescribed limit, in the case of this low polyfluorene diester is manufactured diaryl ester as raw material, has permissible Amount of metal contained by this diaryl ester is reduced to the tendency of prescribed limit.

From the aspect of the amount of metal reduced contained by diaryl ester, the content of above-mentioned carboxylic acid be preferably 8 mass % with Under, below more preferably 5 mass %, more preferably below 4 mass %, be further preferably below 3 mass %, especially It is preferably below below 2 mass %, most preferably 1 mass %.It addition, carboxylic acid content is the fewest more preferred, if wanting to be 0 matter Amount %, in order to prevent that impurity is mixed into wait likely with significant cost raise or production efficiency reduction.Maintain productivity ratio and can The content of the carboxylic acid reached is usually more than 0.1 mass %.

Think above-mentioned carboxylic acid when low polyfluorene diester manufactures by hydrolysis by-product.Kind about above-mentioned carboxylic acid does not has It is particularly limited to, such as, can enumerate low polyfluorene monoesters monocarboxylic acid and (in low polyfluorene diester, any one ester group is substituted by carboxylic acid Material), low polyfluorene dicarboxylic acids (in low polyfluorene diester, 2 ester groups are substituted by the material of carboxylic acid).

As the algoscopy of carboxylic acid content, such as, can enumerate and utilize high performance liquid chromatography that the carboxylic acid separated is carried out quantitatively Method.

As the method making carboxylic acid amount be above-mentioned scope, such as, can enumerate common method for refining, such as utilize aqueous alkali Filter operation, the column chromatographies etc. such as water washing operations, recrystallization, reprecipitation method, Hydrolysis kinetics, filter filtration.It addition, utilizing two In the case of the reaction of coating systems manufactures the low polyfluorene diester B of the present invention, by the low temperature of reaction temperature, the contracting in response time Short grade suppresses hydrolysis critically important.

It addition, other physics value of the low polyfluorene diester B of the present invention is not particularly limited, preferably meet above-mentioned " invention 3 " The physical property of low polyfluorene A1 of 1 reactive functional groups<1.6 have>item in illustrated physics value.

Manufacture method about low polyfluorene B of the present invention is not particularly limited, such as, can utilize and < the low polyfluorene of 1.3.4 The manufacture method of diester (1) > described in the identical method of method manufacture.

Embodiment

Illustrating in greater detail the present invention below by embodiment and comparative example, but as long as without departing from its main points, the present invention is also Do not limited by following example.

" embodiment 1-1～1-6, comparative example 1-1～1-17 "

The quality evaluation of low polyfluorene monomer and the evaluating characteristics of resin and hyaline membrane of the present invention are carried out as follows. It should be noted that evaluating characteristics is not limited to following method, those skilled in the art can suitably select.

(1) aluminum in fluorenes system monomer, sodium content

Following mensuration comprises the aluminum in the monomer (hereinafter sometimes called fluorenes system monomer) of fluorenes ring, sodium content.To analyzing examination After sample carries out wet type resolution process, utilize ICP-AES (HORIBA Jobin Yvon society manufacture ULTIMA2C) carry out aluminum content and Sodium content quantitative.Additionally, about sodium content, according to the difference of analysis sample, also share and utilized atom light absorption method (VARIAN SpectrAA-220P processed) analysis that carries out.

(2) chlorinity in fluorenes system monomer

The following chlorinity measured in fluorenes system monomer.Use the burner AQF-that Mitsubishi chemical Co., Ltd manufactures 2100M makes analysis sample burn, and makes the GAS ABSORPTION of generation in pure water.Thereafter, the pure water absorbing gas is imported Japan The chromatography of ions DX-500 that Dionex Co., Ltd. manufactures, has carried out the quantitative of 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 society manufactures Analysis apparatus TG-DTA6300 is measured.About 4mg fluorenes system monomer is put in the aluminum dish that this society manufactures and sealed, The nitrogen of 200mL/ minute flows down, and is warming up to 600 DEG C with programming rate 10 DEG C/min by room temperature (20～30 DEG C).According to gained The TG data (Thermogravimetric Data) arrived, reduce the temperature of 5wt% as 5wt% weightless temperature using sample weight.For containing solvent Monomer, with measure start time weight compared with decrease by¹After the weight of solvent of H-NMR estimation, weight will not be occurred to become This initial stage weight, as initial stage weight, is reduced the temperature of 5wt% as 5wt% weightless temperature by the weight in the moment changed.It addition, According to obtained TG data (Thermogravimetric Data), confirming less than the minimizing of weight and this peak of observing 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

The very big wavelength of absorption in the UV, visible light region (UV-Vis:280～800nm) of fluorenes system monomer uses (strain) Shimadzu system Ultravioletvisible absorption spectrophotometer UV-1650PC manufactured by work is measured.About measuring solution, oxolane is used to make For solvent, it is 10 μMs according to the concentration in terms of fluorenes ring and accurately prepares.Cell uses the quartz cell that 1cm is square, in temperature It is measured in the environment of spending 23 ± 5 DEG C.In the range of 280nm～800nm, measure the absorption spectrum of solution, will absorb Maximum as absorb 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 friend's physics and chemistry Industry society manufacture Ubbelohde viscosity pipet, be measured temperature 20.0 DEG C ± 0.1 DEG C, determine solvent by time t₀And solution By time t.Use obtained t₀With the value of t, obtain relative viscosity η by following formula (I)_rel, and then use obtained Relative viscosity η_rel, obtain specific viscosity η 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), obtain reduced viscosity η_sp/c.This value is the highest, point Son amount is the biggest.

(6) melt viscosity of resin

Granular resin is vacuum dried more than 5 hours at 90 DEG C.Use dry granule, utilize Toyo Seiki strain formula meeting The capillary rheometer that society manufactures is measured.To measure temperature be 240 DEG C, shear rate is 9.12～1824sec^-1Between measure Melt viscosity, uses 91.2sec^-1Time the value of melt viscosity.It should be noted that it is φ 1mm, length that hole employs mode diameter Hole for 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 society manufactures DSC6220 is measured.About 10mg resin put in the aluminum dish that this society manufactures and seal, at the nitrogen of 50mL/ minute Flow down, be warming up to 250 DEG C with programming rate 20 DEG C/min by 30 DEG C.After temperature is kept 3 minutes, with the speed of 20 DEG C/min It is cooled to 30 DEG C.Keep 3 minutes at 30 DEG C, be again warming up to 200 DEG C with the speed of 20 DEG C/min.Warming middle-JIAO is risen according to the 2nd time The DSC data obtained obtains extrapolation glass transition initial temperature, and this extrapolation glass transition initial temperature is by low temperature side Baseline extends the slope of curve of straight line and the stepped changing unit at glass transition obtained and reaches maximum to high temperature side The temperature of the intersection point that the tangent line that point is drawn intersects, using this extrapolation glass transition initial temperature as glass transition temperature. When this glass transition temperature is more than 125 DEG C, it is evaluated as excellent heat resistance.

(8) molding of film

Unstretching film is made by following two kinds of methods.

In embodiment 1-1 described later and comparative example 1-1～1-12, carry out compression molding in the following order, make Unstretching film.For being vacuum dried the about 4g resin particle of more than 5 hours at 90 DEG C, use long 14cm, wide 14cm, thickness The sept of 0.1mm, at the laying polyimide film up and down of sample, preheats 3 minutes temperature 200 DEG C～230 DEG C, at pressure After pressurizeing 5 minutes under conditions of 40MPa, together take out with sept and cool down, making membrane.In the method, it is impossible to 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, about thickness Degree precision, the thickness of each position of measurement film, it is shown that the difference of the maximum of mobility scale or minima and setting value is relative to flat The ratio of average.

Thickness and precision [%]=| the maximum of thickness or minima-meansigma methods |/meansigma methods × 100

It addition, in embodiment 1-2 described later～1-6 and comparative example 1-13～1-17, made by extrusion by melting Long unstretching film.Extrusion by melting is carried out as follows.For being vacuum dried the resin particle of more than 5 hours at 90 DEG C, profit Single screw extrusion machine (screw diameter 25mm, the barrel design temperature: 220 DEG C～240 manufactured with い The ず Chemical Co., Ltd DEG C), from T mould (wide 200mm, design temperature: 200～240 DEG C) extrusion.For the film of extrusion, (set temperature with chill roll Degree: 120～150 DEG C) cooling be web-like with coiling machine, produce long unstretching film.It addition, in the above-mentioned methods, By adjusting die lip width or the distance etc. of the temperature of chill roll, T mould and chill roll of T mould, it is possible to achieve the film of less than 5% Thickness and precision.

(9) mensuration of refractive index

Long 40mm, the rectangle of wide 8mm is cut out by the unstretching film made above by pressure sintering or extrusion by melting Test film, as measure sample.Use the interference light filter of 589nm (D line), the multi-wavelength manufactured by (strain) Atago Abbe index meter DR-M4/1550 determines refractive index n_D.Mensuration uses single bromonaphthalene as interface liquid, carry out at 20 DEG C Measure.

(10) mensuration of total light transmittance

Made the unstretching film of thickness about 100 μm by above-mentioned extrusion by melting, utilize Japan's electricity color industry strain formula The scopometer COH400 that commercial firm manufactures determines total light transmittance.

(11) photoelastic coefficient

Use and will comprise the double refraction detection device of He-Ne laser instrument, polarizer, compensating plate, analyzer, photodetector The device combined with oscillating mode determination of viscoelasticity device (Rheology society manufactures DVE-3) is measured.(detailed content is joined Will Vol.19, p93-97 (1991) is learned according to Japan Rheology.)

Cut out wide 5mm, the sample of long 20mm by the unstretching film made by any of the above-described kind of method, be fixed on viscoelastic Property determinator, under the room temperature of 25 DEG C with frequency 96Hz measure storage modulus E '.Meanwhile, the laser making injection passes sequentially through partially Shake element, sample, compensating plate, analyzer, and utilizes photodetector (photodiode) to be picked up so that it is is amplified by locking Device, the waveform for angular frequency or 2 ω is obtained the phase contrast relative to its amplitude and strain, and is obtained strain optical coefficient O’.Now, adjust the direction of polarizer and analyzer, make them orthogonal, and make them become with the prolonging direction of sample respectively The angle of π/4.Photoelastic coefficient C uses storage modulus E ' and strain optical coefficient O ' obtained by following formula.

C=O '/E '

When this photoelastic coefficient is less than 20, it is evaluated as photoelasticity excellent.

(12) elastic modelling quantity

Cut out wide 5mm, the rectangular test film of long 50mm by the film obtained by said method, determine energy storage mould Amount (E ') and loss modulus (E ").In mensuration, use the flow graph RSA-III that TA Instruments society manufactures, with stretching die Temperature is warming up to each from 20mm, 3 DEG C/min of programming rate, frequency 1Hz, the condition of strain 0.1% by formula, jaw separation from 0 DEG C More than the glass transition temperature of sample, being measured using up to sample and stopping.Storage modulus in the present invention uses The storage modulus of 30 DEG C.

(13) water absorption rate

Producing thickness by any of the above-described kind of method is 100 μm～the unstretching film of 300 μm, cut growth 100mm, width The square of 100mm, produces sample.Use this sample, according to " water absorption rate of plastics and boiling described in JIS K 7209 Moisture content test method " determine water absorption rate.

(14) toughness (crooked test) of film

Producing thickness by any of the above-described kind of method is 100 μm～the unstretching film of 200 μm, this film production go out length 40mm, the rectangular test film of wide 10mm.40mm is opened at the interval on composition surface, vice left and right, the two ends of test film are solid It is scheduled in composition surface.Then make the interval on composition surface, left and right reduce with 2 mm/second speed below, be expressed into always not making film In the case of outside the composition surface of vice, will bend to approximate the film reduced overall of U-shaped in this composition surface.Near composition surface Between the most closely sealed till test film be cleaved into the situation of 2 (or fragmentations of more than 3) as " having crackle " at bending section, even if will Between composition surface, complete closely sealed test film does not splits and situation about bending is as " flawless " yet.5 are implemented for same kind of film Secondary repeat test, will be for more than 4 times wherein the situation of " having crackle " as " ×: generation brittle break ", by less than 3 times for " to have Crackle " situation as " zero: brittle break does not occurs ", the situation that brittle break does not occurs is evaluated as tenacity excellent.

(15) stretching of film

According to the manufacture method of above-mentioned unstretching film, produce phase retardation film by two kinds of following methods.

For the unstretching film made by pressure sintering, following method is utilized to be stretched.Cut out by unstretching film Wide 50mm, the diaphragm of 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 glass transition temperature+15 DEG C of resin, 300%/minute draw speed 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 300%/minute draw speed, the stretching times of 2 times Rate, the draft temperature of glass transition temperature+10 DEG C of resin stretch, and have obtained stretched film if unbroken, then with often The mode of secondary 1 DEG C reduces draft temperature, carries out to film fracture in stretching.Use occur fracture temperature once before Draft temperature under obtain stretched film, carried out evaluation described later.

(16) phase contrast of stretched film, wavelength dispersion, birefringence

The central part of the stretched film obtained by said method is cut into wide 4cm, long 4cm, utilizes prince to measure machine The measuring difference of phases device KOBRA-WPR that Co., Ltd. manufactures, measure wavelength 450,500,550,590,630nm measure phase place Difference, measures wavelength dispersibility.Wavelength dispersibility is used in the ratio (R450/ of phase contrast R450 with R550 that 450nm and 550nm measures 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 uses, the ideal value of R450/R550 is 0.818 (450/550=0.818).

Obtained value, divided by the molar ratio of fluorenes system monomer, is made by the value that will be deducted the value of R450/R550 by 1 and obtain During expression power scattered for inverse wave length, if this value is more than 0.01, then evaluate the scattered expression power of inverse wave length excellent.

It should be noted that as the formula (1) of the present invention 1～the value of the B (R450/R550) of (3), use in following evaluation The value of the wavelength dispersion of middle mensuration, this evaluation employs the stretched film obtained by the unstretching film made by above-mentioned pressure sintering.

It addition, use phase contrast R550 and the thickness of stretched film of 550nm, following formula obtain birefringence n.

Birefringence=R550 [nm]/(thickness [mm] × 10⁶)

Birefringent value is the biggest, represents that the degree of orientation of polymer is the highest.It addition, birefringent value is the biggest, more can reduce For obtaining the thickness of the film of desired phase difference value.

In above-mentioned various evaluations, when there is not the project being evaluated as difference, it is evaluated as the balancing good of various characteristic.

Below, the synthetic method of monomer used in the manufacture of resin is illustrated.

The synthesis of [synthesis example 1] double (fluorenes-9-base) methane (compound 1)

[changing 125]

In 1L four-hole boiling flask, load fluorenes (120g, 722mmol), DMF (480ml), carry out nitrogen and put Less than 5 DEG C it are cooled to after changing.Add Sodium ethylate (24.6g, 361mmol), add on a small quantity several times, every time paraformaldehyde (8.7g, 289mmol), make temperature be less than 10 DEG C, and be stirred.After 2 hours, dropping 1N hydrochloric acid (440ml), stopped reaction.To institute The aaerosol solution obtained carries out sucking filtration, utilizes deionized water (240ml) to carry out drip washing.Thereafter, obtained thick product is made to divide It is scattered in deionized water (240ml), stirs 1 hour.After this suspension is carried out sucking filtration, deionized water (120ml) is utilized to carry out Drip washing.After making obtained thick product be distributed in toluene (480ml), Dean-Stark apparatus is utilized to be heated to reflux bar It is dehydrated under part.Recover to room temperature (20 DEG C), carrying out sucking filtration, at 80 DEG C of drying under reduced pressure until reaching constant, thus obtaining Double (fluorenes-9-base) methane (compound 1) 84.0g (yield: 84.5%, HPLC purity: 94.0%) as white solid.Chemical combination Thing 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 group) fluorenes-9-base] methane (compound 2)

[changing 126]

Double (fluorenes-9-base) methane (compound 1,80g, 232.3mmol), N-obtained above is loaded in 1L there-necked flask Benzyl-N, N, N-triethyl ammonium chloride (10.6g, 46.5mmol), dichloromethane (400ml), use water-bath after carrying out nitrogen displacement Control is 15 DEG C～20 DEG C, and after adding 50% sodium hydrate aqueous solution (64ml), the color of solution is changing into light red.Thereafter, With dropping ethyl acrylate (50.5ml, 465mmol) in 5 minutes.Add further after 1 hour ethyl acrylate (25.3ml, 232mmol), with the carrying out of HPLC following response, while stirring 9 hours.Utilize HPLC to confirm singly to add adult and reach 5% After below, cool down with ice bath, control temperature dropping 3N hydrochloric acid (293ml), be quenched.Water is utilized to clean organic layer straight After being neutrality to fluidity, utilizing anhydrous magnesium sulfate to be dried, filter, decompression is distilled off solvent.Make obtained thick generation Thing is dispersed in methanol (400ml), carries out 30 minutes being heated to reflux, thus carries out heat suspension washing.Thereafter recover to room temperature (20 DEG C), after sucking filtration, at 80 DEG C of drying under reduced pressure until reaching constant, thus obtain double [9-(the 2-ethyoxyl carbonyls as white solid Base ethyl) fluorenes-9-base] methane (compound 2) 96.1g (yield: 75.9%, 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).

It addition, the 5wt% weightless temperature (under nitrogen atmosphere) of compound 2 is 295 DEG C, fusing point is 141 DEG C.

The synthesis of [synthesis example 3] double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 3)

[changing 127]

Double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] methane (chemical combination obtained above is loaded in 1L four-hole boiling flask Thing 2,50.0g, 91.80mmol), diphenyl carbonate (98.3g, 459mmol), original four-isopropyl titanate (1.3mL, 4.59mmol), vacuum being adjusted to 3kPa, the temperature range 145 DEG C～150 DEG C is distilled off by-product and enters Row stirring in 6 hours.It is cooled to 90 DEG C, after confirming reaction terminating by HPLC, adds toluene (100ml), be cooled to 50 DEG C.Xiang Qi Middle addition methanol (250ml), after being cooled to 5 DEG C, carries out sucking filtration.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, add methanol (200ml).After being cooled to room temperature (20 DEG C), carry out sucking filtration, 100 DEG C drying under reduced pressure is until reaching constant, thus obtains double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] as white solid Methane (compound 3) 50g (yield: 85%, 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).

It addition, the 5wt% weightless temperature (under nitrogen atmosphere) of compound 3 is 336 DEG C, fusing point is 176 DEG C.

The synthesis of [synthesis example 4] 1,2-double (fluorenes-9-base) ethane (compound 4)

[changing 128]

Fluorenes (2.0g, 12mmol), oxolane (35ml) is loaded in 100ml four-hole boiling flask, after carrying out nitrogen displacement, Ethanol-the dry ice bath is cooled to less than-50 DEG C.Several times, every time a small amount of add 1.6mol/L n-BuLi (7.8ml, 12.5mmol) make temperature be less than-40 DEG C, and be stirred.Thereafter, it is warming up to 10 DEG C, after carrying out stirring in 1 hour, adds 1, 2-Bromofume (0.55ml, 6.4ml), carries out stirring in 2 hours further.Thereafter, dropping 1N hydrochloric acid (0.5ml), to generate Aaerosol solution carries out sucking filtration, after washing, at 80 DEG C of drying under reduced pressure to reaching constant, thus obtains 1 as white solid, and 2-is double (fluorenes-9-base) ethane (compound 4) 0.63g (yield: 29.2%, HPLC purity: 98.0%).It addition, decompression is distilled off filter The solvent of liquid, adds ethanol (25ml), carries out 30 minutes being stirred.Suspension is carried out sucking filtration, straight at 80 DEG C of drying under reduced pressure To reaching constant, thus obtain 1 as white solid, double (fluorenes-9-base) ethane (compound 4) 0.44g of 2-(yield: 20.5%, HPLC purity: 84.0%).If obtained white solid is merged, then it is 1.07g (yield: 49.7%).Chemical combination Thing 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 group) fluorenes-9-base] ethane (compound 5) of [synthesis example 5] 1,2-

[changing 129]

1L four-hole boiling flask loads double (fluorenes-9-base) ethane (compound 4,85g, 237mmol) of 1,2-obtained above, Oxolane (725ml), DMF (85ml), carry out adding after nitrogen displacement Sodium ethylate (3.23g, 47.5mmol), it is warming up to room temperature (20 DEG C), carries out stirring in 30 minutes.Utilize 2.5 hours dropping ethyl acrylate (59.3ml, 545mmol).After confirming raw material disappearance by HPLC, in reactant liquor, drip 0.1N hydrochloric acid (55ml), stopped reaction.Decompression After oxolane is distilled off, add toluene (425ml), utilize pure water clean organic layer until fluidity is neutrality, afterwards profit Being dried with anhydrous magnesium sulfate, filter, decompression is distilled off solvent.Obtained thick product is made to be dispersed in methanol (400ml), in, it is heated to reflux 1 hour carrying out heat suspension washing.Thereafter recover to room temperature (20 DEG C), after sucking filtration, subtract at 80 DEG C Pressing dry dry until reaching constant, thus obtain 1 as white solid, 2-is double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] Ethane (compound 5) 101g (yield: 76.1%, HPLC purity: 98.6%).Compound 5¹Chemical potential in H-NMR spectrum Move 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).

It addition, the 5wt% weightless temperature (under nitrogen atmosphere) of compound 5 is 306 DEG C, fusing point is 150 DEG C.

The synthesis of double [9-(the 2-phenyloxycarbonyl ethyl) fluorenes-9-base] ethane (compound 6) of [synthesis example 6] 1,2-

[changing 130]

Double [9-(2-ethoxycarbonylethyl group) fluorenes-9-of 1,2-obtained by said method is loaded in 1L four-hole boiling flask 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, carries out stirring in 24 hours.On the way, little through 12 Time moment, through the moment of 20 hours, add diphenyl carbonate (38.3g, 179mmol) by several times.Confirmed instead by HPLC After should terminating, add toluene (400ml), be heated to reflux 1 hour.After being cooled to room temperature (20 DEG C), carry out sucking filtration.Make obtained White solid is dispersed in toluene (300ml), is heated to reflux 1 hour.After being cooled to room temperature (20 DEG C), carry out sucking filtration, at 80 DEG C Drying under reduced pressure is until reaching constant, thus obtains 1 as white solid, double [9-(the 2-phenyloxycarbonyl ethyl) fluorenes-9-of 2- Base] ethane (compound 6) 82g (yield: 70.0%, 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).

It addition, the 5wt% weightless temperature (under nitrogen atmosphere) of compound 6 is 337 DEG C, fusing point is 232 DEG C.

The synthesis of [synthesis example 7] double [9-(3-hydroxypropyl)-fluorenes-9-base] methane (compound 7)

[changing 131]

Double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] first obtained in synthesis example 2 are loaded in 500ml four-hole boiling flask Alkane (compound 2,50g, 91.8mmol), toluene (250ml), after carrying out nitrogen displacement, utilize ice bath to be cooled to less than 5 DEG C, Be maintained at while less than 10 DEG C double (2-methoxy ethoxy) sodium aluminum hydride of dropping 65wt% toluene solution (82.7ml, 275mmol), stirring in 1 hour is carried out.After confirming raw material disappearance by HPLC, dropping ethyl acetate (9.9ml), carry out 30 points After clock stirring, dropping 3.1N sodium hydrate aqueous solution further, carry out stirring in 2 hours.Obtained aaerosol solution is taken out Filter, utilizes deionized water (100ml) to carry out drip washing.Thereafter, obtained thick product is made to be dispersed in deionized water (150ml) In, carry out stirring in 30 minutes.Carry out drip washing after sucking filtration, until fluidity is neutrality, utilize toluene (50ml) to carry out drip washing.Make gained To thick product be dispersed in oxolane (150ml), dissolved by heating.Tetrahydrofuran solution recovers to room temperature After (20 DEG C), by short silica gel Filter column (50g), utilize oxolane (350ml) eluting, utilize vaporizer to obtained molten Liquid carries out decompression and solvent is distilled off.Make obtained thick product be dispersed in toluene (250ml), carry out 30 minutes heating back Stream, thus carry out heat suspension washing.Recover to room temperature (20 DEG C) to carry out sucking filtration, afterwards at 80 DEG C of drying under reduced pressure until reaching permanent Amount, thus obtain double [9-(3-hydroxypropyl)-fluorenes-9-base] methane (compound 7) 35.5g as white solid (yield: 83.9%, HPLC purity: 99.8%).Sodium content, aluminum content in solid are respectively less than 1ppm.Compound 7¹In H-NMR spectrum Chemical shift 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).

It addition, the 5wt% weightless temperature (under nitrogen atmosphere) of compound 7 is 301 DEG C, fusing point is 214 DEG C.

The synthesis of double [9-(the 3-hydroxypropyl)-fluorenes-9-base] ethane (compound 8) of [synthesis example 8] 1,2-

[changing 132]

The 1,2-obtained in synthesis example 5 is loaded double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] in 1L four-hole boiling flask Ethane (compound 5,100g, 179mmol), oxolane (500ml), after carrying out nitrogen displacement, utilize ice bath be cooled to 5 DEG C with Under, it is maintained at less than the 15 DEG C 65wt% toluene solutions dripping double (2-methoxy ethoxy) sodium aluminum hydrides (161ml, 537mmol), carries out stirring in 1 hour.After confirming raw material disappearance by HPLC, dropping ethyl acetate (32ml), enter After row stirring in 45 minutes, dropping 3.1N sodium hydrate aqueous solution (257ml) further, carry out stirring in 1 hour.Decompression is distilled off After oxolane, obtained aaerosol solution is carried out sucking filtration, utilize deionized water (100ml) to carry out drip washing.Thereafter, gained is made To thick product be dissolved in ethyl acetate (700ml), utilize deionized water (100ml) to clean 3 times.Organic layer is utilized sulfur Acid magnesium is dried, by short silica gel Filter column (50g), utilizes oxolane (800ml) eluting, utilizes vaporizer to obtained Solution carries out decompression and solvent is distilled off.Make obtained thick product be dispersed in toluene (400ml), be heated to reflux 30 points Clock, thus carries out heat suspension washing.Recover to carry out sucking filtration, afterwards at 100 DEG C of drying under reduced pressure until reaching to room temperature (20 DEG C) To constant, thus obtain 1 as white solid, double [9-(3-hydroxypropyl)-fluorenes-9-base] ethane (compound 8) 75.6g of 2- (yield: 89.0%, HPLC purity: 98.7%).Sodium content in solid is 2ppm, aluminum 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).

It addition, the 5wt% weightless temperature (under nitrogen atmosphere) of compound 8 is 312 DEG C, fusing point is 253 DEG C.

The synthesis of [synthesis example 9] double (9-hydroxymethyl fluorenes-9-base) methane (compound 9)

[changing 133]

500mL four-hole boiling flask loads in synthesis example 1 obtain double (fluorenes-9-base) methane (compound 1,100g, 290mmol), DMF (400ml), after carrying out nitrogen displacement, add paraformaldehyde (18.3g, 610mmol). After being cooled to less than 5 DEG C, add Sodium ethylate (0.698g, 13mmol), be stirred making temperature be less than 10 DEG C.After 1.5 hours, Adding 1N hydrochloric acid (32ml) makes temperature be less than 25 DEG C, stopped reaction.Add water (300ml) further, be stirred, to gained To aaerosol solution carry out sucking filtration, utilize deionized water (100ml) to carry out drip washing.Obtained thick product is made to be dispersed in tetrahydrochysene After in furan (400ml), carry out 1 hour be heated to reflux.Recover to room temperature (20 DEG C), after sucking filtration at 80 DEG C of drying under reduced pressure until Reach constant, obtain white solid 108g (yield: 91%, HPLC purity: 99.1%).The obtained sodium in white solid contains Amount is 620ppm.Thereafter make white solid be dispersed in toluene (800ml) and water (200ml) mixed liquor, carry out 1 hour heating back Stream, filters, dried, is measured the sodium content in obtained solid, and result is 390ppm.Make obtained further White solid is dispersed in DMF (500ml), after uniform solution is made in heating, is cooled to less than 40 DEG C, It is added drop-wise to lentamente in the hydrochloric acid (1500ml) of 0.03N.Obtained aaerosol solution is carried out sucking filtration so that it is be dispersed in deionization In water (200ml), carry out stirring in 1 hour.After this suspension is carried out sucking filtration, deionized water (100ml) is utilized to carry out drip washing.Make After obtained product is dispersed in toluene (800ml), under being heated to reflux, carry out azeotropic dehydration.Recover to room temperature (20 DEG C), after sucking filtration, at 100 DEG C of drying under reduced pressure until reaching constant, thus obtain as white solid double (9-hydroxymethyl fluorenes- 9-yl) methane (compound 9) 104g (yield 87%, HPLC purity: 99.8%).Sodium in solid, the content of chlorine are 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).

It addition, the very big wavelength X of absorption in the UV-Vis spectrum of compound 9 (solvent: THF)_maxBe present in 263nm, 292nm and 304nm.And the 5wt% weightless temperature (under nitrogen atmosphere) of compound 9 is 289 DEG C, and fusing point is 226 DEG C.

The synthesis of double (the 9-hydroxymethyl fluorenes-9-base) ethane (compound 10) of [synthesis example 10] 1,2-

[changing 134]

1L four-hole boiling flask loads in synthesis example 4 double (fluorenes-9-base) ethane of the 1,2-obtained (compound 4,100g, 278.9mmol), paraformaldehyde (17.6g, 585.8mmol), DMF (400ml), after carrying out nitrogen displacement, It is cooled to less than 10 DEG C.Add Sodium ethylate (1.80g, 27.9mmol), be warming up to room temperature (20 DEG C), carry out stirring in 1 hour.Utilize After HPLC confirms raw material disappearance, reactant liquor is added drop-wise in 0.1N hydrochloric acid (440ml), stopped reaction.To obtained suspension Solution carries out sucking filtration, utilizes deionized water (100ml) to carry out drip washing.Thereafter, obtained thick product is made to be dispersed in N, N-bis- In methylformamide (300ml), carry out stirring in 1 hour.This hanging drop is added in 0.005N hydrochloric acid (1000ml), stirs 30 After minute, carry out sucking filtration.Make obtained thick product be dispersed in deionized water (500ml), carry out stirring in 1 hour.To this After suspension carries out sucking filtration, deionized water (200ml) is utilized to carry out drip washing.Obtained thick product is made to be dispersed in toluene (500ml), after in, Dean-Stark apparatus is utilized to be dehydrated under heated reflux condition.Recover to room temperature (20 DEG C), enter Row sucking filtration, at 100 DEG C of drying under reduced pressure until reaching constant, thus obtains 1 as white solid, 2-pair (9-hydroxymethyl fluorenes- 9-yl) ethane (compound 10) 112.4g (yield: 96.3%, 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).

It addition, the very big wavelength X of absorption in the UV-Vis spectrum of compound 10 (solvent: THF)_maxBe present in 264nm, 291nm and 302nm.It addition, the 5wt% weightless temperature (under nitrogen atmosphere) of compound 10 is 301 DEG C, fusing point is 278 DEG C.

The synthesis of [synthesis example 11] 1,2-double (fluorenes-9-base) butane (compound 11)

[changing 135]

In the SUS316 autoclave of capacity 70ml load fluorenes (3.5g, 21mmol), 1,4-butanediol (4.9g, 54mmol), 85%KOH (1.52g, 23mmol), TEG dimethyl ether (4.9g), carry out 8 at 250 DEG C in a nitrogen atmosphere Hour reaction.After cooling, make content be dispersed in oxolane and water, utilize dilute hydrochloric acid to neutralize.Molten by obtained suspension Liquid filters and separates out powder, wash, thus obtain the Isosorbide-5-Nitrae as white solid-bis-(fluorenes-9-base) butane (compound 11) 1.7g (yield: 41.9%, 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-base) butane (compound 12) of [synthesis example 12] 1,2-

[changing 136]

500mL four-hole boiling flask loads double (fluorenes-9-base) butane of 1,2-obtained above (compound 11,37.0g, 95.7mmol), paraformaldehyde (6.03g, 201mmol), DMF (148ml), after carrying out nitrogen displacement, cooling To less than 10 DEG C.Add Sodium ethylate (0.65g, 9.6mmol), be warming up to room temperature (20 DEG C), carry out stirring in 1 hour.Pass through HPLC After confirming raw material disappearance, reactant liquor is added drop-wise in 0.1N hydrochloric acid (162ml), stopped reaction.To obtained aaerosol solution Carry out sucking filtration, utilize deionized water (37ml) to carry out drip washing.After making obtained thick product be dispersed in toluene (185ml), Dean-Stark apparatus is utilized to be dehydrated under heated reflux condition.Recover to room temperature (20 DEG C), carry out sucking filtration, 80 DEG C drying under reduced pressure is until reaching constant, thus obtains 1 as white solid, and double (the 9-hydroxymethyl fluorenes-9-base) butane of 2-(is changed Compound 12) 39.8g (yield: 93.1%, 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).

It addition, the very big wavelength X of absorption in the UV-Vis spectrum of compound 12 (solvent: THF)_maxBe present in 291nm and 302nm.It addition, the 5wt% weightless temperature (under nitrogen atmosphere) of compound 12 is 314 DEG C, fusing point is 212 DEG C.

The synthesis of [synthesis example 13] α, α '-bis-(9-hydroxymethyl fluorenes-9-base)-1,4-dimethylbenzene (compound 13)

[changing 137]

α, α '-bis-(fluorenes-9-base)-1,4-dimethylbenzene ((130g, 0.3mol), poly first is loaded in tetra-mouthfuls of eggplant-shape bottles of 1L Aldehyde (18.9g, 0.63mol), DMF (520ml), carry out adding after nitrogen displacement Sodium ethylate (2.04g, 0.03mol), under room temperature (20 DEG C), carry out stirring in 1 hour.Deionized water 520ml and 1N hydrochloric acid is loaded in 1L beaker (45ml), add reactant liquor after being stirred, make reaction be quenched.Obtained crystallization is carried out sucking filtration, utilizes deionized water (100ml) drip washing is carried out.After making obtained thick product be dispersed in deionized water (500ml), carry out sucking filtration, utilize go from Sub-water (100ml) carries out drip washing.After making obtained thick product be dispersed in toluene (500ml), Dean-Stark is utilized to fill Put and be dehydrated under heated reflux condition.Recover to room temperature (20 DEG C), carry out sucking filtration, at 70 DEG C of drying under reduced pressure to reaching permanent Amount, thus obtain white solid (compound 13) 130g (yield: 87%, 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).

It addition, the 5wt% weightless temperature (under nitrogen atmosphere) of compound 13 is 327 DEG C, fusing point is 198 DEG C.

The synthesis of double (9-hydroxyphenyl fluorene-9-base) ethane (compound 14) of [synthesis example 14] 1,2-

[changing 138]

1L four-hole boiling flask loads double (fluorenes-9-base) ethane of the 1,2-obtained by the method for synthesis example 4 (compound 4, 20g, 59mmol), DMF (200ml), add tributyl phosphite (37.9ml, 140mmol), carry out nitrogen After displacement, add benzyltrimethylammonium hydroxide (40% methanol solution) (25ml), make air (100ml/ minute) and nitrogen The mixed gas of (300ml/ minute) circulates in reaction system.After stirring 3 hours, add benzyltrimethylammonium hydroxide (40% methanol solution) (10ml), stirs 5 hours.Add benzyltrimethylammonium hydroxide (40%MeOH solution) further (10ml), so stirring 1 hour.Add 1N hydrochloric acid (200ml), stopped reaction, add ethyl acetate (400ml), carry out separatory Operation.Further with saturated aqueous common salt (100ml), organic layer is carried out 3 times to clean.Magnesium sulfate is utilized to make organic layer dried, Filtering, decompression is distilled off organic solvent.Toluene (100ml), hexane is added in obtained aaerosol solution (200ml), after stirring 30 minutes, carrying out sucking filtration, at 80 DEG C of drying under reduced pressure until reaching constant, thus obtaining as white solid Double (9-hydroxyphenyl fluorene-9-base) ethane (compound 14) 13.9g (yield: 63.8%, HPLC purity: 92.5%) of 1,2-.Chemical combination Thing 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-oxethyl) phenyl] fluorenes-9-base } ethane (compound 15)

[changing 139]

300mL four-hole boiling flask loads utilize double (fluorenes-9-base) ethane of 1,2-that said method obtains (compound 14, 17g, 45mmol), phenyl phenol (37g, 267mmol), after carrying out nitrogen displacement, be cooled to less than 10 DEG C.Add borontrifluoride Boron-diethyl ether complex (5.6ml, 45mmol), after stirring 3 hours, adds boron trifluoride-two under room temperature (20 DEG C) further Etherate (5.6ml, 45mmol), chloroform (35ml), stir at 40 DEG C 4 hours, stir 2 hours at 60 DEG C.Enter one Step adds boron trifluoride-diethyl ether complex (5.6ml, 45mmol), crosses hot reflux 2 hours.After being cooled to room temperature (20 DEG C), make It is neutralized with saturated sodium bicarbonate aqueous solution, removes insoluble matter by sucking filtration afterwards.Add ethyl acetate (120ml), will have Machine layer utilizes saturated aqueous common salt to clean 2 times, utilizes deionized water to clean 1 time, utilizes magnesium sulfate dried, filters, decompression Organic solvent is distilled off.Again it is dissolved in ethyl acetate (150ml), addition activated carbon (NORIT Co., Ltd. of Japan, SXPLUS, pH=7,2.5g), after carrying out stirring in 1 hour, carry out kieselguhr filtration, decompression is distilled off organic solvent.Add first Alcohol (100ml), stirring 1 hour, carries out sucking filtration, at 80 DEG C of drying under reduced pressure until reaching constant, thus obtaining as white solid Double { [4-(2-hydroxyl-oxethyl) phenyl] fluorenes-9-base } ethane (compound 15) 15.8g (yield: 56.1%, 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-diethanol (compound 16)

[changing 140]

Synthesize according to the method described in Japanese Unexamined Patent Publication 2010-261008 publication.

The shorthand notations of the compound used in following embodiment and comparative example etc. are as follows.

Double [4-(2-hydroxyl-oxethyl) the phenyl]-fluorenes of BHEPF:9,9-(OSAKA GAS CHEMICALS Co., Ltd. system Make)

Double (4-hydroxy-3-methyl phenyl)-fluorenes of BCF:9,9-(OSAKA GAS CHEMICALS Co., Ltd. manufacture)

DPC: diphenyl carbonate (Mitsubishi chemical Co., Ltd's manufacture)

ISB: isosorbide (Roquette Freres society manufacture, trade name: POLYSORB)

CHDM:1,4-cyclohexanedimethanol (cis, trans mixture, society of SK Chemical manufacture)

TCDDM: Tricyclodecane Dimethanol (manufacture of Oxea society)

SPG: the spiroglycol (Mitsubishi Gas Chemical Co., Ltd's manufacture)

Double [4-hydroxy phenyl] propane (Mitsubishi chemical Co., Ltd's manufacture) of BPA:2,2-

PEG: Polyethylene Glycol number-average molecular weight: 1000 (Sanyo Chemical Industries Co., Ltd.'s manufactures)

CHDA:1,4-cyclohexane dicarboxylic acid (cis, trans mixture, Eastman chemistry society manufacture)

DMT: dimethyl terephthalate (DMT) (Tokyo HuaCheng Industry Co., Ltd's manufacture)

[embodiment 1-1]

Double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 3) 38.06 mass parts (0.059mol) of general, ISB53.73 mass parts (0.368mol), CHDM 9.64 mass parts (0.067mol), DPC 81.28 mass parts (0.379mol) And the calcium acetate monohydrate 3.83 × 10 as catalyst^-4Mass parts (2.17 × 10^-6Mol) put in reaction vessel, To carrying out nitrogen displacement of reducing pressure in reaction unit.In a nitrogen atmosphere, in 150 DEG C of stir abouts 10 minutes while making raw material molten Solve.As the operation of reaction the 1st step, utilize 30 minutes and be warming up under 220 DEG C, normal pressure carry out reaction in 60 minutes.Next utilize 90 minutes by pressure by atmospheric depressurized to 13.3kPa, keep 30 minutes at 13.3kPa, the phenol of generation be retracted to reactant Outside system.It follows that as the operation of reaction the 2nd step, utilize heat medium temperature was warming up to 240 DEG C in 15 minutes, utilize 15 simultaneously Minute by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction system.Reach the stirring moment of torsion of regulation After, recover to normal pressure with nitrogen, terminate reaction, the polyestercarbonate of generation is expressed in water, cut strands and obtain granule. The granule using obtained polyestercarbonate has carried out above-mentioned various evaluation.Evaluation result is listed in table 1.

About the polyestercarbonate of embodiment 1-1, few from the content of the oligomeric fluorene structural units of compound 3, it is 27.0 Quality %, the wavelength dispersion (R450/R550) of phase retardation film is shown as 0.835, it will be understood that the scattered expression power of inverse wave length High, be 0.025.Additionally, the photoelastic coefficient of the polyestercarbonate of embodiment 1-1 is low, glass transition temperature is 143 DEG C, it is The value of the balancing good of melt processable and thermostability.

[comparative example 1-1]

Except using double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] ethane (compound 6) 45.69 mass parts of 1,2- (0.070mol), ISB 43.13 mass parts (0.295mol), CHDM 15.64 mass parts (0.108mol), DPC 72.36 mass Part (0.338mol), calcium acetate monohydrate 3.55 × 10^-4Mass parts (2.02 × 10^-6Mol) beyond, as embodiment 1-1 Ground synthesizes, and obtains the granule of polyestercarbonate.The granule using obtained polyestercarbonate has carried out above-mentioned various comment Valency.Evaluation result is listed in table 1.

The scattered expression power of inverse wave length of the polyestercarbonate of comparative example 1-1 is the highest, it may have excellent mechanical properties, but Photoelasticity characteristic is poor.

[comparative example 1-2]

Except use double [9-(3-hydroxypropyl)-fluorenes-9-base] methane (compound 7) 35.02 mass parts (0.076mol), ISB40.75 mass parts (0.279mol), CHDM 12.71 mass parts (0.088mol), DPC 95.85 mass parts (0.447mol), calcium acetate monohydrate 3.90 × 10^-4Mass parts (2.22 × 10^-6Mol) beyond, in the same manner as embodiment 1-1 Synthesize, obtain the granule of Merlon.The granule using obtained Merlon has carried out above-mentioned various evaluation.Evaluate Result is listed in table 1.

The Merlon of comparative example 1-2 also has the characteristic that comparison is excellent, but the scattered expression power of inverse wave length is poor.

[comparative example 1-3]

Except using double [9-(3-hydroxypropyl)-fluorenes-9-base] ethane (compound 8) 37.92 mass parts of 1,2- (0.080mol), ISB 42.45 mass parts (0.290mol), CHDM 8.47 mass parts (0.059mol), DPC 92.84 mass Part (0.433mol), calcium acetate monohydrate 3.78 × 10^-4Mass parts (2.15 × 10^-6Mol) beyond, as embodiment 1-1 Ground synthesizes, and obtains the granule of Merlon.The granule using obtained Merlon has carried out above-mentioned various evaluation.Comment Valency result is listed in table 1.

The scattered expression power of inverse wave length of the Merlon of comparative example 1-3, photoelasticity characteristic are poor.

[comparative example 1-4]

Except using double (9-hydroxymethyl fluorenes-9-base) methane (compound 9) 28.19 mass parts (0.070mol), ISB 42.45 mass parts (0.290mol), CHDM 16.95 mass parts (0.118mol), DPC 103.35 mass parts (0.482mol), Calcium acetate monohydrate 1.68 × 10^-3Mass parts (9.55 × 10^-6Mol), beyond, synthesize in the same manner as embodiment 1-1, Granule to Merlon.The granule using obtained Merlon has carried out above-mentioned various evaluation.Evaluation result is listed in table 1。

Compound 9 be can import with in embodiment 1-1 or comparative example 1-1～1-3 use fluorenes system monomer as low The compound of polyfluorene construction unit, but use the Merlon of compound 9 unexpectedly not demonstrate inverse wave length dispersibility.Speculate it Reason is, the fluorenes ring of compound 9 is not to be orientated in vertical direction relative to draw direction.

[comparative example 1-5]

Except use double (9-hydroxymethyl fluorenes-9-base) ethane (compound 10) 47.08 mass parts (0.112mol) of 1,2-, ISB29.71 mass parts (0.203mol), CHDM 12.71 mass parts (0.088mol), DPC 87.40 mass parts (0.408mol), calcium acetate monohydrate 7.12 × 10^-4Mass parts (4.04 × 10^-6Mol) beyond, in the same manner as embodiment 1-1 Synthesize, obtain the granule of Merlon.The granule using obtained Merlon has carried out above-mentioned various evaluation.Evaluate Result is listed in table 1.

The resin of this example does not demonstrates inverse wave length dispersibility in the same manner as comparative example 1-4.

[comparative example 1-6]

Except use double (9-hydroxymethyl fluorenes-9-base) butane (compound 12) 32.13 mass parts (0.072mol) of 1,2-, ISB43.30 mass parts (0.296mol), CHDM 12.71 mass parts (0.088mol), DPC 98.74 mass parts (0.461mol), calcium acetate monohydrate 8.04 × 10^-4Mass parts (4.56 × 10^-6Mol) beyond, in the same manner as embodiment 1-1 Synthesize, obtain the granule of Merlon.The granule using obtained Merlon has carried out above-mentioned various evaluation.Evaluate Result is listed in table 1.

[comparative example 1-7]

Except use double (9-hydroxymethyl fluorenes-9-base) methane (compound 9) 33.85 mass parts (0.084mol), CHDM28.97 mass parts (0.201mol), CHDA 48.03 mass parts (0.279mol) and as catalyst metatitanic acid four just Butyl ester 9.49 × 10^-3Mass parts (2.79 × 10^-5Mol), beyond, synthesize in the same manner as embodiment 1-6, obtain polyester Grain.The granule using obtained polyester has carried out above-mentioned various evaluation.Evaluation result is listed in table 1.

In this example, the compound 9 used in the Merlon of comparative example 1-4 synthesize polyester, but polyester has not shown yet Go out inverse wave length dispersibility.

[comparative example 1-8]

Except using α, α '-bis-(9-hydroxymethyl fluorenes-9-base)-1,4-dimethylbenzene (compound 13) 38.00 mass parts (0.077mol), ISB 33.96 mass parts (0.232mol), CHDM 16.95 mass parts (0.118mol), DPC 92.32 mass Part (0.431mol), calcium acetate monohydrate 7.52 × 10^-4Mass parts (4.27 × 10^-6Mol) beyond, as embodiment 1-1 Ground synthesizes, and obtains the granule of Merlon.The granule using obtained Merlon has carried out above-mentioned various evaluation.Comment Valency result is listed in table 1.

The resin of this example does not demonstrates inverse wave length dispersibility in the same manner as comparative example 1-4.Knot by comparative example 1-4～1-8 Fruit is it is believed that the distance of the carbonyl that contains in carbonate group or ester group and fluorenes ring creates shadow to the presence or absence of inverse wave length dispersibility Ring.Can speculate: if the hypotelorism of carbonyl and fluorenes ring, then make the fluorenes ring cannot be in preferably side due to the sterically hindered of carbonyl To orientation, thus inverse wave length dispersibility cannot be shown.

[comparative example 1-9]

Except using double { [4-(2-hydroxyl-oxethyl) phenyl] fluorenes-9-base } ethane (compound 15) 37.46 mass parts (0.059mol), ISB 39.05 mass parts (0.267mol), CHDM 12.71 mass parts (0.088mol), DPC 89.73 mass Part (0.419mol), calcium acetate monohydrate 7.31 × 10^-4Mass parts (4.15 × 10^-6Mol) beyond, as embodiment 1-1 Ground synthesizes, and obtains the granule of Merlon.The granule using obtained Merlon has carried out above-mentioned various evaluation.Comment Valency result is listed in table 1.

The value of the wavelength dispersion (R450/R550) of the resin of this example, close to 1, has smooth wavelength dispersibility.Can push away Survey: in the resin of this example, if increasing the amount of the construction unit from compound 15, demonstrating inverse wave length dispersibility, but can sentence The disconnected scattered expression power of inverse wave length is low.

[comparative example 1-10]

Except using fluorenes-9,9-diethanol (compound 16) 32.66 mass parts (0.128mol), ISB 54.34 mass parts (0.372mol), DPC 109.30 mass parts (0.510mol), calcium acetate monohydrate 1.32 × 10^-3Mass parts (7.50 × 10^-6Mol) beyond, synthesize in the same manner as embodiment 1-1, obtain the granule of Merlon.Use obtained Merlon Granule has carried out above-mentioned various evaluation.Evaluation result is listed in table 1.

The resin of this example demonstrates inverse wave length dispersibility, but the expression power of inverse wave length dispersibility is poor, and photoelastic coefficient also becomes High.It addition, in this example, the foaming of resin during polymerization or during melted masking is the most, for the situation of poor heat stability.

[comparative example 1-11]

Except using BHEPF 68.07 mass parts (0.155mol), ISB 22.84 mass parts (0.156mol), PEG 0.97 mass parts (9.75 × 10^-4Mol), DPC 67.60 mass parts (0.316mol), magnesium acetate 4 hydrate 5.36 × 10^-4Matter Amount part (2.50 × 10^-6Mol) beyond, synthesize in the same manner as embodiment 1-1, obtain the granule of Merlon.Use gained To the granule of Merlon carried out above-mentioned various evaluation.Evaluation result is listed in table 1.

In the resin of this example, the content from the construction unit of BHEPF is 67.8 mass %, the most, it is known that this structure The scattered expression power of inverse wave length of unit is poor.It addition, the value of photoelastic coefficient is the highest.

[comparative example 1-12]

Use BCF 41.17 mass parts (0.109mol), SPG 51.59 mass parts (0.170mol), DPC 63.19 mass Part (0.295mol), calcium acetate monohydrate 4.90 × 10^-3Mass parts (2.78 × 10^-5Mol), making final polymerization temperature is 260 DEG C, synthesize in the same manner as embodiment 1-1 in addition, obtain the granule of Merlon.Use obtained Merlon Granule carried out above-mentioned various evaluation.Evaluation result is listed in table 1.

The resin of this example demonstrates the optical characteristics that comparison is excellent, but obtained film is highly brittle, and is easily broken, toughness Difference.

In below example 1-2～6 and comparative example 1-13～1-17, larger polymerization unit is used to synthesize Resin, makes long film by extrusion by melting, and has carried out the evaluation of various characteristic.Herein, particularly attached in fracture gauge Stretch under conditions of Jin, have rated the birefringence (orientation) of stretched film.

[embodiment 1-2]

Use by possessing stirring paddle and controlling to be gathering of constituting of two vertical reactors of reflux condenser of 100 DEG C in batches Locking device, is polymerized.Put into double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 3) 36.94 mass parts (0.058mol), ISB 64.02 mass parts (0.438mol), DPC 82.43 mass parts (0.385mol) and as catalyst Calcium acetate monohydrate 3.86 × 10^-4Mass parts (2.19 × 10^-6mol).To carrying out nitrogen displacement of reducing pressure in reaction unit After, utilize thermal medium to heat, the moment reaching 100 DEG C in interior temperature starts stirring.Heat up and make Nei Wenda after starting 40 minutes To 220 DEG C, it is controlled keeping this temperature, starts simultaneously at decompression, with 90 minutes for 13.3kPa after reaching 220 DEG C.Will be with The phenol vapor of polyreaction together by-product imports in the reflux condenser of 100 DEG C, makes the monomer contained on a small quantity in phenol vapor Composition is back to reactor, reclaims in the condenser of uncooled phenol vapor importing 45 DEG C.Nitrogen is imported to the 1st reactor And once recovering to atmospheric pressure, the reactant liquor through oligomeric materialization in the 1st reactor is moved to the 2nd reactor.It follows that open Begin the liter gentleness decompression in the 2nd reactor, with within 50 minutes, to make interior temperature be 240 DEG C, pressure is 0.2kPa.Thereafter, it is polymerized to Reach the stirring power of regulation.When reaching regulation power, import nitrogen to reactor and recover pressure, the polyester that will generate Carbonic ester is extruded to water, cuts strands and obtains granule.

Use above-mentioned extrusion by melting, obtained polyestercarbonate make the length of long 3m, wide 200mm, thick 72 μm Unstretching film.It follows that utilize said method to carry out vertical simple tension, near fracture gauge under conditions of make phase contrast Film.The result of various evaluations is listed in table 2.

The phase retardation film of this example demonstrates inverse wave length dispersibility, and then the degree of orientation, photoelastic coefficient, thermostability, toughness etc. Complete characteristic is excellent.

[embodiment 1-3]

Use double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 3) 38.06 mass parts (0.059mol), ISB43.06 mass parts (0.295mol), CHDM 20.28 mass parts (0.141mol), DPC 81.46 mass Part (0.380mol), calcium acetate monohydrate 3.83 × 10^-4Mass parts (2.18 × 10^-6Mol), the thickness making unstretching film is 66 μm, make phase retardation film in addition in the same manner as embodiment 1-2.The result of various evaluations is listed in table 2.

The phase retardation 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 [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 3) 31.02 mass parts (0.048mol), ISB43.08 mass parts (0.295mol), TCDDM 25.26 mass parts (0.129mol), DPC 81.26 mass Part (0.379mol), calcium acetate monohydrate 3.73 × 10^-4Mass parts (2.12 × 10^-6Mol), the thickness making unstretching film is 73 μm, make phase retardation film in addition in the same manner as embodiment 1-2.The result of various evaluations is listed in table 2.

The phase retardation film of this example has the orientation that comparison is high, and photoelastic coefficient reduces.

[embodiment 1-5]

Use double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 3) 29.60 mass parts (0.046mol), ISB29.21 mass parts (0.200mol), SPG 42.28 mass parts (0.139mol), DPC 63.77 mass parts (0.298mol), calcium acetate monohydrate 1.19 × 10^-2Mass parts (6.78 × 10^-5Mol), the thickness making unstretching film is 62 μ M, makes phase retardation film in addition in the same manner as embodiment 1-2.The result of various evaluations is listed in table 2.

The phase retardation film of this example birefringence and photoelastic coefficient compared with embodiment 1-2 is excellent.

[embodiment 1-6]

Use double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 3) 29.18 mass parts (0.046mol), ISB30.38 mass parts (0.208mol), SPG 41.27 mass parts (0.136mol), DPC 64.55 mass parts (0.298mol), calcium acetate monohydrate 1.21 × 10^-2Mass parts (6.86 × 10^-5Mol), the thickness making unstretching film is 58 μ M, makes phase retardation film in addition in the same manner as embodiment 1-2.The result of various evaluations is listed in table 2.

The phase retardation film of this example compared with embodiment 1-2 by weakening inverse wave length dispersibility, thus compared with embodiment 1-2 Birefringent value can be increased, the degree of orientation of polymer can be improved.The deviation compared with embodiment 1-2 of the phase retardation film of this example The ideal value of R450/R550, but can be suitable for using the phase of embodiment 1-6 when paying attention to the filming of film according to the difference of purposes Potential difference film.

[comparative example 1-13]

Use BHEPF 63.72 mass parts (0.145mol), ISB 26.74 mass parts (0.183mol), PEG 0.97 matter Amount part (9.75 × 10^-4Mol), DPC 71.24 mass parts (0.333mol), magnesium acetate 4 hydrate 7.06 × 10^-4Mass parts (3.29×10^-6Mol), the thickness making unstretching film is 76 μm, makes phase retardation film in addition in the same manner as embodiment 1-2. The result of various evaluations is listed in table 2.

The phase retardation film of this example is compared with embodiment, it is known that the scattered expression power of orientation, inverse wave length and photoelastic coefficient Difference.

[comparative example 1-14]

Use BHEPF 68.07 mass parts (0.155mol), ISB 22.84 mass parts (0.156mol), PEG 0.97 matter Amount part (9.75 × 10^-4Mol), DPC 67.60 mass parts (0.316mol), magnesium acetate 4 hydrate 5.36 × 10^-4Mass parts (2.50×10^-6Mol), the thickness making unstretching film is 87 μm, makes phase retardation film in addition in the same manner as embodiment 1-2. The result of various evaluations is listed in table 2.

The phase retardation film of this example makes the wavelength dispersibility ideal value close to R450/R550 of comparative example 1-13, but by increasing Strong inverse wave length dispersion, thus orientation reduces, the scattered expression power of inverse wave length is the poorest.

[comparative example 1-15]

Use BCF 32.20 mass parts (0.085mol), SPG 60.43 mass parts (0.199mol), DPC 64.40 mass Part (0.301mol), calcium acetate monohydrate 5.00 × 10^-3Mass parts (2.84 × 10^-5Mol), making final polymerization temperature is 260 DEG C, the thickness making unstretching film is 76 μm, makes phase retardation film in addition in the same manner as embodiment 1-2.The knot of various evaluations Fruit is listed in table 2.

The shortcoming that the phase retardation film of this example has orientation and the scattered expression power of inverse wave length is poor and film is crisp.

[comparative example 1-16]

Use BHEPF 80.49 mass parts (0.184mol), BPA13.23 mass parts (0.058mol), DPC 53.29 matter Amount 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 making unstretching film is 98 μm, makes phase retardation film in addition in the same manner as embodiment 1-2.Various evaluations Result is listed in table 2.

The phase retardation film of this example birefringence compared with embodiment is greatly reduced.And photoelastic coefficient also becomes big.Can examine Consider, owing to the amount of the aromatic structure on main chain is many, so that for showing the amount of the aromatic component against dispersibility also Many, therefore can cause the reduction of optical characteristics.

[comparative example 1-17]

Use BHEPF 86.84 mass parts (0.198mol), DMT 14.95 mass parts (0.077mol), DPC 28.90 matter Amount part (0.135mol), tetra-n-butyl titanate 1.35 × 10^-2Mass parts (3.96 × 10^-5Mol), making final polymerization temperature is 260 DEG C, the thickness making unstretching film is 148 μm, makes phase retardation film in addition in the same manner as embodiment 1-2.The knot of various evaluations Fruit is listed in table 2.

The phase retardation film of this example birefringence compared with embodiment is also greatly reduced, and photoelastic coefficient also becomes big.

[table 1]

[table 2]

" embodiment 2-1～2-2, reference example 2-1～2-2 "

The quality evaluation of the three fluorenes diester of the present invention and the evaluating characteristics of resin combination and hyaline membrane are by following side Method is carried out.It should be noted that evaluating characteristics maneuver is not limited to following method, those skilled in the art can suitably select Select.

It addition, the shorthand notations of the compound used in following synthesis example and embodiment etc. are as follows.

ISB: isosorbide (Roquette Freres society manufacture, trade name: POLYSORB)

DPC: diphenyl carbonate (Mitsubishi chemical Co., Ltd's manufacture)

SPG: the spiroglycol (Mitsubishi Gas Chemical Co., Ltd's manufacture)

THF: oxolane (manufactures without stabilizer, WAKO society)

(1) heat decomposition temperature (TG-DTA) of low polyfluorene monomer

The decomposition initial temperature of low polyfluorene monomer, fusing point use differential thermogravimetric analytical equipment (SII simultaneously Nanotechnology society manufactures TG-DTA6300) it is measured.By about 4mg analysis sample put into this society manufacture aluminum dish in also Sealing, the nitrogen at 200mL/ minute flows down, and is warming up to 600 with programming rate 10 DEG C/min by room temperature (20～30 DEG C) ℃.According to obtained TG data (Thermogravimetric Data), the low temperature side baseline extrapolated baseline that weight reduces behavior reduces with weight The temperature of the intersection point that the tangent line of maximum inclination point intersects is as decomposing initial temperature.It addition, according to obtained TG data (thermogravimetric Data), using this summit fusing point as sample reducing and observing precipitous endothermic peak to sample weight unconfirmed.

(2) content ratio of Na, K, Cs, the Fe in resin combination

Accurate weighing about 0.5g resin combination sample in the microwave decomposition container that PerkinElmer society manufactures, adds 97% sulphuric acid (rub chemistry manufacture ultra-high purity sulphuric acid) 2mL so that it is for air-tight state more, carry out at 230 DEG C 10 minutes micro- Wave heating.After being cooled to room temperature (less than 30 DEG C), add 68% nitric acid (the ultra-high purity nitric acid that the chemistry that rubs manufactures more) 1.5mL, It is air-tight state, after carrying out 10 minutes microwave heatings at 150 DEG C, is again cooled to room temperature (less than 30 DEG C), add 68% nitric acid 2.5mL, is air-tight state again, carries out 10 minutes microwave heatings, make content divide completely at 230 DEG C Solve.Microwave applicator uses the Multiwave3000 that PerkinElmer society manufactures, defeated by adjusting between 300W to 1000W Go out power to adjust temperature.After being cooled to room temperature (less than 30 DEG C), utilize pure water to dilute liquid obtained above, utilize The ICP-MS that ThermoQuest society manufactures is carried out quantitatively.

(3) the remaining monohydroxy compound in resin combination

Accurate weighing about 1g resin combination sample, is dissolved in dichloromethane 5mL, adds acetone afterwards, makes the total amount be 25mL.Solution utilizes 0.2 μm disc filter filter, utilize liquid chromatography carry out phenol quantitative after, calculate Content ratio.

(4) toughness (crooked test) of film

Thickness 100 μm～the film of 200 μm is molded, by the long 40mm of this film production, width by above-mentioned method based on hot pressing The rectangle test film of 10mm.40mm is opened at the interval on composition surface, vice left and right, the two ends of test film are fixed on joint In face.Then make the interval on composition surface, left and right reduce with 2 mm/second speed below, be expressed into connecing of vice not making film In the case of outside conjunction face, the film reduced overall of " く " word will be bent in this composition surface.The most closely sealed between near composition surface it is Only test film is cleaved into the situation of 2 (or fragmentations of more than 3) as " having crackle " at bending section, even if by complete between composition surface The situation that closely sealed test film does not splits yet and bends is as " flawless ".Same kind of film is implemented to repeat test for 5 times, will Be for more than 4 times wherein the situation of " having crackle " as " ×: occur brittle break ", by the situation work that less than 3 times is " having crackle " For " zero: brittle break does not occurs ".

(5) refractive index and the mensuration of Abbe number

By the film obtained by above-mentioned method based on hot pressing cuts out long 40mm, the rectangle test film of wide 8mm, as Measure sample.Utilize multi-wavelength Abbe index meter (Co., Ltd. Atago DR-M4/1550), use wavelength 656nm (C Line), 589nm (D line), the interference light filter of 486nm (F line), measure the refractive index of each wavelength, nC, nD, nF.Mensuration uses Single bromonaphthalene, as interface liquid, is measured at 20 DEG C.Abbe number ν d is calculated by following formula.

ν d=(1-nD)/(nC-nF)

Abbe number is the biggest, represents that the wavelength dependency of refractive index is the least.

The reduced viscosity of resin combination, glass transition temperature, melt viscosity, photoelastic coefficient measure with above-mentioned Embodiment 1-1 is identical.

Double { [9-(2-ethoxycarbonylethyl group) fluorenes-9-base]-methyl } fluorenes (compound 3) and double [9-(2-ethoxy carbonyl Ethyl) fluorenes-9-base] synthesis of methane (compound 2)

[changing 141]

Double (fluorenes-9-base) methane (compound 1) 35.0g (102mmol), THF175mL is added in the removable flask of 1L, It is stirred in 15 DEG C in a nitrogen atmosphere.Add 50wt% sodium hydrate aqueous solution 28.68g, benzyltriethylammoinium chloride After 4.61g (20.2mL), stir 15 minutes.After utilizing within 60 minutes, add ethyl acrylate 22.4mL (224mmol), ripe at 16 DEG C Change 2 hours.Having carried out the HPLC in reaction terminating moment to analyze, result compound 2 (13.5min) is 75.3 area %, compound 3 (15.2min) it is 8.4 area %.After utilizing 3N hydrochloric acid to be neutralized, separatory and remove water layer.It is added to toluene 70mL, The cleaning of 5 organic layers has been carried out with water 105mL.After organic layer adds toluene 35mL, THF35mL, interior temperature is remained 60 More than DEG C, heating simultaneously is evaporated to 70mL.After adding toluene 35mL, naturally cool to 45 DEG C, add methanol 210mL, Carry out the crystallize of double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] methane (compound 2).Crystallize thing is filtered, will filter Liquid is several days standing in room temperature, is recovered by filtration double { [9-(2-ethoxycarbonylethyl group) fluorenes-9-base]-methyl } fluorenes generated The white crystals of (compound 3).

Double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] methane (compound 2): 37.47g (68.7mmol, yield: 67.6%), white powder

HPLC analysis result compound 2 (13.5min): 91.7 area %, compound 3 (15.2min): 5.2 area %

Decomposition initial temperature (under nitrogen atmosphere): 295 DEG C

M.p.:141 DEG C

Double { [9-(2-ethoxycarbonylethyl group) fluorenes-9-base]-methyl } fluorenes (compound 3): 0.20g (0.3mmol, yield: 0.3%), white crystals

HPLC analysis result 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)

Decomposition initial temperature (under nitrogen atmosphere): 364 DEG C

M.p.:166 DEG C

It should be noted that the HPLC after reaction terminating, after crystallize and filtration implements the most under the following conditions.

Post: Inertsil ODS-3V 150mm × 4.8mm φ

Temperature: 40 DEG C

Eluent condition: 0-5min: oxolane /=50/50,20min: oxolane/water=100/0

Flow velocity: 1.0ml/min

Injection rate: 2 μ l

Double { [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base]-methyl } fluorenes (compound 5) and double [9-(2-phenyloxycarbonyl Ethyl) fluorenes-9-base] synthesis of methane (compound 4)

[changing 142]

In the removable flask of 1L, to containing double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] methane (compound 2, 84.1g, 154.5mmol) and double { [9-(2-ethoxycarbonylethyl group) fluorenes-9-base]-methyl } fluorenes (compound 3,3.3g, After oxolane 6.9mmol)/o-Dimethylbenzene mixed solution adds diphenyl carbonate (147.5g, 5685.5mmol), by interior Temperature is warming up to 104 DEG C at leisure, is decompressed to 3kPa afterwards, solvent is distilled off.Recover pressure, add original four-isopropyl titanate (2.45g, 8.61mmol), is again decompressed to 3kPa, is warming up to 184 DEG C at leisure, while being distilled off reacting distillation. After arriving 184 DEG C, react 3 hours, be cooled to 90 DEG C afterwards, recover pressure, be analyzed to identify the carrying out of reaction by HPLC.Add Entering o-Dimethylbenzene (144ml), be cooled to 41 DEG C, results verification is to the precipitation of crystallization.After being cooled to 40 DEG C, add methanol (356mL), and then after being cooled to 5 DEG C, sucking filtration is carried out.Make obtained coarse crystallization be dispersed in o-Dimethylbenzene (272mL), add After water (0.32g), it is warming up to 80 DEG C so that it is dissolve.Carry out the cleaning of 2 organic layers with water (240mL) after, filter by PTFE film Device (0.5 μm) carries out pressure filtration (0.25MPa).Thereafter, after solvent 110g being distilled off with vaporizer, it is cooled to 50 DEG C, knot Fruit observes the precipitation of crystallization.And then after being cooled to 40 DEG C, add methanol (336mL), after being cooled to room temperature (20 DEG C), take out Filter, at 80 DEG C of drying under reduced pressure until reaching constant, as double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 4) 59.9g (yield: 55.6%, 46.8mmol) and double { [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base]-methyl } fluorenes (chemical combination Thing 5) mixture of 0.2g (yield: 2.2%, 0.15mmol) and obtain white solid.

HPLC analysis result compound 4 (15.3min): 98.17 area %, compound 5 (16.5min): 0.15 area %

Post: Inertsil ODS-3V 150mm × 4.8mm φ

Temperature: 40 DEG C

Eluent condition: 0-5min: oxolane /=50/50,20min: oxolane/water=100/0

Flow velocity: 1.0ml/min

Injection rate: 2 μ l

¹H-NMR measurement result compound 4

M.p. (compound 4): 176 DEG C

LC/MS measurement result

Compound 4 (13.1min): (exact mass) 640

(just) 663 [M+Na]⁺、679[M+K]⁺, (bearing) 639 [M-H]^-

Compound 5 (14.2min): (exact mass) 818

(just) 841 [M+Na]⁺、875[M+K]⁺, (bearing) 817 [M-H]^-

It should be noted that LC-MS condition determination is implemented under the following conditions.

LC system: Agilent 1200

Post: Inertsil ODS-3 5 μm 4.6 × 150mm No.2EI85047

Temperature: 40 DEG C

Eluent condition: 0-5min: oxolane /=50/50,20min: oxolane/water=100/0

Flow velocity: 1.0ml/min

Injection rate: 0.2 μ l

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 condition: SG=12L/min, ST=300 DEG C, NV=1000

[synthesis example of polymer]

Will be containing double { [9-(2-ethoxycarbonylethyl group) fluorenes-9-base]-methyl } fluorenes (compound 3) 0.05 mass parts Double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] methane (compound 2) 26.44 mass parts (0.0489 of (0.0001 mole) Mole), CHDM 10.37 mass parts (0.072 mole) and the tetra-n-butyl titanate 14.65 × 10 as catalyst^-3Mass parts (4.30×10^-5Mole) put in reaction vessel, in a nitrogen atmosphere, react 120 minutes at ambient pressure in 220 DEG C.It follows that Utilize 30 minutes by pressure to 13.3kPa, keep 30 minutes at 13.3kPa, the ethanol of generation be retracted to reaction vessel Outward.Thereafter, reactant liquor is temporarily cooled to room temperature (20 DEG C), by ISB 31.43 mass parts (0.215 mole), DPC51.66 matter Amount part (0.241 mole) puts in identical reaction vessel, and in a nitrogen atmosphere, making heating tank temperature is 150 DEG C and according to need It is stirred, makes material dissolution (about 10 minutes) simultaneously.After dissolving, as the operation of reaction the 1st step, utilize intensification in 30 minutes To 220 DEG C, reaction 60 minutes at ambient pressure.Next utilize 90 minutes make pressure from atmospheric depressurized to 13.3kPa, with 13.3kPa keeps 30 minutes, is retracted to outside reaction vessel by the phenol of generation.

It follows that as the operation of reaction the 2nd step, utilize the temperature of heating tank was warming up to 240 DEG C in 15 minutes, profit simultaneously With 15 minutes by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction vessel.Arrive the moment of torsion of regulation After, terminate reaction, the polymer of generation is expressed in water, obtains the granule of polycarbonate resin.

Obtained by the glass transition temperature etc. of resin combination, the refraction of stretched film when carrying out film molding and stretch Rate anisotropy, phase contrast ratio (Re450/Re550), the measurement result such as toughness of film are listed in table 3.

Will be containing double { [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base]-methyl } fluorenes (compound 5) 0.1 mass parts (0.0458 rubs methane (compound 4) 29.5 mass parts double [9-(the 2-phenyloxycarbonyl ethyl) fluorenes-9-base] 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 as the calcium acetate monohydrate 9.91 × 10 of catalyst^-4Mass parts (5.63 × 10^-6Mole) put into reaction vessel In, in a nitrogen atmosphere, make heating tank temperature be 150 DEG C and be stirred as required, make material dissolution (about 10 points simultaneously Clock).After dissolving, as the operation of reaction the 1st step, utilize 30 minutes and be warming up to 220 DEG C, at ambient pressure reaction 60 minutes.Connect down Utilize 90 minutes and make pressure from atmospheric depressurized to 13.3kPa, keep 15 minutes with 13.3kPa, the phenol of generation is retracted to Outside reaction vessel.

It follows that as the operation of reaction the 2nd step, utilize the temperature of heating tank was warming up to 245 DEG C in 15 minutes, profit simultaneously With 15 minutes by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction vessel.Arrive the moment of torsion of regulation After, terminate reaction, the polymer of generation is expressed in water, obtains the granule of polyestercarbonate.

Double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] methane (compound 2) 22.65 mass parts (0.042mol) 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) put into reaction vessel, in a nitrogen atmosphere, react 120 minutes at ambient pressure in 220 DEG C.30 minutes will it follows that utilize Pressure, to 13.3kPa, keeps 30 minutes with 13.3kPa, is retracted to outside reaction vessel by the ethanol of generation.Thereafter, will be anti- Answer liquid to be temporarily 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 be 150 DEG C and be stirred as required, make raw material simultaneously Dissolve (about 10 minutes).After dissolving, as the operation of reaction the 1st step, utilize within 30 minutes, be warming up to 220 DEG C, react at ambient pressure 60 minutes.Next utilize 90 minutes and make pressure from atmospheric depressurized to 13.3kPa, keep 30 minutes with 13.3kPa, by produce Phenol is retracted to outside reaction vessel.

It follows that as the operation of reaction the 2nd step, utilize the temperature of heating tank was warming up to 240 DEG C in 15 minutes, profit simultaneously With 15 minutes by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction vessel.Arrive the moment of torsion of regulation After, terminate reaction, the polymer of generation is expressed in water, obtains the granule of polyestercarbonate resins.

By double for 9,9-(4-(2-hydroxyl-oxethyl) phenyl) fluorenes (BHEPF) 62.40 mass parts (0.142mol), 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) putting into reaction vessel, in a nitrogen atmosphere, making heating tank temperature is 150 DEG C and according to need It is stirred, makes material dissolution (about 10 minutes) simultaneously.After dissolving, as the operation of reaction the 1st step, utilize intensification in 30 minutes To 220 DEG C, reaction 60 minutes at ambient pressure.Next utilize 90 minutes make pressure from atmospheric depressurized to 13.3kPa, with 13.3kPa keeps 30 minutes, is retracted to outside reaction vessel by the phenol of generation.

It follows that as the operation of reaction the 2nd step, utilize the temperature of heating tank was warming up to 240 DEG C in 15 minutes, profit simultaneously With 15 minutes by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction vessel.Arrive the moment of torsion of regulation After, terminate reaction, the polymer of generation is expressed in water, obtains the granule of Merlon.

[table 3]

Table 3

The relation of chemical constitution Yu optical characteristics in order to study low polyfluorene, as follows to the repetition deriving from low polyfluorene monomer The energy of the specific conformation (configuration) of unit carries out calculating and calculating fluorenes ring in this conformation with main chain angulation.

About software, AM1 method uses the PC Spartan Pro 1.0.5 that Wavefunction society of the U.S. manufactures (32 versions of Windows (registered trade mark)).It should be noted that the input value focusing on decision content etc. relevant to computational accuracy is complete Portion uses the default value of this software.

About derive from following shown in compound 3, the structure of compound 2 calculated.Herein, about as diester The compound 3 of monomer, compound 2, it is assumed that for the resin carrying out being polymerized by ester exchange reaction, for carrying out methyl by two ester groups The structure of esterification calculates.

As follows, it is 180 ° (i.e. side chain is transoid conformation) and be by dihedral angle formed by following keyed jointing A and keyed jointing B 60 ° and-60 ° (i.e. side chain is the gauche conformation of two kinds), as nascent structure, obtain balanced structure and its energy by AM1 method (generating heat), this keyed jointing A is the keyed jointing between 9 carbon atoms of fluorenes with the carbon atom being bonded with fluorenes in adjacent fluorenes side, and this keyed jointing B is The atom of the side chain being bonded with fluorenes is with the interatomic keyed jointing with the main chain of this atomic linkage.Herein, by the tool in each compound The substituent group with the methyl ester of 9 carbon atom bondings of fluorenes is had to be referred to as side chain.Herein, in order in the polymer to each repetitive Stereochemical structure speculates, makes the both of which of 2 side chains present in each compound be changed.That is, the transoid conformation in table 4 Referring to the structure that both of 2 side chains present in each monomer are transoid conformation, gauche conformation refers to present in each monomer 2 The structure that both are gauche conformation of side chain.Additionally, gauche conformation has 60 ° and-60 ° two kinds, for both 2 side chains it is 60 ° calculate with-60 ° of both of these cases.

Now, calculate present in each monomer 2 side chains both for transoid conformation and be the structure of two kinds of gauche conformations As the energy difference of isomer, most stable of conformation in these 3 kinds of conformations is set to 0 (kJ/mol), by energy difference (kJ/ now Mol) table 4 it is recorded in.It addition, in the case of energy difference is more than 4kJ/mol, energy (generating heat) low conformation (is set to 0 (kJ/mol) conformation) as Stable conformation.About the reasonability of the result of the AM1 method in this calculating, in Japan's Patent In No. 2013-214986, it is thus identified that with the calculating B3LYP/6-31G of higher degree^*Method demonstrates same tendency.

It addition, about transoid conformation and two kinds of gauche conformations, calculate main chain and fluorenes ring angulation and record.

It should be noted that main chain such as gets off to determine with fluorenes ring angulation.First, by the methine carbon atom of two ends The straight line being connected to each other as main chain direction, using by the plane of the 3 of fluorenes, 6,9 carbon atoms as fluorenes plane.This Time, the straight line in fluorenes plane intersected with main chain direction infinitely exists, but is in minimum fluorenes plane with the angle in main chain direction Straight line be well-determined.Using this angle as main chain and fluorenes ring angulation.Herein, due to compound 3 in the molecule There are 3 fluorenyls, therefore, use the fluorenes ring at center to calculate main chain and fluorenes ring angulation.

[changing 143]

[table 4]

Table 4

In table 4 compound 3 and compound 2 are compared, be all that the energy (generating heat) of transoid conformation is twisted with 2 kinds Difference is equal, or trans body is the most stable for the energy (generating heat) of conformation.

In the comparison of compound 3 and compound 2, about main chain and the fluorenes ring angulation of transoid conformation, there are 3 The compound 3 of fluorenyl is 84.2 °, and the compound 2 with 2 fluorenyls is 74.6 °, and compound 3 demonstrates the value close to 90 °.

The inventors discovered that, by make fluorenes ring in resin combination orthogonal relative to main chain, thus show its optics Characteristic.Additionally, confirm in Japan's Patent 2013-214986: the main chain in the Stable conformation obtained by calculating with Fluorenes ring angulation is relevant with the difference spectra that polarisation ATR analyzes and inverse wave length dispersing characteristic, the angle obtained by calculating Closer to 90 °, then the difference spectra that the polarisation ATR observed analyzes is the biggest, can obtain the strongest inverse wave length dispersing characteristic.Trans When the angle of conformation is more than 50 °, preferably more than 60 °, more preferably more than 70 °, particularly preferably more than 80 °, show Inverse wave length dispersibility, can predict that used repetitive structure all shows inverse wave length dispersibility.

According to reference example 2-1 and the comparison of reference example 2-2, assume that the phase retardation film demonstrating inverse wave length dispersibility is used In the case of Tu, in order to show identical phase contrast ratio (Re450/Re550) 0.90, use the reference example 2-1 of two fluorenes diester (polyestercarbonate) with use BHEPF reference example 2-2 (Merlon) compared with, containing fluorenes ring monomer much less, thus it can be said that The effect showing inverse wave length dispersibility when using compound 2 compared with during use BHEPF is high.This is presumably because, two fluorenes two The compound 2 of ester fluorenes ratio compared with BHEPF is high, and, compared with BHEPF, the ratio of alkylidene chain soft in compound 2 Low, thus upright and outspoken, so fluorenes ring is the state kept straight on easily with respect to main chain.

Thinking according to analog result, about compound 2, transoid conformation is equal or trans with the stability of gauche conformation Conformation is the most stable, and on the other hand, about compound 3, transoid conformation is stable, and it is high that it exists ratio.Additionally, in compound 3 and change In the respective transoid conformation of compound 2, main chain and fluorenes ring angulation are more than 70 °, can predict and show high head sea Long dispersibility.Additionally, in compound 3, main chain and fluorenes ring angulation are more than 80 °, it is believed that show compound more than 2 Inverse wave length dispersibility, it is thus regarded that so that the inverse wave length dispersion equal with compound 2 can be shown less than the consumption of compound 2 Property.

It addition, compound 3 fusing point compared with compound 2 is high more than 20 DEG C, decompose initial temperature the highest, thus assume that make Glass transition temperature during resin is higher than the resin using compound 2, it is believed that heat stability is the highest.

Arrange in table 5 and the chemical structural formula of the repetitive containing fluorenes ring monomer source of synthesis in synthesis example 2-1 is shown 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 The form of atom (not including hydrogen atom) carries out calculating.

Molecular weight × 100 of the molecular weight/repetitive 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, can show desired efficiently Optical characteristics, the fluorenes ratio of compound 2, compound 3, compound 4 and compound 5 is more than 70%, it is taken as that use The resin combination of their present invention is suitable to show desired optical characteristics efficiently.On the other hand, the feelings of BHEPF Under condition, the fluorenes ratio in the repetitive in its source, less than 50%, is not to have for showing desired optical characteristics Effect, in order to show desired optical characteristics, it is believed that needs to improve the use ratio of the monomer with fluorenes.

According to foregoing, in the case of being assumed to demonstrate the phase retardation film purposes of inverse wave length dispersibility, containing tool The resin combination having the polymer of three fluorene repeat units of the present invention demonstrates in the case of a small amount of use three fluorenes diester The various physical property such as thermostability, the most intrinsic birefringence, phase contrast ratio can be realized.

" embodiment 3-1 "

The shorthand notations of the compound used in following embodiment etc. are as follows.

ISB；Isosorbide (Roquette Freres society manufacture, trade name: POLYSORB)

DPC；Diphenyl carbonate (Mitsubishi chemical Co., Ltd's manufacture)

CHDM；1,4 cyclohexane dimethanol (cis, trans mixture, society of SK Chemical manufacture)

THF: oxolane (manufactures without stabilizer, WAKO society)

[embodiment of monomer]

<embodiment 3-1>9-{ [(2-ethoxycarbonylethyl group) fluorenes-9-base]-methyl } synthesis of fluorenes (compound 2)

[changing 144]

The synthesis of<synthesis example 3-1A>double (fluorenes-9-base) methane (compound 1)

In 1L four-hole boiling flask, load fluorenes (120g, 722mmol), DMF (480ml), carry out nitrogen and put Less than 5 DEG C it are cooled to after changing.Add Sodium ethylate (24.6g, 361mmol), add on a small quantity several times, every time paraformaldehyde (8.7g, 289mmol) so that temperature is less than 10 DEG C, it is stirred.After 2 hours, dropping 1N hydrochloric acid (440ml), stopped reaction.To gained To aaerosol solution carry out sucking filtration, utilize deionized water (240ml) to carry out drip washing.Thereafter, obtained thick product is made to disperse In deionized water (240ml), carry out stirring in 1 hour.After this suspension is carried out sucking filtration, deionized water (120ml) is utilized to enter Row drip washing.After making obtained thick product be dispersed in toluene (480ml), Dean-Stark apparatus is utilized to be heated to reflux Under the conditions of be dehydrated.Recover to room temperature (20 DEG C), carry out sucking filtration, at 80 DEG C of drying under reduced pressure until reaching constant, thus To double (fluorenes-9-base) methane (compound 1) 84.0g (yield: 84.5%, HPLC purity: 94.0%) as white solid.

<synthesis example 3-1B-1>9-{ [(2-ethoxycarbonylethyl group) fluorenes-9-base]-methyl } synthesis of fluorenes (compound 2)

The removable flask of 1L loads in synthesis example 3-1A obtain double (fluorenes-9-base) methane (compound 1,34.0g, 98.7mmol), N-benzyl-N, N, N-triethyl ammonium chloride (4.47g, 19.6mmol), oxolane (170ml), carry out nitrogen After displacement, interior temperature control is made as 15 DEG C～18 DEG C, adds 50wt/wt% sodium hydrate aqueous solution (25.93g), afterwards solution Color becomes light yellow.Thereafter, utilize dropping ethyl acrylate (10.7ml, 103mmol) in 30 minutes, utilize HPLC to carry out afterwards Analyze.

(HPLC condition)

Post: Inertsil ODS-3V 150mm × 4.8mm φ

Temperature: 40 DEG C

Eluent condition: 0～5min: oxolane/water=50/50,20min: oxolane/water=100/0

Flow velocity: 1.0ml/min

Injection rate: 2 μ L

(HPLC analysis result)

Compound 1 (13.9min): 15 area %, compound 2 (13.1min): 61 area %, compound 3 (13.5min): 15 area %

<synthesis example 3-1B-2>9-{ [(2-ethoxycarbonylethyl group) fluorenes-9-base]-methyl } fluorenes (compound 2)

In 50mL there-necked flask add compound 1 (1.0g, 2.9mmol), benzyltriethylammoinium chloride (132mg, 0.58mmol), THF (5mL), be stirred in room temperature in a nitrogen atmosphere.Utilize 30 minutes add ethyl acrylate (290mg, After 2.9mmol), in room temperature curing 3 hours.After 16 DEG C of ripenings 1 hour, 3N hydrochloric acid is utilized to be neutralized.Hitherward add first Benzene (5mL), cleans 1 toluene phase with saturated sodium bicarbonate aqueous solution (5mL), cleans 3 toluene phases with water (5mL).Utilize and steam Sending out after toluene distillation removes by device, residue silica gel chromatography refines, obtain compound 2 (0.63g, 1.4mmol, yield: 49%, 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 in the case of raw material addition 1 equivalent ethyl acrylate, third When the speed of the additive reaction of olefin(e) acid ethyl ester is identical in first addition with second addition, in theory should be according to compound 1: compound 2: the mode that ratio is 1:2:1 of compound 3 generates.However, surprisingly it was that, the area of HPLC in the present reaction Ratio is 1:4:1, it is known that be selectively generating the compound 2 singly adding adult.It is thought that because, for compound 3,2 The structure that individual fluorenes ring is piled up is rock-steady structure, on the other hand, for compound 1 and compound 2,2 fluorenes ring reversions Structure is rock-steady structure, thus during to the 2nd ethyl acrylate of compound 2 addition, needs a fluorenes ring reversion to add Become.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 of compound 3 source is observed in the side, highfield of δ 6.77-7.03ppm, it was observed that be strong The impact of strong screening effect, this also supports fluorenes ring and takes packed structures.

Generally have at 2 in the case of substituent group imported parts, be sometimes difficult to the most only import at 1 reactivity Functional group, but in the case of specific Oligofluorenylene compounds, due to three-dimensional reactive equal, having can easy selectivity Ground only imports the tendency of specific reactive functional groups at 1, it is believed that industrially can also manufacture.

It addition, for the Oligofluorenylene compounds of compound 1 etc, additive reaction or substitution reaction import reactivity and take In the case of Dai Ji, it is believed that there is tendency equally that can be selectively generating the low polyfluorene with 1 reactive functional groups, because of And think and can also be widely used in beyond ethyl acrylate.

Such as, about the monoesters body of compound 2 etc, it is believed that by using as the raw material of polyester or polyestercarbonate, Thus as end terminator generation effect, it is taken as that the molecular weight regulator as polyester or Merlon is useful.

Such as, about the monoesters body of compound 2 etc, importing hydroxyl is as reactive substituents further, such that it is able to Synthesis has the Oligofluorenylene compounds of 2 different reactive functional groups, and only this i.e. can get the polyester that fluorenes content is high, thus recognizes For being useful.

" embodiment 4-1～4-4, comparative example 4-1～4-2 "

The quality evaluation of the low polyfluorene monomer of the present invention and the evaluating characteristics of resin combination and hyaline membrane are by following Method is carried out.It should be noted that evaluating characteristics maneuver is not limited to following method, those skilled in the art can suitably select Select.

ISB: isosorbide (Roquette Freres society manufacture, trade name: POLYSORB)

DPC: diphenyl carbonate (Mitsubishi chemical Co., Ltd's manufacture)

(1) powder X-ray diffraction of low polyfluorene diester

The x-ray diffractogram of powder spectrum of low polyfluorene diester utilizes powder X-ray diffraction determinator (Spectris PANalitical division department X-Pert ' Pro) it is measured.

(2) particle size distribution of low polyfluorene diester

About the particle size distribution of low polyfluorene diester, use laser diffraction and scattering formula particle size distribution analyzer (MicrotracBEL society manufactures MT3300EX), is scattered in solvent methanol and is measured.

(3) the rotation angle of repose of low polyfluorene diester

About the rotation angle of repose of low polyfluorene diester, use Three-wheel type determinator angle of repose (cylinder well Physicochemical apparatus society system Make), it is measured by cylinder circumgyration.

(4) Evaluation of Thermal Stability of low polyfluorene diester

Low polyfluorene diester 500mg is added in 30mL flask, carries out stirring in 7 hours in 185 DEG C in a nitrogen atmosphere.Logical Cross the tone visually confirmed before and after heating.It addition, the 1wt%THF solution of the low polyfluorene diester before and after preparation heating, use purple Outer visible absorbance spectrophotometer (society of Shimadzu Seisakusho Ltd. manufactures UV-1650PC) determines the absorbance of the wavelength of 400nm.

[changing 145]

The synthesis of<embodiment 4-1A>double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] methane (compound 2)

Double (fluorenes-9-base) methane (50g, 145.2mmol), benzyltriethylammoinium chloride is loaded in the removable flask of 1L (6.6g, 29.0mmol), oxolane (250mL), after carrying out nitrogen displacement, utilizing water-bath to control is 17 DEG C～19 DEG C, adds 50wt/vol% sodium hydrate aqueous solution (26.5mL), the color of result solution becomes pale red.Thereafter dropping in 30 minutes is utilized Ethyl acrylate (15.1mL, 145.2mmol).Thereafter, benzyltriethylammoinium chloride (6.6g, 29.0mmol) is added, further Add ethyl acrylate (30.2mL, 290.2mmol), with the carrying out of HPLC following response, while stirring 2 hours.Logical Cross HPLC to confirm and singly add after adult is less than 2%, utilize ice bath to cool down, control temperature dropping 3N hydrochloric acid (166.4mL), it is quenched.After discarded for water layer, add toluene 100mL, clean with saturated sodium bicarbonate aqueous solution (150mL) After organic layer, clean organic layer with deionized water (150mL) further.Thereafter, after decompression is distilled off oxolane, add first Alcohol (200mL), carries out crystallize.After sucking filtration, at 100 DEG C of drying under reduced pressure to reaching constant, thus obtain as white solid double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] methane (compound 1) 61.9g (yield: 78.0%, HPLC purity: 87.4 Long-pending %).

Post: Inertsil ODS-3V 150mm × 4.8mm φ

Temperature: 40 DEG C

Eluent condition: 0-5min: oxolane/water=50/50,20min: oxolane/water=100/0

Flow velocity: 1.0mL/min

Injection rate: 2 μ L

HPLC analysis result 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 trace is represented in ().

M.p.:141 DEG C

The synthesis of<embodiment 4-1B>double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2)

1L four-hole boiling flask loads double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] methane (compound 1,49.7g, 91.2mmol), diphenyl carbonate (98.3g, 459mmol), original four-isopropyl titanate (1.3mL, 4.59mmol), by vacuum adjust Whole is 3～2kPa, and by-product is distilled off by the temperature range 140 DEG C～150 DEG C, carries out stirring in 10 hours simultaneously.Cooling To 90 DEG C, after confirming reaction terminating by HPLC, add toluene (100mL), be cooled to 50 DEG C.It is added thereto to methanol (250mL) sucking filtration is carried out after, being cooled to room temperature.Make obtained white solid be dispersed in toluene (100mL), be heated to reflux 30 Minute.After being cooled to 50 DEG C, add methanol (250mL).After being cooled to room temperature (20 DEG C), carry out sucking filtration, at 100 DEG C of drying under reduced pressure To reaching constant, thus obtain double [9-(the 2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2) as white solid 35.2g (yield: 60%, HPLC purity: 98.4 area %).

M.p.:176 DEG C

Ti content ratio: 330 mass ppm

The synthesis of<embodiment 4-2>double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2)

In 250L GL reactor, add diphenyl carbonate (74.9 mass parts), make it dissolve at 120 DEG C.Add wherein Enter double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] methane (compound 1,38.1 mass parts), original four-isopropyl titanate (1.0 Mass parts), vacuum is adjusted to 3.0kPa, by-product is distilled off, stirring reaches 185 DEG C to interior temperature in 7 hours simultaneously. After recovering normal pressure with nitrogen, it is cooled to 90 DEG C, after confirming reaction terminating by HPLC, adds toluene (66 mass parts), conveying To 400L GL reactor, it is cooled to 50 DEG C.It is added thereto to methanol (151 mass parts), after being cooled to 5 DEG C, was centrifuged Filter.Make obtained thick product be dispersed in toluene (66 mass parts), be heated to reflux 30 minutes.After being cooled to 50 DEG C, add Methanol (151 mass parts), after being cooled to 22 DEG C, is centrifuged filtering.Obtained thick product is made to be dispersed in toluene further In (66 mass parts), it is heated to reflux 30 minutes.After being cooled to 50 DEG C, add methanol (151 mass parts), after being cooled to 22 DEG C, enter Row centrifugal filtration.At 80 DEG C of drying under reduced pressure until reaching constant, thus obtain double [9-(the 2-phenoxy group carbonyls as white solid Base ethyl) fluorenes-9-base] methane (compound 2) 27.2g (yield: 61%, HPLC purity: 99.5 area %).

Ti content ratio: 40 mass ppm

The synthesis of<embodiment 4-3>double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2)

Double [9-(the 2-phenyloxycarbonyl ethyl) fluorenes-9-base] obtained in embodiment 4-2 is added in the removable flask of 1L Methane (compound 2,60g), toluene (120mL), be warming up to 80 DEG C make it dissolve after, add deionized water (180mL), carry out 30 After minute stirring, by the separatory discarded water layer of operation.Again add deionized water (180mL), after carrying out stirring in 30 minutes, pass through After the discarded water layer of separatory operation, organic layer is carried out pressure filtration (0.2MPa, ADVANTEC PTFE film filter, aperture 0.5 μ M:H050A47A), organic layer is added in the removable flask of 1L, stir and be cooled to 40 DEG C.It is added thereto to methanol (300mL) sucking filtration is carried out after, being cooled to 22 DEG C.At 80 DEG C of drying under reduced pressure until reaching constant, thus obtain as white solid Double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2) 54.1g (yield: 90%).

Ti content ratio: < 0.1 mass ppm

Double [9-(the 2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2,61.7g) that will obtain in embodiment 4-2 It is dissolved in chloroform, utilizes silica gel column chromatography (eluent: chloroform) to refine.For obtained chloroformic solution, utilize and steam Send out device decompression and chloroform is distilled off, add MeOH (300mL).After being cooled to room temperature (20 DEG C), carry out sucking filtration, dry 80 DEG C of decompressions Dry until reaching constant, thus obtain double [9-(the 2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (chemical combination as white solid Thing 2) 59.8g (yield: 97%, HPLC purity: 99.5 area %).

Ti content ratio: < 0.1 mass ppm

The synthesis of<comparative example 4-1>double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2)

500mL four-hole boiling flask loads double [9-(2-ethoxycarbonylethyl group) fluorenes-9-base] methane (compound 1, 35.0g, 64.3mmol), diphenyl carbonate (68.8g, 321mmol), original four-isopropyl titanate (0.95mL, 3.24mmol), will Vacuum is adjusted to 2.8kPa～3.2kPa, and by-product is distilled off by the temperature range 135 DEG C～150 DEG C, carries out 6 simultaneously Hour stirring.It is cooled to 90 DEG C, after confirming reaction terminating by HPLC, adds toluene (70mL), be cooled to 50 DEG C.Wherein Add methanol (175mL), after being cooled to 5 DEG C, carry out sucking filtration.Make obtained white solid be dispersed in toluene (70mL), add Hot reflux 30 minutes.After being cooled to 50 DEG C, add methanol (175mL).After being cooled to room temperature (20 DEG C), carry out sucking filtration, at 80 DEG C Drying under reduced pressure is until reaching constant, thus obtains double [9-(the 2-phenyloxycarbonyl ethyl) fluorenes-9-base] first as white solid Alkane (compound 2) 32.2g (yield: 78%, HPLC purity: 99.0 area %).

Ti content ratio: 770 mass ppm

[changing 146]

The synthesis of<comparative example 4-2A>double [9-(2-dion e) fluorenes-9-base] methane (compound 3)

Double (fluorenes-9-base) methane (10.01g, 29.06mmol), N-benzyl-N, N, N-is loaded in 200mL four-hole boiling flask Triethyl ammonium chloride (1.32g, 5.78mmol), oxolane (50mL), after carrying out nitrogen displacement, utilize water-bath to control at 15 DEG C ～20 DEG C, after adding 50% sodium hydrate aqueous solution (8ml), the color of solution becomes light red.Thereafter utilize ice bath by interior temperature Control at 17 DEG C～18 DEG C, utilize dropping acrylic acid methyl ester. (7.8mL, 86mmol) in 3 hours.While entering with HPLC following response OK, stirring 3 hours, utilize ice bath to cool down afterwards, in controlling, temperature is less than 18 DEG C while dripping 3N hydrochloric acid (22mL), it is quenched.Toluene (20mL) is added in the organic layer that separatory obtains, after utilizing deionized water to be carried out, will Solvent under reduced pressure is distilled off, and concentrates.Make concentrated solution recover to room temperature (20 DEG C), add methanol (40mL) and carry out crystallize.Take out After filter, at 80 DEG C of drying under reduced pressure until reaching constant, thus obtain the double [9-(2-dion e) as white solid Fluorenes-9-base] methane (compound 3) 7.05g (yield: 47.0%, HPLC purity: 80.0 area %).

Post: Inertsil ODS-3V 150mm × 4.8mm φ

Temperature: 40 DEG C

Eluent condition: 0-5min: oxolane/water=50/50,20min: oxolane/water=100/0

Flow velocity: 1.0ml/min

Injection rate: 2 μ L

HPLC analysis result compound 4 (5.9min): 12.8 area % (12.8 mass %), compound 6 (detection): not Detection, compound 3 (11.8min): 80.0 area % (84.6 mass %)

The quantitative values calculated by calibration trace is 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).

The synthesis of<comparative example 4-2B>double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2)

50mL there-necked flask loads double [9-(2-dion e) fluorenes-9-base] methane (compound 3,6.0g, 11.6mmol), diphenyl carbonate (12.1g, 56.6mmol), original four-isopropyl titanate (0.16mL, 0.55mmol), be warming up to 145 DEG C, carry out stirring in 1 hour.Confirm to react by HPLC and do not carry out, add original four-isopropyl titanate the most further (0.32mL, 1.1mmol), carries out HPLC analysis again after 1 hour, the disappearance of results verification to the peak of compound 4 and reaction Carry out, stir 1 hour at 145 DEG C the most further.After confirming reaction terminating by HPLC, add toluene (15ml), heating Reflux 1 hour.After being cooled to 50 DEG C, add methanol (18mL).After being cooled to room temperature (20 DEG C), carry out sucking filtration.Make obtained White solid is dispersed in toluene (12mL), is heated to reflux 1 hour.After being cooled to 50 DEG C, add methanol (18mL).It is cooled to room After temperature (20 DEG C), carry out sucking filtration, at 100 DEG C of drying under reduced pressure to reaching constant, thus obtain the double [9-(2-as white solid Phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2) 5.39g (yield: 64%, HPLC purity: 98.1 area %).

Ti content ratio: 3300 mass ppm

At enamel 12m³In reactor will double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2, 1201 mass parts) 32.7wt% o-xylene solution lower the temperature at leisure from 86 DEG C, arrive 60 DEG C moment add methanol (551 mass parts), and then add crystal seed in the moment arriving 55 DEG C, make crystallization.Thereafter, utilize within 5 hours, be cooled to 40 DEG C, Utilize within 1 hour, add methanol (3548 mass parts), and then utilize 5 hours to be cooled to 21 DEG C.It is divided into 10 batches by centrifugal filtration To crystallization, utilize cone drier to be divided into 2 batches and be dried to reaching constant at 80 DEG C, thus obtain the double [9-as white solid (2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2) 1125 mass parts (response rate: 94%, HPLC purity: 99.8 Long-pending %).

Mean diameter: 178 μm, 50 μm above particle-size accumulation %:99%

Rotate angle of repose: 55 °

X-ray diffractogram of powder compose: 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°

At enamel 12m³In reactor will double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2, 1224 mass parts) 32.0wt% o-xylene solution lower the temperature at leisure from 81 DEG C, arrive 68 DEG C moment add crystal seed.Its After be cooled to 49 DEG C, utilize within 1 hour, add methanol (4579 mass parts), be cooled to 21 DEG C further with 5 hours, by centrifugal Filtration is divided into 6 batches and is crystallized, and utilizes cone drier to be divided into 2 batches and is dried to reaching constant at 80 DEG C, thus obtains as in vain Double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2) 1043 mass parts (response rate: 85%, of color solid HPLC purity: 99.8 area %).

Mean diameter: 44 μm, 50 μm above particle-size accumulation %:30%

Rotate angle of repose: 62 °

To enamel 1m³After reactor carries out nitrogen displacement, add double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] first Alkane (compound 2,250 mass parts), o-Dimethylbenzene (450 mass parts), be warming up to more than 100 DEG C and make it dissolve.Thereafter it is cooled to 80 DEG C, after adding crystal seed, it is cooled to 20 DEG C with 1 hour with the rate of cooling of 10 DEG C, starts centrifugal filtration.

It is centrifuged for 1st time and can successfully filter, but the gradually micronization of the crystallization in reactor, thus slurry character is sharp It is deteriorated, can filter being centrifuged to the 3rd time, but extract out afterwards and become difficulty, interrupted centrifugal filtration.Obtained by the 3rd Secondary centrifugal till material be dried to reaching constant at 80 DEG C, thus obtain double [9-(the 2-phenyloxycarbonyl as white solid Ethyl) fluorenes-9-base] methane (compound 2) 63.2 mass parts (response rate: 25%).

It is centrifuged for 1st time

X-ray diffractogram of powder compose: 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°

Mean diameter: 220 μm, 50 μm above particle-size accumulation %:88%

It is centrifuged for 3rd time

Mean diameter: 25 μm, 50 μm above particle-size accumulation %:5%

Embodiment 4-1 and embodiment 4-2 are compared, it is known that: by increasing the crystallize number of times of toluene and methanol, target The Ti content of oligomeric fluorene diaryl ester (compound 2) reduces to 40ppm from 330ppm.It addition, to embodiment 4-1 and comparative example In the comparative example 4-1 that 4-1 compares, it is known that: by making toluene and methanol recrystallization temperature be reduced to 5 DEG C from room temperature, thus yield It is improved as 78% from 60%, but the remaining quantity of Ti is significantly deteriorated as 770ppm from 330ppm.It addition, in comparative example 4-2, make In order to contain the raw material of low polyfluorene dicarboxylic acids more than the ratio of 10 mass % in the case of, the ester exchange reaction of ormal weight is utilized to urge Agent cannot make reaction carry out, and needs to add catalyst for ester exchange reaction.It is thought that because, low polyfluorene dicarboxylic acids and ester exchange The Ti compound of catalysts forms complex, so that its inactivation.Thus, it can be known that obtained oligomeric fluorene diaryl ester The Ti content of (compound 2) is significantly increased.In embodiment 4-3, the compound 2 obtained in embodiment 4-2 is implemented washing work Sequence and pressure filtration, in embodiment 4-4, refine the compound silica gel column chromatography obtained in embodiment 4-2, thus Ti content can be reduced to detection limit.Particularly, the cost ratio of the process for purification of washing step and pressure filtration is utilized Relatively low, industrially can also implement, thus can be described as the process for purification of excellence.

The Ti content illustrated in the low polyfluorene diester of each embodiment and comparative example and Evaluation of Thermal Stability is arranged in table 6 Result.

[table 6]

Table 6

Then, tone variations based on the table 6 crystallization to adding under thermogenetic molten condition is discussed.Before heating Tone, embodiment 4-1 is the light yellow of yellowish, but embodiment 4-2, embodiment 4-3 and embodiment 4-4 is white Color.On the other hand, comparative example 4-1, comparative example 4-2 are coloured to yellow before heating.And then carried out 7 hours at 185 DEG C Heating, does not observes coloring in acetonideexample 4-3, embodiment 4-4, has obtained water white crystallization.Embodiment 4-2, reality Execute in example 4-1, comparative example 4-1 and comparative example 4-2 along with Ti content increases, it was observed that 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, changed the tone variations before and after heating by the absorbance of the 400nm of 1wt%THF solution Discuss.As shown in Figure 1, embodiment 4-2 (40ppm), embodiment 4-3 (< 0.1ppm), embodiment 4-4 (< 0.1ppm) are adding Before and after heat, the absorbance of THF solution does not sees change.At embodiment 4-1 (330ppm) and comparative example 4-1 (770ppm) Middle Ti content is about 2 times, but observes that its absorbance difference has the difference of nearly 4 times.Thus it has been confirmed that tone is produced by Ti content The biggest gap is there is in raw impact between the 330ppm and the 770ppm of comparative example 4-1 of embodiment 4-1.It addition, about 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.

Result above shows, the low polyfluorene diester of the application of the invention, even if tone variations is also few in the molten state, It is thus able to suppress the coloring through the producible resin combination of smelting process.

As in figure 2 it is shown, at 12m³Enamel reactor in carried out the reference example 4-1 and reference example 4-2 of crystallize and entered Row compares, and the mean diameter of crystallization obtained in reference example 4-2 is little, is 44 μm, and the rotation as powder fluidity index is stopped Only angle is 62 °, also shows that high level.On the other hand, by being added separately methanol in reference example 4-1, the mean diameter of crystallization becomes Greatly 178 μm, rotate and are also improved as 55 ° angle of repose.Result above shows, the knot that the mean diameter of the application of the invention is big Crystalline substance, even if using as resin raw material, feeding intake property is the most no problem.

Having carried out crystallize merely with the o-Dimethylbenzene as good solvent in reference example 4-3, result understands, and has obtained the 1st time Mean diameter after centrifugal drying is crystallization 220 μm, big and good, the character of pulp solution through time to be changed to viscosity high The suspension of thick soup shape, the mean diameter after the 3rd centrifugal drying is micronized to 25 μm.It addition, be centrifuged and flow afterwards for the 3rd time Property be deteriorated further, therefore the extraction from reactant liquor become difficulty, centrifugal filtration interrupt, by its re-dissolved.It 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 °, the peak of 19.1 °, do not observe this 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, along with phase transfer becomes to stablize shape at leisure, thus carries out micronization.

Good solvent at reference example 4-1 uses o-Dimethylbenzene, poor solvent to use in the case of methanol, do not observe 2 θ= , there is not micronization, thereby through good solvent in 5.6 °, 8.5 °, 11.0 °, 12.5 °, 12.9 °, 14.9 °, 16.3 °, the peak of 19.1 ° The aromatic hydrocarbon with o-Dimethylbenzene as representative, poor solvent is used to use the alcohol series solvent with methanol as representative, it is thus regarded that can The granule big to obtain mean diameter.

[synthesis example of polymer]

Double [9-(2-phenyloxycarbonyl ethyl) fluorenes-9-base] methane (compound 2) 26.63 mass parts (0.042 mole) 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 as the calcium acetate monohydrate 5.36 × 10 of catalyst^-4Mass parts (3.04 × 10^-6Mole) put into reaction vessel, Making heating tank temperature under nitrogen atmosphere is 150 DEG C, is stirred as required making material dissolution (about 10 minutes).Molten Xie Hou, as the operation of reaction the 1st step, utilizes 30 minutes and is warming up to 220 DEG C, at ambient pressure reaction 60 minutes.It follows that utilize 90 minutes by pressure from atmospheric depressurized to 13.3kPa, keep 30 minutes at 13.3kPa, the phenol of generation be retracted to reaction and hold Outside device.

It follows that as the operation of reaction the 2nd step, utilize the temperature of heating tank was warming up to 240 DEG C in 15 minutes, profit simultaneously With 15 minutes by pressure to below 0.10kPa, the phenol of generation is retracted to outside reaction vessel.Arrive the moment of torsion of regulation After, terminate reaction, the polymer of generation is expressed in water, obtains the granule of polyestercarbonate.

The refractive anisotrop of stretched film when obtained resin combination being carried out film molding and stretches, phase contrast It is listed in table 7 than measurement results such as (Re450/Re550).

By double for 9,9-(4-(2-hydroxyl-oxethyl) phenyl) fluorenes (BHEPF) 62.40 mass parts (0.142 mole), ISB28.78 mass parts (0.197 mole), DPC73.40 mass parts (0.343 mole) and magnesium acetate four water as catalyst Compound 7.28 × 10^-4Mass parts (3.39 × 10^-6Mole) put into reaction vessel, making heating tank temperature in a nitrogen atmosphere is 150 DEG C, it is stirred as required making material dissolution (about 10 minutes).After dissolving, as the operation of reaction the 1st step, profit It is warming up to 220 DEG C, at ambient pressure reaction 60 minutes with 30 minutes.It follows that utilize 90 minutes by pressure from atmospheric depressurized to 13.3kPa, keeps 30 minutes at 13.3kPa, is retracted to outside reaction vessel by the phenol of generation.

[table 7]

Table 7

As shown in Table 7, reference example 4-4 is used the polyestercarbonate of compound 2 and the use BHEPF of reference example 4-5 Merlon compare, in reference example 4-4, amount of monomer is less, phase contrast ratio (Re450/Re550) equal, thus it is shown that Strong inverse wave length dispersibility.Additionally, photoelastic coefficient is also the value of less than half.It can be said that, the low polyfluorene of the present invention Diester is the most excellent monomer.

With reference to particular implementation, the present invention is described in detail, but it will be understood by those skilled in the art that known Without departing from the spirit and scope of the present invention the present invention can be imposed various change, correction.The application is based on 2014 The Japan Patent that the Japanese patent application (Japanese Patent Application 2014-037216) that on February 27, in submits to, on March 19th, 2014 submit to The Japanese patent application (Japanese Patent Application 2014-078068) that application (Japanese Patent Application 2014-056873), on April 4th, 2014 submit to And the Japanese patent application (Japanese Patent Application 2014-084649) that on April 16th, 2014 submits to, with the form of reference by its content Introduce this specification.

Claims

1. a resin, it is the resin of the polycondensation system with the constitutional repeating unit comprising aromatic structure, the spy of this resin Levy and be,

This resin has at least one construction unit in the construction unit represented by following formula (1) and formula (2),

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 composition resin, unit is quality %,

The ratio R450/ of B: the stretched film the being formed from a resin phase contrast R450 at 450nm and the phase contrast R550 at 550nm 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 The alkylidene of 1～4,

R⁴～R⁹Be each independently hydrogen atom, with or without substituent group the alkyl that carbon number is 1～10, have or Not there is the aryl that carbon number is 4～10 of substituent group, with or without the acyl that carbon number is 1～10 of substituent group Base, the acyloxy that carbon number is 1～10 with or without substituent group, the carbon number with or without substituent group are The alkoxyl of 1～10, with or without the aryloxy group that carbon number is 1～10 of substituent group, with or without substituent group Amino, the vinyl that carbon number is 1～10 with or without substituent group, the carbon atom with or without substituent group Number is the acetenyl of 1～10, has the sulphur atom of substituent group, has the silicon atom of substituent group, halogen atom, nitro or cyano group；Its In, R⁴～R⁹In, at least 2 adjacent groups can be mutually bonded formation ring.

2. a resin, it is the resin of the polycondensation system with the constitutional repeating unit comprising aromatic structure, the spy of this resin Levy and be,

The content of the aromatic structure in this constitutional repeating unit meets following formula (III), and the glass transition temperature of this resin Degree is more than 110 DEG C less than 160 DEG C,

5≤A≤-22.5×B+34.8 (III)

Wherein, 0.75≤B≤0.93,

The ratio R450/ of B: the stretched film the being formed from a resin phase contrast R450 at 450nm and the phase contrast R550 at 550nm R550。

3. resin as claimed in claim 1 or 2, wherein, the refractive index at sodium d line (589nm) of this resin be 1.49～ 1.56。

4. the resin as according to any one of claims 1 to 3, wherein, the storage modulus of this resin is more than 1GPa 2.7GPa Below.

5. the resin as according to any one of Claims 1 to 4, wherein, this resin is measuring temperature 240 DEG C, shear rate 91.2sec^-1Under the conditions of melt viscosity be above below the 5000Pa s of 700Pa s.

6. the resin as according to any one of Claims 1 to 5, wherein, described resin is for selecting free Merlon, polyester, gathering At least one resin in the group of ester carbonic ester composition.

7. the resin as according to any one of claim 1～6, wherein, the aromatic series knot that described constitutional repeating unit is comprised Structure is only fluorenes.

8. the resin as according to any one of claim 1～7, wherein, this resin contains the structure list represented by following formula (3) Unit,

[changing 2]

9. a hyaline membrane, it contains the resin according to any one of claim 1～8.

10. a phase retardation film, it obtains by stretching the hyaline membrane described in claim 9 at least one direction Arrive.

11. phase retardation films as claimed in claim 10, wherein, this phase retardation film is made up of simple layer, and thickness is more than 10 μm Below 60 μm.