CN103709449B

CN103709449B - Cellulose ester film, polarizer and liquid crystal display device

Info

Publication number: CN103709449B
Application number: CN201310445603.8A
Authority: CN
Inventors: 稻田宽; 桑山靖和; 野吕正树; 深川伸隆
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2012-09-28
Filing date: 2013-09-26
Publication date: 2017-11-17
Anticipated expiration: 2033-09-26
Also published as: CN103709449A

Abstract

The present invention provides hardness height and the cellulose ester film of light excellent in te pins of durability.A kind of cellulose ester film, it contains following formulas（I）Shown compound.Formula（I）In, R¹、R²、R⁴~R⁷And R⁹~R¹¹Hydrogen atom or substituent, R are represented respectively³、R⁸Represent hydrogen atom or non-conjugated substituent, X¹And X²Respectively singly-bound or aliphatic linker, L represent singly-bound, N（R¹²）Or C（R¹³）（R¹⁴）, R¹²~R¹⁴Hydrogen atom or substituent are represented respectively.

Description

Cellulose ester film, polarizer and liquid crystal display device

Technical field

The present invention relates to cellulose ester film, polarizer and liquid crystal display device.Protected more particularly to as polarizer Film and useful cellulose ester film and its polarizer and the liquid crystal display device with above-mentioned polarizer are used.

Background technology

In recent years, centered on TV purposes, the maximization and slimming of liquid crystal display device continue to develop, and are accompanied by this, Optical compensating film as component parts（Protective film）Also must be thinned.All the time, for optical compensating film, from From the viewpoint of processability, appropriate hardness, good severing are also constantly subjected to pay attention to, but due to slimming, especially Ask the raising of these performances.

In order to solve the above problems, carry out adding U.S. Patent No. into cellulose acylate film all the time No. 2824017, U.S. Patent No. 2824016, U.S. Patent No. 2824018 and Japanese Unexamined Patent Publication 2003-012823 publications Described in as method of the compound as additive.

The content of the invention

Invent problem to be solved

Present inventor is studied above-mentioned document, is as a result known, because U.S. Patent No. 2824017, the U.S. are special Compound described in profit the 2824016th, U.S. Patent No. 2824018 and Japanese Unexamined Patent Publication 2003-012823 publications is made Played a role for so-called plasticizer, so cannot get sufficient hardness, and then, due in the wavelength zone for decomposing reaction Have in domain and absorb, so light durability has problem.Here light durability, can be included by light irradiation in protective film Decompose reaction and make film deterioration, become to be easily peeled off with the reduction of the adaptation of the polarizer in inside.In addition, in film In the case of, in order to maintain the hardness equal with thick film or severing, it is necessary to further improve, particularly in visuognosis person side The protective film that uses of polarizer surface in, the influence brought by these performances significantly shows.

For solving the method for problem

On the basis of above-mentioned problem, present inventor has made intensive studies, and as a result finds, has specifically by coordinating The compound of structure, can solve above-mentioned problem.Think, by using with amido link, ester bond, phenyl and with specific Skeleton structure compound, pass through the local position of these groups and cellulose ester film（Acetyl group or hydroxyl）Form hydrogen Key, it is suppressed so as to the motion of cellulose esters chain, hardness improves.Even more surprisingly find, the light durability of the compound Also improve, be finally completed the present invention.Specifically, following proposal is passed through<1>, preferably pass through<2>~<10>Solve above-mentioned Problem.

<1>A kind of cellulose ester film, wherein, contain following formulas（I）Shown compound.

Formula（I）

（Formula（I）In, R¹、R²、R⁴~R⁷And R⁹~R¹¹Hydrogen atom or substituent, R are represented respectively³And R⁸Hydrogen is represented respectively Atom or non-conjugated substituent, X¹And X²Respectively singly-bound or aliphatic linker, L represent singly-bound ,-N（R¹²）- or-C（R¹³）（R¹⁴）-, R¹²~R¹⁴Hydrogen atom or substituent are represented respectively.）

<2>According to<1>Described cellulose ester film, wherein, R⁸Selected from hydrogen atom, halogen atom, alkyl and alkoxy.

<3>According to<1>Or<2>Described cellulose ester film, wherein, R¹~R⁷、R⁹And R¹⁰Respectively hydrogen atom or non-common Yoke substituent.

<4>According to<1>~<3>Any one of cellulose ester film, wherein, X¹And X²Respectively singly-bound or carbon are former Subnumber is 1~3 aliphatic linker.

<5>According to<1>~<4>Any one of cellulose ester film, wherein, R¹²Selected from hydrogen atom, alcohol radical, alkyl And following formulas（IV）Shown group, R¹³And R¹⁴Selected from hydrogen atom, alcohol radical, alkyl, hydroxyl, following formulas（II）Shown Group and following formulas（III）Shown group.

Formula（II）

（Formula（II）In, R⁶、R⁷And R⁹~R¹¹Hydrogen atom or substituent, R are represented respectively⁸Represent hydrogen atom or non-conjugated take Dai Ji, X²Represent singly-bound or aliphatic linker.）

Formula（III）

（Formula（III）In, R¹、R²、R⁴And R⁵Hydrogen atom or substituent, R are represented respectively³Represent hydrogen atom or non-conjugated take Dai Ji, X¹Represent singly-bound or aliphatic linker.）

Formula（IV）

（Formula（IV）In, R⁶、R⁷、R⁹And R¹⁰Hydrogen atom or substituent, R are represented respectively⁸Represent hydrogen atom or non-conjugated take Dai Ji.）

<6>According to<1>~<5>Any one of cellulose ester film, wherein, R¹¹Selected from hydrogen atom, alcohol radical, alkane Base.

<7>A kind of polarizer, it has<1>~<6>Any one of cellulose ester film and the polarizer.

<8>A kind of liquid crystal display device, it has<7>Described polarizer.

<9>According to<8>Described liquid crystal display device, wherein, polarizer is arranged at visuognosis side.

<10>A kind of cellulose ester film carboxylic acid amide esters system additive, wherein, contain following formulas（I）Shown chemical combination Thing.

The effect of invention

In accordance with the invention it is possible to provide hardness height, the cellulose ester film of light excellent in te pins of durability.Furthermore it is possible to providing makes With the liquid crystal display device of the polarizer of the present invention.

Brief description of the drawings

Fig. 1 is an example of the position relationship for representing the polarizer and liquid crystal display device of the present invention.

Embodiment

Hereinafter, present disclosure is described in detail.In addition, "~" is with comprising before and after it in present specification The numerical value of record uses as the meaning of lower limit and higher limit.In this manual, alkyl etc. " group " is as long as no special Narration, can have substituent, can also not have substituent.And then in the case of the group that carbon number is defined, on State the number that carbon number refers to include carbon number possessed by substituent.

The cellulose ester film of the present invention is characterised by, contains formula（I）Shown compound.By using such It compound, can improve the hardness of film, and then the film of light excellent in te pins of durability can be provided.Generally, using plasticizer etc. During as additive, it is difficult to take into account appropriate hardness and fragility improvement（Flexibility improves）, but pass through formula（I）Shown chemical combination Thing, which can be reached, to be taken into account.

R¹、R²、R⁴~R⁷、R⁹And R¹⁰Hydrogen atom or substituent, preferably hydrogen atom or non-conjugated substituent are represented respectively, More preferably hydrogen atom, halogen atom, alkyl, alkoxy, more preferably hydrogen atom, fluorine atom, chlorine atom, by fluorine atom And/or chlorine atom substitution alkyl, unsubstituted alkyl, alkoxy, be still more preferably hydrogen atom, fluorine atom, chlorine atom, The alkyl for being 1~5 by alkyl that the carbon number that fluorine atom and/or chlorine atom substitute is 1~3, unsubstituted carbon number, carbon Atomicity is 1~3 alkoxy, particularly preferably hydrogen atom, methyl, ethyl, methoxyl group, ethyoxyl.

R⁸For hydrogen atom or non-conjugated substituent.This is because, when for conjugated system substituent when, except require the transparency Beyond optical thin film colours, decomposition reaction is also caused inside protective film by light irradiation, makes the reduction of light durability Wavelength region in there is absorption band.

Therefore, formula（I）Molar absorption coefficient of the dichloromethane solution of shown compound under 290nm be preferably Less than 1500.

Non-conjugated substituent in the present invention refers to the substituent without conjugacy group., can as conjugacy group Include carbonyl, imino group, vinyl, cyano group, nitro, aromatic group etc..R⁸Preferably hydrogen atom, halogen atom, alkyl, Alkoxy, more preferably hydrogen atom, fluorine atom, chlorine atom, the alkyl substituted by fluorine atom and/or chlorine atom, unsubstituted alkane Base, alkoxy, more preferably hydrogen atom, fluorine atom, chlorine atom, the carbon number that is substituted by fluorine atom and/or chlorine atom for 1~ The alkoxy that alkyl that 3 alkyl, unsubstituted carbon number are 1~5, carbon number are 1~3, particularly preferably hydrogen atom, Methyl, ethyl, methoxyl group, ethyoxyl.

R¹¹Represent hydrogen atom or substituent, preferably hydrogen atom or non-conjugated substituent.R as substituent¹¹More preferably For hydrogen atom, alcohol radical, alkyl, primary alconol base that more preferably hydrogen atom, carbon number are 1~3, carbon number are 1~5 Alkyl, particularly preferably hydrogen atom.

X¹And X²Respectively singly-bound or aliphatic linker.

Aliphatic linker refers to the group that must have the non-aromatic of carbon atom.Specifically, fat can be exemplified Fat race alkyl（For example, alkylidene, alkynylene or alkenylene）Or the base being made up of the combination of aliphatic alkyl and other groups Group, can exemplify aliphatic alkyl or by aliphatic alkyl and-O- ,-C（=O）- and-S- at least one kind of combination form Group.More preferably alkylidene or the group being made up of alkylidene and-O- combination, more preferably alkylidene, it is especially excellent Elect unsubstituted alkylidene as.Carbon number possessed by aliphatic linker is preferably 1~3.

L represents singly-bound ,-N（R¹²）- or-C（R¹³）（R¹⁴）-, R¹²~R¹⁴Hydrogen atom or substituent are represented respectively.

R¹²Represent hydrogen atom or substituent, preferably hydrogen atom or non-conjugated substituent.R as substituent¹²More preferably For hydrogen atom, alcohol radical, alkyl, following formulas（IV）Shown group, more preferably hydrogen atom, carbon number are 1~3 Primary alconol base, the alkyl that carbon number is 1~5, following formulas（IV）Shown group, it is still more preferably following formulas（IV） Shown group, particularly preferably hydrogen atom.

R¹³And R¹⁴Hydrogen atom or substituent, preferably hydrogen atom or non-conjugated substituent are represented respectively.

R as substituent¹³And R¹⁴Hydrogen atom, alcohol radical, alkyl, hydroxyl, following formulas are more preferably respectively（II）It is shown Group, following formulas（III）Shown group, more preferably hydrogen atom, the primary alconol base that carbon number is 1~3, carbon are former The alkyl, hydroxyl, following formulas that subnumber is 1~5（II）Shown group, following formulas（III）Shown group.

Formula（II）

Formula（III）

Formula（IV）

Formula（II）In R⁶~R¹¹And X²Respectively with formula（I）In R⁶~R¹¹And X²Synonymous, preferable scope is also same Justice.

Formula（III）In R¹~R⁵And X¹Respectively with formula（I）In R¹~R⁵And X¹Synonymous, preferable scope is also same Justice.

Formula（I）The molecular weight of shown compound is preferably 250~600, and more preferably 350~500.

It is illustrated below go out the present invention in the formula that preferably uses（I）Shown compound, but the present invention does not limit certainly In these.

Then, the film substrate i.e. cellulose esters used in the cellulose ester film of the present invention is illustrated.As fibre Tie up plain ester, preferred cellulose acylate.Hereinafter, cellulose acylate is illustrated.

（Cellulose acylate）

The substitution value of cellulose acylate means the Component units in cellulose（（β）The glucose of 1,4- glycoside links） Present in the ratio that is acylated of 3 hydroxyls.Substitution value（Acylation degree）Can be by determining each Component units matter of cellulose The bonding aliphatic acid amount of amount calculates.In the present invention, the substitution value of cellulose bodies can be weighed by the way that cellulose bodies are dissolved into Determined in the dimethyl sulfoxide (DMSO) equal solvent of hydrogen substitution¹³C-NMR spectrum, obtained by the peak strength ratio of the carbonyl carbon in acyl group and calculated Go out.Can the remaining hydroxyl of cellulose acylate is replaced to it is different from the acyl group that cellulose acylate itself has other After acyl group, pass through¹³C-NMR measure is obtained.On the detailed content of assay method, Shou mound he（Carbohydrate.Res., 273（1995）83-91）In it is on the books.

Full acyl substitution available for the cellulose acylate of the present invention is preferably 2.0~2.97, more preferably 2.2~ 2.95, particularly preferably 2.3~2.95.The formula used in the present invention（I）Shown compound particularly with it is such complete The cellulose acylate and used time hardness improvement of the scope of acyl substitution are high.If the particularly full acyl of cellulose acylate Base substitution value is 2.5~2.95, then the tendency that hardness further improves be present, it is advantageous to.Although mechanism is unclear, think It is due to that, by using such cellulose acylate, the mutual interaction of hydroxyl present in cellulose acylate reduces, Formula in the present invention（I）Shown compound more effectively can interact with cellulose acylate.

As available for the present invention cellulose acylate acyl group, particularly preferred acetyl group, propiono, bytyry, more Particularly preferred acetyl group.

The mixed aliphatic ester being made up of acyl group of more than two kinds can also be preferred as cellulose acylate in the present invention Use.In this case, as acyl group, it is also preferred that acetyl group and the acyl group that carbon number is 3~4.In addition, using mixing fat During fat acid esters, the substitution value of acetyl group is preferably shorter than 2.5, even more preferably below 1.9.On the other hand, carbon number is 3~4 The substitution value of acyl group be preferably 0.1~1.5, more preferably 0.2~1.2, particularly preferably 0.5~1.1.

In the present invention, it can be used by 2 kinds of different cellulose acylates of substituent and/or substitution value and with, mixing, The film that the multilayer formed by different cellulose acylates is formed can also be formed by common curtain coating method described later etc..

And then described in the paragraph 0023~0038 of Japanese Unexamined Patent Publication 2008-20896 publications have fatty acid acyl and The mixed acid ester of substituted or unsubstituted aromatic acyl can also be preferred for the present invention.

The cellulose acylate used in the present invention is preferably right with 250~800 matter homopolymerization, further preferably has 300~600 matter homopolymerization is right.In addition, the cellulose acylate used in the present invention preferably has 70000~230000 number Average molecular weight, further preferably with 75000~230000 number-average molecular weight, most preferably with 78000~120000 number Average molecular weight.

The cellulose acylate used in the present invention can use acid anhydrides or acyl chlorides as acylating agent to synthesize.Above-mentioned acylation When agent is acid anhydrides, as reaction dissolvent, organic acid is used（For example, acetic acid）Or dichloromethane., can be with addition, as catalyst Use protic catalyst as sulfuric acid.When acylating agent is acyl chlorides, as catalyst, alkali compounds can be used.In work In synthetic method in industry most typically, by cellulose with including organic acid corresponding with acetyl group and other acyl groups（Acetic acid, third Acid, butyric acid）Or their acid anhydrides（Acetic anhydride, propionic andydride, butyric anhydride）Mixed organic acid composition be esterified and carry out synthetic fibers Plain ester.

In the above-mentioned methods, cellulose as cotton linter or wood pulp is carried out in the organic acid as acetic acid mostly After activation process, in the presence of sulfuric acid catalyst, it is esterified using the mixed liquor of Determination of Organic Acids as described above.It is organic Acid anhydrides composition is used generally relative to the amount of hydroxyl present in cellulose with excess quantity.In the esterification treatment, except carrying out Beyond esterification, cellulosic backbone is also carried out（β）1,4- glycosidic bonds）Hydrolysis（Depolymerization reaction）.If carry out main chain The degree of polymerization of hydrolysis then cellulose esters reduces, and the physical property of the cellulose ester film of manufacture reduces.Therefore, reaction temperature is such Reaction condition it is preferred consider obtained by the degree of polymerization of cellulose esters, molecular weight determines.

Content

Above-mentioned formula（I）The content of shown compound is not particularly limited, but relative to 100 parts by mass of cellulose esters, Preferably 3~50 mass parts, more preferably 3~15 mass parts, particularly preferably 5~10 mass parts.

In the cellulose ester film of the present invention, except cellulose esters and formula（I）Beyond shown compound, it can also contain There are other additives.As these additives, known plasticizer, organic acid, pigment, polymer, delay tune can be exemplified Whole dose, ultra-violet absorber, antioxidant, delustering agent etc..Their record may be referred to Japanese Unexamined Patent Publication 2012-155287 public affairs The record of the paragraph 0062~0097 of report, their content are incorporated into present specification.Their total use level is excellent Below the 50 mass % of cellulose esters are elected as, more preferably below 30 mass %.

The manufacture method of the cellulose ester film of the present invention is not particularly limited, but preferably passes through melted masking method or solution Film method manufactures.

More preferably utilize the manufacture of solution film-forming method.

Melted masking method and solution film-forming method can manufacture the cellulose of the present invention in the same manner as the method generally carried out Ester film.For example, on melted masking, Japanese Unexamined Patent Publication 2006-348123 publications are referred to manufacture, on solution system Film, Japanese Unexamined Patent Publication 2006-241433 publications are referred to manufacture.

One example of the method for the cellulose ester film that the present invention is made by solution film-forming legal system is illustrated.

Solution film-forming method is solution obtained from cellulose esters is dissolved into organic solvent by modulation（Rubber cement）, and will be above-mentioned Solution curtain coating manufactures film to supporting body surface.

Ketone that ether that it is 3~12 selected from carbon number that above-mentioned organic solvent, which preferably comprises, carbon number are 3~12, carbon are former Solvent in the halogenated hydrocarbons that the ester and carbon number that subnumber is 3~12 are 1~6.

Above-mentioned ether, ketone and ester can also have cyclic structure.In addition, the function with the above-mentioned ether of more than 2, ketone and ester Group（That is ,-O- ,-CO- and-COO-）Any one of compound can also be used as above-mentioned organic solvent.It is above-mentioned organic molten Agent can also have other functional groups as alcohol hydroxyl group.In the case of the organic solvent with functional group of more than two kinds, Its carbon number is preferably in the above-mentioned preferable carbon atom number range of the solvent with any functional group.

Above-mentioned carbon number is in the example of 3~12 ethers, includes diisopropyl ether, dimethoxymethane, dimethoxy Ethane, 1,4- dioxanes, 1,3- dioxolanes, tetrahydrofuran, anisole and phenetole.

Above-mentioned carbon number is in the example of 3~12 ketone, includes acetone, MEK, diethyl ketone, diisobutyl ketone, ring Hexanone and methyl cyclohexanone.

Above-mentioned carbon number is in the example of 3~12 esters, includes Ethyl formate, propyl formate, amyl formate, acetic acid Methyl esters, ethyl acetate and amyl acetate.

In addition, in the example of the organic solvent with functional group of more than two kinds, acetic acid -2- ethoxy ethyl esters, 2- first are included Ethoxy-ethanol and butoxy ethanol.

Carbon number is that the carbon number of 1~6 halogenated hydrocarbons is preferably 1 or 2, most preferably 1.The halogen of halogenated hydrocarbons is preferred For chlorine.The ratio that the hydrogen atom of halogenated hydrocarbons is optionally substituted by halogen is preferably 25~75 moles of %, more preferably 30~70 moles of %, enters one Step is preferably 35~65 moles of %, most preferably 40~60 moles of %.Dichloromethane is representational halogenated hydrocarbons.

In addition it is also possible to organic solvent of more than two kinds is used in mixed way.

Cellulose ester solution（Rubber cement）Can be by being included in more than 0 DEG C of temperature（Normal temperature or high temperature）It is lower to be handled The in general method of step is modulated.The modulation of cellulose ester solution can use the tune of the rubber cement in common solvent cast method Method and device processed is implemented.In addition, in the case of in general method, as organic solvent, preferably using halogenated hydrocarbons（Especially It is dichloromethane）.

The amount of cellulose esters in cellulose ester solution in resulting solution in the way of 10~40 mass % are included It is adjusted.The amount of cellulose esters is more preferably 10~30 mass %.Organic solvent（Main solvent）In, after can also adding The arbitrary additive stated.

Cellulose ester solution can be by normal temperature（0~40 DEG C）It is lower to stir cellulose esters and organic solvent to be adjusted System.The solution of high concentration can also be stirred under pressurization and heating condition.Specifically, by cellulose esters and organic solvent Add it is in pressurizing vessel and closed, more than the boiling point that side is heated in the normal pressure of solvent under elevated pressure and scope that solvent does not seethe with excitement Temperature side be stirred.Heating-up temperature is usually more than 40 DEG C, preferably 60~200 DEG C, more preferably 80~110 ℃。

Each composition is added in container after can slightly being mixed in advance.In addition it is also possible to put into successively in container.Container must It must be formed in the way of it can stir.The inertness gas such as nitrogen can be injected to pressurize to container.In addition it is also possible to Utilize the rising of the vapour pressure of the solvent caused by heating.Or after container closure, will can also add under stress it is each into Point.

In case of heating, preferably heated from the outside of container.The heater of such as jacket type can be used. In addition it is also possible to by setting baffle heater in the outside of container, install pipeline and make liquid circulation so as to overall to container Heated.

Stirring sets agitating paddle preferably inside container and makes to use it to carry out.Agitating paddle preferred length is to reach container Agitating paddle near wall.In order to update the liquid film on wall of a container, the scraping wing is preferably set in the end of agitating paddle.

The tester class such as pressure gauge, thermometer can also be set in a reservoir.Each composition is dissolved into container molten In agent.The rubber cement modulated is cooled down after taking out or take out from container after the cooling period using heat exchanger etc..

Cellulose ester solution can also be modulated by hot-cold lysis method.On the detailed content of hot-cold lysis method, can make With the technology described in 0115~paragraph of paragraph 0122 of Japanese Unexamined Patent Publication 2007-86748 publications.

By the cellulose ester solution modulated（Rubber cement）Cellulose ester film is manufactured by solvent cast method.It is preferred that in rubber cement Middle addition delay visualization reagent.Rubber cement is in drum or takes curtain coating, solvent is evaporated and is formed film.Rubber cement before curtain coating preferably according to The mode that solid constituent amount reaches 18~35% adjusts concentration.The surface of drum or band is preferably to be finish-machined to mirror status.Rubber cement is excellent It is selected in surface temperature and is less than 10 DEG C and rouses or take curtain coating.

On the drying means in solvent cast method, in U.S. Patent No. 2,336,310, United States Patent (USP) 2,367,603 Number, United States Patent (USP) 2,492,078, United States Patent (USP) 2,492,977, United States Patent (USP) 2,492,978, United States Patent (USP) 2,607, No. 704, each specification of United States Patent (USP) 2,739,069 and United States Patent (USP) 2,739,070, British Patent No. 640731 and Each specification and Japanese Patent Publication 45-4554, Japanese Patent Publication 49-5614, the Japanese Unexamined Patent Publication of BP 736892 Clear No. 60-176834, it is on the books in each publication of Japanese Unexamined Patent Application 60-203430 and Japanese Unexamined Patent Application 62-115035. Drying on band or drum can be carried out by being sent into the inertness such as air, nitrogen gas.

In addition it is also possible to from drum or take and strip resulting film, so with untill 100 DEG C~160 DEG C successively The high warm air for changing temperature is dried, and evaporates residual solvent.Method above is in Japanese Patent Publication 5-17844 publications It is on the books.According to this method, can shorten from the time being cast to untill stripping.In order to implement this method, the drum in curtain coating Or rubber cement must gelation under the surface temperature of band.

In the manufacture method of cellulose ester film, the process of stretching being film-made is preferably included.The drawing of cellulose ester film It is preferably cellulose ester film direction of transfer to stretch direction（MD directions）The direction orthogonal with direction of transfer（TD directions）In appoint One, but from followed by the use cellulose ester film polarization machining process from the viewpoint of, particularly preferably The direction orthogonal with cellulose ester film direction of transfer（TD directions）.

The method stretched along TD directions is documented in such as Japanese Unexamined Patent Application 62-115035, Japanese Unexamined Patent Publication 4- No. 152125, Japanese Unexamined Patent Publication 4-284211, Japanese Unexamined Patent Publication 4-298310, each public affairs such as Japanese Unexamined Patent Publication 11-48271 In report.In the case of the stretching in MD directions, if such as regulation cellulose ester film transfer roller speed, it is thin with cellulose esters Film strips coiling speed of the speed compared to quickening cellulose ester film, then cellulose ester film is stretched.Drawing in TD directions In the case of stretching, keep the width edge of cellulose ester film to be transmitted with stenter by side, extend stenter at leisure Width, cellulose ester film can also be stretched.It can also be stretched after the drying of cellulose ester film using stretching-machine （Preferably use the uniaxial tension of long stretching-machine）.

In the case where using cellulose ester film as the diaphragm of the polarizer, in order to suppress from it is oblique see polarizer when Light leak, it is necessary to the slow axis in the face of the axis of homology of the polarizer and cellulose ester film is abreast configured.Due to continuously making The axis of homology of the polarizer for the wound membrane shape made is typically parallel with the width of wound membrane, so for being polarized above-mentioned wound membrane shape The diaphragm that device is formed with by the cellulose ester film of wound membrane shape is continuously bonded, and slow axis is necessary in the face of the diaphragm of wound membrane shape It is parallel with the width of cellulose ester film.Therefore preferably more stretched along TD directions.In addition, stretch processing can be with Carried out in the way of film making process, stretch processing can also be carried out to the blank after being film-made and batching.

The stretching of the stretching preferably 5~100% in TD directions, more preferably carry out 5~80%, particularly preferably carry out 5~40% drawings Stretch.In addition, non-stretched refer to be stretched as 0%.Stretch processing can be carried out in the way of film making process, can also be to being film-made and rolling up Blank after taking carries out stretch processing.In the case of the former, it can be stretched in the state of containing residual solvent amount, can be with It is preferred that residual solvent amount=（Remaining volatile ingredient quality/heating rear film quality）× 100% is 0.05~50% time progress Stretching.5~80% stretchings are carried out in the state of being particularly preferably 0.05~5% in residual solvent amount.

By to containing formula（Ⅰ）The cellulose ester film of shown compound implements stretch processing, can further carry The case hardness of high film.

Modulated cellulose ester solution can also be used（Rubber cement）Carry out more than 2 layers of curtain coating and carry out filming.This In the case of kind, cellulose ester film is preferably made by solvent cast method.Rubber cement drum or take curtain coating, make solvent evaporation and Form film.Rubber cement before curtain coating preferably adjusts concentration in the way of the scope that solid constituent amount reaches 10~40 mass %.Drum Or the surface of band is preferably finish-machined to mirror status.

When more than 2 layers of multiple cellulose ester solutions are cast, multiple cellulose ester solutions can be cast, also may be used It is cast respectively comprising the molten of cellulose esters by the multiple curtain coating mouths vacated interval on the direct of travel of supporter and set with side Liquid simultaneously makes it be laminated side making film.They can use such as Japanese Unexamined Patent Application 61-158414, Japanese Unexamined Patent Publication 1- Method described in each publication of No. 122419 and Japanese Unexamined Patent Publication 11-198285.In addition it is also possible to by being cast from 2 Mouth curtain coating cellulose ester solution, carries out filming.It can use such as Japanese Patent Publication 60-27562, Japanese Unexamined Patent Application No. 61-94724, Japanese Unexamined Patent Application 61-947245, Japanese Unexamined Patent Application 61-104813, Japanese Unexamined Patent Application 61-158413, And the method described in each publication of Japanese Unexamined Patent Publication 6-134933.And then Japanese Unexamined Patent Application 56-162617 can also be used The fluid by high-viscosity cellulose ester solution described in number publication is encased and the height is viscous with the cellulose ester solution of low viscosity The casting method for the cellulose ester film that degree and the cellulose ester solution of low viscosity are extruded simultaneously.

In addition it is also possible to using 2 curtain coating mouths, the film shaped by the first curtain coating mouth on supporter is stripped, The side that is contacted with intermediate layer carries out the second curtain coating, thus makes film.Such as Japanese Patent Publication 44- can be included Method described in No. 20235 publications.

The cellulose ester solution being cast can use same solution, can also use two or more different cellulose Ester solution.In order that multiple cellulose ester layer have function, if by corresponding to the cellulose ester solution of the function from each curtain coating Mouth extrusion.And then the cellulose ester solution in the present invention can also be with other functional layers（For example, adhesive linkage, dyestuff Layer, antistatic backing, antihalation layer, UV-absorbing layer, polarization layer etc.）It is cast simultaneously.

The length of the above-mentioned cellulose ester film obtained as described above is preferably batched with every 100~10000m of volume 1, more Preferably 500~7000m, more preferably 1000~6000m.When batching, annular knurl preferably at least is assigned to one end, annular knurl Width is preferably 3mm~50mm, more preferably 5mm~30mm, in fact it is highly preferred that is 0.5~500 μm, more preferably 1~200 μm. It bilateral can also be pressurized with unilateral compression.

As big picture with the optical compensating film of liquid crystal display device in use, it is preferred that being for example set to thin-film width More than 1470mm is formed.In addition, in the polarizer protection film of the present invention, not only include and cut into and can be directly inserted into The film of the mode of the diaphragm of size in liquid crystal display device, also include and strip is fabricated to and to roll up by continuous production The film for the mode that shape is rolled.The polarizer protection film of the mode of the latter is taken care of and transmitted in this condition, in reality When being bonded when being inserted into liquid crystal display device or with the polarizer etc., desired size is cut into use.In addition, with by Polarizer of the compositions such as the polyvinyl alcohol film of strip etc. is similarly fabricated to actually to be inserted after the state fitting of strip When entering into liquid crystal display device, desired size is cut into use.As the optical compensating film rolled with web-like One mode, it can include in a manner of rolling up a length of more than 2500m web-like and roll.

Case hardness：

The cellulose ester film of the present invention is by that containing above-mentioned compound, can have high case hardness.Cellulose The case hardness of ester film can pass through formula（Ⅰ）The species or content of shown compound adjusts.It is thin as cellulose esters The index of the case hardness of film, Knoop hardness can be used.Knoop hardness can pass through the method shown in Production Example described later It is measured.

Tearing strength：

The tearing strength of cellulose ester film represents that it is based on JIS K-7128-2：1998 tear test method （Elmendorf method of Tearing）It is converted into 60 μm of value.From in thickness described later（20~100 μm）In also can fully keep film Intensity from the aspect of, tearing strength is 2g above is preferable.More preferably 5~25g, more preferably 6~25g. In addition, in terms of 60 μm of conversions, preferably more than 8g, more preferably 8~15g.Specifically, can be by coupons 51mm × 64mm Determined after damping in 2 hours is carried out under conditions of 25 DEG C, 65%RH using underload tear strength test machine.

Modulus of elasticity：

The practical sufficient modulus of elasticity of cellulose ester film display.The scope of modulus of elasticity is not particularly limited, but from From the viewpoint of manufacture adaptive and treatability are such, preferably 1.0~6.0GPa, more preferably 2.0~5.0GPa.By will be upper The compound stated is added in cellulose ester film, has due to cellulose ester film hydrophobization is improved into the work of modulus of elasticity With the advantages of this point is also in the present invention.

Photoelastic coefficient：

The absolute value of the photoelastic coefficient of cellulose ester film is preferably 8.0 × 10^-12m²/ below N, more preferably 6 × 10^-12m²/ below N, more preferably 5 × 10^-12m²/ below N.By reducing the photoelastic coefficient of cellulose ester film, Neng Gou When the cellulose ester film of the present invention is inserted into liquid crystal display device as polarizer protection film, under suppressing hot and humid Uneven generation.Photoelastic coefficient is just set to the value for determining and calculating by following method as long as no specifying.

The lower limit of photoelastic coefficient is not particularly limited, but is actually 0.1 × 10^-12m²/ more than N.

As the measure of coefficient of elasticity, cellulose ester film is cut into 3.5cm × 12cm, uses ellipsometer test（M150, day This light splitting（Strain））Determine the Re under no-load, each load of 250g, 500g, 1000g, 1500g, the change by Re relative to stress The slope of straight line calculate, thus determine photoelastic coefficient.

Moisture content：

The moisture content of cellulose ester film can be evaluated by determining the equilibrium moisture content under certain humiture.It is flat Weighing apparatus moisture content is the moisture for the sample for having reached balance after being placed 24 hours under above-mentioned humiture with Karl_Fischer method measure Amount, by amount of moisture（g）Divided by sample mass（g）And the value calculated.

Moisture content under 25 DEG C of relative humidity 80% of cellulose ester film is preferably below 5 mass % more preferably 4 Below quality %, more preferably less than 3 mass %., can be by the present invention by reducing the moisture content of cellulose ester film Cellulose ester film when being inserted into as polarizer protection film in liquid crystal display device, the liquid crystal under suppressing hot and humid The generation of the display inequality of showing device.The lower limit of moisture content is not particularly limited, but is actually more than 0.1 mass %.

Moisture permeability：

The moisture permeability of cellulose ester film can pass through the moisture permeability test according to JIS Z0208（Cup type method）, in temperature 40 DEG C, in relative humidity 90%RH atmosphere, measure, by the quality of the vapor of sample, is converted into every 1m in 24 hours²Sample The value of area is evaluated.

The moisture permeability of cellulose ester film is preferably 500~2000g/m²My god, more preferably 900~1300g/m²My god, Particularly preferably 1000~1200g/m²My god.

Mist degree：

The mist degree of cellulose ester film is preferably less than 1%, more preferably less than 0.7%, particularly preferably less than 0.5%.It is logical Cross and mist degree is set to below above-mentioned higher limit, the hyalinosis get Geng Gao of cellulose ester film be present, be easier as optically thin Film uses the advantages of such.Mist degree is just set to the value for determining and calculating by following methods as long as no specifying.Mist degree Lower limit is not particularly limited, but is actually more than 0.001%.

On mist degree, by cellulose ester film 40mm × 80mm in the environment of 25 DEG C, relative humidity 60%, mist degree is used Meter（HGM-2DP、Suga Test Instruments）, it is measured according to JIS K7136.

Thickness：

The average film thickness of cellulose ester film can suitably provide according to purposes, but for example, 20~100 μm.Cellulose esters The average film thickness of film is preferably 10~100 μm, more preferably 15~80 μm, more preferably 20~70 μm.By being set to More than 20 μm, make tablet（web）The treatability during film of shape improves, it is advantageous to.In addition, by being set to less than 70 μm, Easily reply humidity change, easily maintains optical characteristics.

In addition, when cellulose ester film tool haves three layers the stepped construction of the above, the thickness of sandwich layer is preferably 3~70 μm, more Preferably 5~60 μm, epidermis A and epidermis B thickness is more preferably 0.5~20 μm, particularly preferably 0.5~10 μm, Most preferably 0.5~3 μm.Sandwich layer refers to the layer for being located at central part in 3-tier architecture, and epidermis refers to be located at outside in 3-tier architecture Layer.

（Saponification process）

Above-mentioned cellulose ester film can be assigned and the polarizer as polyvinyl alcohol by carrying out saponification process The adaptation of material, is used as polarizer protection film.

On the method for saponification, in paragraph 0211 and paragraph 0212 that Japanese Unexamined Patent Publication 2007-86748 publications can be used The method of record.

For example, for the saponification process of cellulose ester film, preferably with after film surface is impregnated into aqueous slkali, The circulation for being neutralized, being washed with acid solution and dried is carried out.As above-mentioned aqueous slkali, it is molten potassium hydroxide can be included Liquid, sodium hydroxide solution, the concentration of hydroxide ion preferably in 0.1~5.0mol/L scope, further preferably 0.5~ 4.0mol/L scope.Aqueous slkali temperature is preferably in the scope of room temperature~90 DEG C, further preferably in 40~70 DEG C of scope.

Japanese Unexamined Patent Publication 6-94915 publications, that described in Japanese Unexamined Patent Publication 6-118232 publications can also be implemented The easy bond processing of sample replaces saponification process.

[polarizer]

Then, the mode of cellulose ester film as the protective film of polarizer using the present invention is illustrated.This One example of the polarizer of invention is by the polarizer and two polarizer protection films for protecting two face（Transparent membrane）Structure Into polarizer protection film of the cellulose ester film with the present invention as at least side.

The cellulose esters of the present invention uses particularly preferable as the protective film of the visuognosis side of upside polarizer 10.Figure 1 is an example of the position relationship for representing the polarizer and liquid crystal display device of the present invention, and 1 represents the cellulose esters of the present invention Film, 2 represent the polarizer, and 3 represent phase-contrast film, and 4 represent liquid crystal cells.Phase-contrast film can also be that other protections are thin Film.In addition, Fig. 1 upside turns into visuognosis side.

As illustrated in Figure 1, the polarizer as the side of no cellulose ester film using the present invention is protected Film, preferably using phase-contrast film 3, but the phase-contrast film is used as, can exemplify and coordinate respectively in cellulose ester film Kind additive is stretched and shows the phase-contrast film of desired phase difference or have on the surface of supporter by liquid crystal The phase-contrast film for the optical anisotropic layer that composition is formed.Specifically, it may be referred to Japanese Unexamined Patent Publication 2008-262161 The record of publication, their content are incorporated into present specification.

In addition, as the polarizer, can use for example by thin film dipped stretched into iodine solution of polyvinyl alcohol and Into the polarizer etc..Using by polyvinyl alcohol it is thin film dipped carried out into iodine solution stretching form the polarizer when, can make The surface treatment face of the cellulose ester film of the present invention is directly bonded on two surfaces of the polarizer with bonding agent.As above-mentioned bonding Agent, polyvinyl alcohol or Pioloform, polyvinyl acetal can be used（For example, polyvinyl butyral resin）The aqueous solution or ethene base system gather Compound（For example, butyl polyacrylate）Latex.Particularly preferred bonding agent is the aqueous solution of fully saponified polyvinyl alcohol.

The mode being bonded with the above-mentioned polarizer of the polarizer protection film of the present invention is preferably according to the axis of homology of the polarizer Parallel mode is substantially achieved with the slow axis of above-mentioned polarizer protection film to be bonded.

Wherein, the axis of homology of the substantial parallel principal refractive index nx for referring to polarizer protection film direction and polarizer Its dislocation of direction is within 5 °, within preferably 1 °, within preferably 0.5 °.If dislocation is within 1 °, the orthogonal Buddhist nun of polarizer Degree of polarization performance under Cole's prism is reduced, and light leak is suppressed, it is advantageous to.

For the present invention polarizer, without departing from the spirit and scope of the invention, it is also preferred that as with for improving The antireflective film of the visibility of display, luminance brightness-improving film or with hard conating, forward scattering layer, anti-dazzle（It is anti- It is dizzy）The functionalization polarizer that the optical thin film of the functional layers such as layer is combined uses.Their details may be referred to Japan The record of the paragraph 0229~0250 of JP 2012-082235 publications, their content are incorporated into present specification.

The liquid crystal display device of the present invention is characterised by, includes at least 1 polarizer of the invention.Liquid crystal display device Details may be referred to Japanese Unexamined Patent Publication 2012-082235 publications paragraph 0251~0260 record, their content It is incorporated into present specification.

Embodiment

Embodiment is exemplified below out further specifically to illustrate the present invention.Material shown in following embodiment The purport without departing from the present invention such as material, usage amount, ratio, process content, processing step, it is possible to suitably changed. Therefore, the scope of the present invention is not limited to specific example as shown below.

（The synthesis of compound 5）

By three（Methylol）Aminomethane（25g）And pyridine（68.6g）In acetonitrile（400mL）In ice-cold stirring, drip benzene Formyl chloride（121.8g）Afterwards, reacted 3 hours at 30~40 DEG C.After reaction solution is cooled into room temperature, with ethyl acetate 300mL and Sodium bicarbonate aqueous solution 400mL carries out liquid separation operation, and after being dried with magnesium sulfate, solvent is distilled off with evaporimeter.By the thick production Thing is purified with silica gel column chromatography, obtains white solid（87g）.The identification of synthesized compound uses¹H-NMR is carried out.

¹H-NMR（300MHz、d-DMSO）：δ4.95（s、6H）、δ7.4-8.0（m、20H）、δ8.5（s、1H）

（The synthesis of compound 9）

By diethanol amine（20g）And pyridine（49.6g）In acetonitrile（300mL）In ice-cold stirring, drip chlorobenzoyl chloride （88.2g）Afterwards, reacted 3 hours at 30~40 DEG C.After reaction solution is cooled into room temperature, with ethyl acetate 300mL and bicarbonate Sodium water solution 400mL carries out liquid separation operation, and after being dried with magnesium sulfate, solvent is distilled off using evaporimeter.The crude product is used Silica gel column chromatography purifies, and obtains colourless liquid（54g）.The identification of synthesized compound uses¹H-NMR is carried out.

¹H-NMR（300MHz、CDCl₃）：δ3.7-4.1（m、4H）、4.3-4.8（m、4H）、δ7.3-7.6（m、11H）、δ 7.9-8.1（m、4H）

（The synthesis of compound 15）

By 2-（2- aminoethylaminos）Ethanol（20g）And pyridine（50.1g）In acetonitrile（300mL）In ice-cold stirring, drop Lower chlorobenzoyl chloride（89g）Afterwards, reacted 3 hours at 30~40 DEG C.After reaction solution is cooled into room temperature, with ethyl acetate 300mL Liquid separation operation is carried out with sodium bicarbonate aqueous solution 400mL, after being dried with magnesium sulfate, solvent is distilled off using evaporimeter.Should Crude product purified by silica gel is column chromatography eluting, obtains white solid（48g）.The identification of synthesized compound uses¹H-NMR enters OK.

¹H-NMR（300MHz、CDCl₃）：δ3.7-3.9（m、4H）、3.9-4.0（m、2H）、4.4-4.5（m、2H）、δ7.2- 7.6（m、12H）、δ7.8（m、2H）、δ7.9（m、2H）

On other compounds, also synthesized using amino alcohol as raw material using same method.

（The modulation of cellulose ester solution）

Following compositions is put into blending tank, stirs and dissolves each composition, modulates Cellulose acylate solutions.

Cellulose ester solution is cast using band casting machine, it is 40% to be dried at 100 DEG C to residual solvent levels Afterwards, film is stripped.The film stripped is further dried 20 minutes under 140 DEG C of atmosphere temperature.Manufactured cellulose esters The thickness of film is 60 μm.

By cellulose ester film obtained above under loading of pressing in 50mN by using the nano impress for exerting formula pressure head Method determines index of the Knoop hardness as case hardness.Unit N/mm²Represent.

Carry out the cross cut test according to JIS K5600.Specifically, applied firmly in the surface coating of the film of above-mentioned making Layer, after UV radiation curing, is carved with 24 hours Xe of indentation front irradiation on film.Sample surfaces after Xe irradiation On so that 1mm intervals are carved into 11 indentations in length and breadth and have made the grid of 100 1mm square.Cellophane tape and agate are being attached thereon Adhesive tape is drawn, promptly peels off and the closely sealed evaluation of progress is observed by visual observation to the position of stripping.Suga is used in Xe irradiation The Super Xenon Weather Meter SX75 of Test Instruments Co. Ltd. systems.

Light durability A：It is 0~40 piece to peel off position.

Light durability B：It is 41~70 pieces to peel off position.

Light durability C：It is more than 71 pieces to peel off position.

The tearing strength of cellulose ester film represents that it is based on JIS K-7128-2：1998 tear test method （Elmendorf method of Tearing）It is converted into 60 μm of value.By coupons 51mm × 64mm, damping 2 is small under conditions of 25 DEG C, 65%RH When after be measured using underload tear strength test machine.

[table 1]

The compound used in comparative example is as follows.

The comparative compound 3 of 1 comparative compound of comparative compound 2

Comparative compound 4

The Knoop hardness of embodiment 8 is most excellent.The compound of the invention with phenyl is believed that by these results not The proton position being only easily accessible in the gap in the strand of cellulose esters, and in amido link or ester bond effectively with acetyl Base, hydroxyl act on and form hydrogen bond, suppress the motion of the strand of cellulose esters.And then understand, even if compound of the invention Irradiation light, also it is able to maintain that high adaptation.

Think in comparative example 4 due to by phenyl ring Direct Bonding have the conjugated structure of amido link, sent out in protective film Have in the wavelength region of raw decomposition reaction and absorb, so the light poor durability compared with embodiment 1~3.

In addition understand, in tearing strength, cellulose ester film of the invention displays that high value, it is possible to takes into account hardness Improved with fragility.TPP shows excellent value in tearing strength, but can not take into account the improvement of hardness as in the present invention.

From above-mentioned result, in order to carry out hardness and fragility improvement, and then in order to improve light durability, the present invention is Effectively.

It is 2.43 instead of the degree of substitution with acetyl group used in Production Example 1, the cellulose esters that the degree of polymerization is 340, uses acetyl The cellulose esters that base substitution value is 2.87, the degree of polymerization is 370, cellulose ester film is made in the same manner as Production Example 1.Manufactured The thickness of cellulose ester film is 60 μm.

It will be shown in by the result evaluated with the same method of Production Example 1 in following tables.

[table 2]

* addition represents the addition relative to 100 parts by mass of cellulose esters.

In embodiment 12~15, in addition to improving light durability, Knoop hardness is further up.May be considered by In the cellulose esters using high substituted degree, so the mutual interaction of hydroxyl present in cellulose esters weakens, so as to this hair Bright formula（I）Shown compound more effectively interacts with cellulose esters.Its result is understood, even in using high In the case of the cellulose esters of substitution value, formula of the invention（I）Shown compound is for hardness and fragility improvement and has Effect.

The saponification process of cellulose ester film

By each cellulose ester film obtained in above-mentioned Production Example 1,2 in 2.3mol/L sodium hydrate aqueous solution, Impregnated 3 minutes at 55 DEG C.Washed in the washing bath of room temperature, at 30 DEG C using 0.05mol/L sulfuric acid in and.Exist again Wash in the washing bath of room temperature, further dried with 100 DEG C of warm air.So operate, table has been carried out to cellulose ester film The saponification process in face.

The making of polarizer

Iodine is adsorbed on the polyvinyl alcohol film of drawn and makes the polarizer.

Cellulose ester film through saponification process is attached to the side of the polarizer using polyvinyl alcohol system bonding agent.It is right Commercially available primary cellulose acetate film（FUJITAC TD80UF, Fuji Photo Film Co., Ltd.'s system）Carry out at same saponification Reason, using polyvinyl alcohol system bonding agent, in the side of each cellulose ester film with being pasted with above-mentioned making into opposite side The primary cellulose acetate film after saponification process is attached on the surface of the polarizer.

Now, configured according to the axis of homology of the polarizer mode orthogonal with the slow axis of resulting cellulose ester film.This Outside, the slow axis of the axis of homology for the polarizer and commercially available primary cellulose acetate film, is also configured according to orthogonal mode.

So operation has made polarizer.

By commercially available LCD TV（The BRAVIA J5000 of SONY Co., Ltd.）Visuognosis side polarizer peel off, As the polarizer of the present invention, the cellulose ester film by each polarizer made in above-described embodiment according to the various embodiments described above The mode for turning into opposite side with liquid crystal cell side respectively attaches via adhesive a piece of in observer side, obtains liquid crystal display device.

The explanation of symbol

The cellulose ester film of 1 present invention

2 polarizers

3 phase-contrast films

4 liquid crystal cells

10 upside polarizers

Claims

1. a kind of cellulose ester film, it contains the compound shown in following logical formula (I)s,

Logical formula (I)

In logical formula (I), R¹、R²、R⁴~R⁷And R⁹~R¹¹Hydrogen atom or substituent, R are represented respectively³And R⁸Respectively represent hydrogen atom or Non-conjugated substituent, X¹And X²Respectively singly-bound or aliphatic linker, L represent singly-bound ,-N (R¹²)-or-C (R¹³)(R¹⁴)-, R¹²~R¹⁴Hydrogen atom or substituent are represented respectively.

2. cellulose ester film according to claim 1, wherein, R⁸Selected from hydrogen atom, halogen atom, alkyl and alkoxy.

3. cellulose ester film according to claim 1 or 2, wherein, R¹~R⁷、R⁹And R¹⁰Respectively hydrogen atom or non-common Yoke substituent.

4. cellulose ester film according to claim 1 or 2, wherein, X¹And X²Respectively singly-bound or carbon number are 1~3 Aliphatic linker.

5. cellulose ester film according to claim 1 or 2, wherein, R¹²Selected from hydrogen atom, alcohol radical, alkyl and following logical Group shown in formula (IV), R¹³And R¹⁴Selected from the group shown in hydrogen atom, alcohol radical, alkyl, hydroxyl, following logical formula (II)s and under The group shown in logical formula (III) is stated,

Logical formula (II)

In logical formula (II), R⁶、R⁷And R⁹~R¹¹Hydrogen atom or substituent, R are represented respectively⁸Hydrogen atom or non-conjugated substituent are represented, X²Singly-bound or aliphatic linker are represented,

Logical formula (III)

In logical formula (III), R¹、R²、R⁴And R⁵Hydrogen atom or substituent, R are represented respectively³Hydrogen atom or non-conjugated substituent are represented, X¹Singly-bound or aliphatic linker are represented,

Logical formula (IV)

In logical formula (IV), R⁶、R⁷、R⁹And R¹⁰Hydrogen atom or substituent, R are represented respectively⁸Represent hydrogen atom or non-conjugated substituent.

6. cellulose ester film according to claim 1 or 2, wherein, R¹¹Selected from hydrogen atom, alcohol radical, alkyl.

7. cellulose ester film according to claim 1 or 2, wherein, R¹~R⁷、R⁹And R¹⁰Respectively hydrogen atom or non-common Yoke substituent, X¹And X²Respectively singly-bound or carbon number are 1~3 aliphatic linker.

8. cellulose ester film according to claim 1 or 2, wherein, R¹~R⁷、R⁹And R¹⁰Respectively hydrogen atom or non-common Yoke substituent, R¹²Selected from the group shown in hydrogen atom, alcohol radical, alkyl and following logical formula (IV)s, R¹³And R¹⁴Selected from hydrogen atom, alcohol Base, alkyl, hydroxyl, the group shown in following logical formula (II)s and the group shown in following logical formula (III)s,

Logical formula (II)

Logical formula (III)

Logical formula (IV)

9. cellulose ester film according to claim 1 or 2, wherein, R¹~R⁷、R⁹And R¹⁰Respectively hydrogen atom or non-common Yoke substituent, R¹¹Selected from hydrogen atom, alcohol radical, alkyl.

10. cellulose ester film according to claim 1 or 2, wherein, R¹~R⁷、R⁹And R¹⁰Respectively hydrogen atom or non-common Yoke substituent, X¹And X²Respectively singly-bound or carbon number be 1~3 aliphatic linker, R¹²Selected from hydrogen atom, alcohol radical, Group shown in alkyl and following logical formula (IV)s, R¹³And R¹⁴Selected from hydrogen atom, alcohol radical, alkyl, hydroxyl, following logical formula (II) institutes Group shown in the group shown and following logical formula (III)s,

Logical formula (II)

Logical formula (III)

Logical formula (IV)

11. cellulose ester film according to claim 1 or 2, wherein, R¹~R⁷、R⁹And R¹⁰Respectively hydrogen atom or non-common Yoke substituent, X¹And X²Respectively singly-bound or carbon number be 1~3 aliphatic linker, R¹¹Selected from hydrogen atom, alcohol radical, Alkyl.

12. cellulose ester film according to claim 1 or 2, wherein, R¹~R⁷、R⁹And R¹⁰Respectively hydrogen atom or non-common Yoke substituent, X¹And X²Respectively singly-bound or carbon number be 1~3 aliphatic linker, R¹¹Selected from hydrogen atom, alcohol radical, Alkyl, R¹²Selected from the group shown in hydrogen atom, alcohol radical, alkyl and following logical formula (IV)s, R¹³And R¹⁴Selected from hydrogen atom, alcohol radical, alkane Base, hydroxyl, the group shown in following logical formula (II)s and the group shown in following logical formula (III)s,

Logical formula (II)

Logical formula (III)

Logical formula (IV)

13. cellulose ester film according to claim 1 or 2, wherein, the content of the compound shown in the logical formula (I) Cellulose esters relative to 100 mass parts is 3~15 mass parts.

14. cellulose ester film according to claim 1 or 2, wherein, the substituent of cellulose esters is acetyl group, full acyl Base substitution value is 2.3~2.95.

15. a kind of polarizer, it has the cellulose ester film and the polarizer described in wantonly 1 in claim 1~14.

16. a kind of liquid crystal display device, it has the polarizer described in claim 15.

17. liquid crystal display device according to claim 16, wherein, the polarizer is arranged at visuognosis side.