CN103665442B - Cellulose acylate film, the polarizer and liquid crystal display device for having used the film - Google Patents

Abstract

The present invention relates to cellulose acylate film, the polarizer and liquid crystal display device of the film are used.A kind of cellulose acylate film, it contains following formulas（I）The compound and cellulose acylate of expression.Formula（I）In, R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴' and R⁵' represent hydrogen atom, substituent；Wherein, R¹Or R³In any one and R¹' or R³' in any one represent hydroxyl；R²And R²' represent specific group（Being bonded the carbon atom of position at least has the specific alkyl of hydrogen atom）；In addition, R³For hydroxyl when, R⁴Represent above-mentioned specific group, R³' when being hydroxyl, R⁴' represent above-mentioned specific group；L represents that the carbon number of the connects chain of the phenyl ring for connecting both ends is the aliphatic group of more than 2 divalent；Formula（I）

Description

Cellulose acylate film, the polarizer and liquid crystal display device for having used the film

Technical field

The present invention relates to cellulose acylate film, the polarizer and liquid crystal display device of the film are used.

Background technology

Optical component of the cellulose acylate film as liquid crystal display device, such as the supporter of optical compensation films, polarization Diaphragm of piece etc. is used for various liquid crystal display devices.

Liquid crystal display device is representative in room in addition to such as use indoors such as TV purposes, such as with portable equipment etc. Outer use chance increases.It is therefore desirable to develop be more tolerant of than ever it is hot and humid under the liquid crystal display device used.

Moreover, to liquid crystal display device, also tolerable requirement is got under the use condition of harshness in a variety of applications where Come higher, require higher levels of durability than ever year by year.

On the other hand, in order to suppress the xanthochromia occurred in melted masking when manufacturing cellulose acylate film（Yellowness index Increase）, it is proposed that the specific amphyl as antioxidant, deterioration preventing agent is added into cellulose acylate film（Ginseng According to patent document 1）.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2006-241428 publications

The content of the invention

Invent problem to be solved

In view of the foregoing, it is an object of the invention to develop to wait under harsh use condition even in hot and humid Tolerable liquid crystal display device, its used cellulose acylate film.

When it is hot and humid it is lower using liquid crystal display device when, produce inequality because the polarizer shrinks, or polarizer is inclined Shake performance degradation, so as to produce the problem of display performance reduces.Moreover, prevent the cellulose acylate manufactured by melted masking The xanthochromia of film and improve it is hot and humid it is lower using liquid crystal display device when durability due to being the difference for including acting factor Phenomenon, can not be directly using molten therefore in order to improve the durability of display performance of the liquid crystal display device under hot and humid Melt the opinion obtained during film.Without can improve in the stage for being assembled into liquid crystal display device and using（Particularly high temperature is high When wet or during light irradiation）In the polarizer durability conventional opinion, it is necessary to develop new Xie Decision means.

According to the research of the present inventors, in conventional opinion, the cellulose such as durability and reduction xanthochromia is improved taking into account In terms of the coloring of acylate film, high technology barriers be present.

Therefore, the present invention is to be completed in this case in order to solve the above mentioned problem that high technology barriers be present Invention, problem of the invention is, there is provided can improve the durability of the polarizer, be greatly lowered through when in light caused by Coloring, and can further improve the cellulose acylate film of the durability of the display performance of liquid crystal display device, use The polarizer and liquid crystal display device of the film.

In addition, the problem of the present invention also resides in, there is provided has used the polarizer and liquid crystal of the cellulose acylate film Showing device.

Means for solving the problems

The present inventors have studied the Sequence of Relative Stability of Free Radicals of various phenol system compounds, reactivity from various viewpoints, knot It is not that Sequence of Relative Stability of Free Radicals when phenolic hydroxyl group forms free radical is important that fruit, which is found that, but retains the reactivity of hydroxyl, and is adjusted Save Sequence of Relative Stability of Free Radicals and reactivity is even more important.

On the other hand, because the compound with the phenolic hydroxyl group for being easy to reaction can pass through when giving the energy such as heat or light Oxidation reaction etc. is decomposed, therefore turns into the reason for coloring etc. sometimes when adding cellulose acylate film, in practicality side Face turns into big problem.

Particularly, in order to take into account the improvement of polarizer durability and sunproof raising（Suppress through when in light irradiation when Coloring）, it is further studied, as a result obtains the present invention.

That is, above-mentioned problem is realized by the following means.

（1）A kind of cellulose acylate film, it contains following formulas（I）At least one kind of and fiber in the compound of expression Plain acylate.

Chemical formula 1

Formula（I）

［ formula（I）In, R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴' and R⁵' hydrogen atom or substituent are represented independently of one another.Its In, R¹Or R³In any one and R¹' or R³' in any one represent hydroxyl.R²And R²' following formulas are represented independently of one another （1）The group of expression.In addition, R³For hydroxyl when, R⁴Represent following formulas（1）The group of expression, R³' when being hydroxyl, R⁴' represent Following formulas（1）The group of expression.L represents that the carbon number of the connects chain of the phenyl ring for connecting both ends is more than 2 divalent Aliphatic group.]

Chemical formula 2

Formula（1）

［ formula（1）In, R^aAnd R^bHydrogen atom is represented independently of one another or can have alkyl, alkenyl or the alkynes of substituent Base, R^aWith R^bIt can be mutually bonded to form ring.

（2）According to（1）Described cellulose acylate film, wherein, the formula（I）The compound of expression is following formulas （IA）Or（IB）The compound of expression.

Chemical formula 3

Formula（IA）

Chemical formula 4

Formula（IB）

［ formula（IA）、（IB）In, R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴’、R⁵’、R^a、R^bWith L and the formula（I）In R¹、 R³、R⁴、R⁵、R¹’、R³’、R⁴’、R⁵’、R^a、R^bIt is identical with L implication.

（3）According to（1）Or（2）Described cellulose acylate film, wherein, the formula（I）Or（IA）The chemical combination of expression Thing is following formulas（IA-1）The compound of expression.

Chemical formula 5

Formula（IA-1）

［ formula（IA-1）In, R^a、R^bWith L and the formula（I）In R^a、R^bIt is identical with L implication.

（4）According to（1）~（3）Any one of cellulose acylate film, wherein, the L be used for connect both ends Phenyl ring connects chain carbon number be 4~20.

（5）According to（1）~（4）Any one of cellulose acylate film, wherein, the L is includes alicyclic structure Divalent aliphatic group.

（6）According to（1）~（5）Any one of cellulose acylate film, wherein, the R^aAnd R^bIndependently of one another The alkyl for being 1~12 for hydrogen atom or carbon number.

（7）According to（1）~（6）Any one of cellulose acylate film, wherein, the R^aAnd R^bIt is hydrogen atom.

（8）According to（1）~（7）Any one of cellulose acylate film, wherein, the acyl of the cellulose acylate Base substitution value（A）Meet following formula.

1.5≤A≤3.0

（9）According to（1）~（8）Any one of cellulose acylate film, wherein, the acyl of the cellulose acylate Base is acetyl group, and degree of substitution with acetyl group（B）Meet following formula.

2.0≤B≤3.0

（10）According to（1）~（9）Any one of cellulose acylate film, its also further containing polycondensation esterification close At least one kind of in thing is used as plasticizer.

（11）According to（10）Described cellulose acylate film, wherein, the polycondensation ester compounds are by that following will lead to Formula（a）At least one kind of dicarboxylic acids and following formulas represented（b）Obtained from least one kind of glycol polycondensation represented.

Formula（a）

HOC（=O）-X-CO₂H

Formula（b）

HO-Z-OH

［ formula（a）、（b）In, X represents that the carbon number of the aliphatic group that the carbon number of divalent is 2~18 or divalent is 6~18 aromatic group, Z represent that the carbon number of divalent is 2~8 aliphatic group.]

（12）According to（10）Or（11）Described cellulose acylate film, wherein, the number of the polycondensation ester compounds is divided equally Son amount is 500~2000.

（13）According to（10）~（12）Any one of cellulose acylate film, wherein, the polycondensation ester compounds End be blocked.

（14）According to（1）~（13）Any one of cellulose acylate film, it also contains monose or by 2~10 At least one kind of plasticizer is used as in the carbohydrate that monosaccharide unit is formed.

（15）According to（14）Described cellulose acylate film, wherein, the carbohydrate is by alkyl, aryl or acyl group Substitution.

（16）A kind of polarizer, it at least has above-mentioned（1）~（15）Any one of cellulose acylate film and The polarizer.

（17）A kind of liquid crystal display device, it at least has above-mentioned（16）Described polarizer.

Invention effect

By means of the invention it is possible to provide improve the polarizer durability, be greatly lowered through when in light caused by Color and it can further improve the cellulose acylate film of the durability of the display performance of liquid crystal display device, use this The polarizer and liquid crystal display device of cellulose acylate film.

Above-mentioned and other feature and advantage of the present invention pass through suitably with reference to appended accompanying drawing and from record hereafter In can understand.

Brief description of the drawings

Fig. 1 is an example of the exploded perspective view for the internal structure for showing schematically liquid crystal display device.

Fig. 2 is flowed with mould using common curtain coating for expression by common curtain coating simultaneously to the cellulose acylate film of 3-tier architecture The skeleton diagram of one example of delay.

Symbol description

1 top layer rubber cement

2 sandwich layer rubber cements

3 common curtain coating die heads

4 curtain coating supporters

21A, 21B polarizer

22 filter substrates

23 liquid crystal layers（Liquid crystal cells）

24 array base paltes

25 light guide plates

26 light sources

31a, 31b cellulose acylate film（Polaroid protective film）

32 polarizers

Embodiment

Hereinafter, embodiment is enumerated to be described in detail the present invention.

It should be noted that in this specification, the number range for using "~" to represent refers to the numerical value that will be recorded before and after it The scope being included as lower limit and higher limit.

In addition, in this specification, the group illustrated as each group refers to that substituted or unsubstituted group, such as alkyl are The alkyl of substituent can be had by referring to, and aliphatic group refers to the aliphatic group of straight chain, branch or ring-type, can be saturation, Can also be unsaturated（Do not form aromatic rings）, can also have substituent.

＜ ＜ cellulose acylate film ＞ ＞

The cellulose acylate film of the present invention contains following formulas（I）The compound and cellulose acylate of expression.

The cellulose acylate film can play the effect for the deterioration for suppressing the polarizer, be suitable for diaphragm.

Hereinafter, material contain in the cellulose acylate film of the present invention or available is described in detail.

The formulas of ＜ 1（I）The compound ＞ of expression

The cellulose acylate film of the present invention contains following formulas（I）The compound of expression.

Chemical formula 6

Formula（I）

Formula（I）In, R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴' and R⁵' hydrogen atom or substituent are represented independently of one another.Wherein, R¹Or R³In any one and R¹' or R³' in any one represent hydroxyl.R²And R²' following formulas are represented independently of one another（1）Table The group shown.In addition, R³For hydroxyl when, R⁴Represent following formulas（1）The group of expression；R³' when being hydroxyl, R⁴' represent following logical Formula（1）The group of expression.L represents that the carbon number of the connects chain of the phenyl ring for connecting both ends is the aliphatic of more than 2 divalent Group.

Wherein, had no particular limits as substituent, alkyl can be included（It is preferred that carbon number is 1~10, such as first Base, ethyl, isopropyl, the tert-butyl group, amyl group, heptyl, 1- ethyl pentyl groups, benzyl, 2- ethoxyethyl groups, 1- carboxymethyl groups etc.）, chain Alkenyl（It is preferred that carbon number is 2~20, such as vinyl, pi-allyl, oleyl etc.）, alkynyl（It is preferred that carbon number be 2~ 20, such as acetenyl, diacetylene base, phenylene-ethynylene etc.）, cycloalkyl（It is preferred that carbon number is 3~20, such as cyclopropyl, ring Amyl group, cyclohexyl, 4- methylcyclohexyls etc.）, aryl（It is preferred that carbon number is 6~26, such as phenyl, 1- naphthyls, 4- methoxyl groups Phenyl, 2- chlorophenyls, 3- aminomethyl phenyls etc.）, heterocyclic radical（It is preferred that carbon number is 0~20 heterocyclic radical, ring forms hetero atom Preferably oxygen atom, nitrogen-atoms, sulphur atom, it can be 5 or 6 yuan of rings, contracting ring can be carried out with phenyl ring, heterocycle, the ring can be Saturated rings, can also be unsaturation ring, aromatic rings, such as 2- pyridine radicals, 4- pyridine radicals, 2- imidazole radicals, 2- benzimidazolyls, 2- Thiazolyl, 2- oxazolyls etc.）, alkoxy（It is preferred that carbon number is 1~20, such as methoxyl group, ethyoxyl, isopropoxy, benzyl Epoxide etc.）, aryloxy group（It is preferred that carbon number is 6~26, such as phenoxy group, 1- naphthoxys, 3- methylphenoxies, 4- methoxyl groups Phenoxy group etc.）、

Alkyl sulfenyl（It is preferred that carbon number is 1~20, such as methyl mercapto, ethylmercapto group, isopropyisulfanyl, benzyl sulfenyl etc.）、 Artyl sulfo（It is preferred that carbon number is 6~26, such as thiophenyl, 1- naphthalenes sulfenyl, 3- methylphenyl-sulfanyls, 4- Methoxv-phenylsulfanvls Deng）, acyl group（Including alkyl-carbonyl, alkenyl carbonyl, aryl carbonyl, heterocyclecarbonyl, carbon number is preferably less than 20, such as Acetyl group, pivaloyl group, acryloyl group, methylacryloyl, benzoyl, nicotinoyl base etc.）, alkoxy carbonyl（It is preferred that carbon is former Subnumber is 2~20, such as ethoxy carbonyl, 2- ethylhexyl Epoxide carbonyls etc.）, aryloxycarbonyl（It is preferred that carbon number be 7~ 20, such as phenyloxycarbonyl, naphthoxycarbonyl etc.）, amino（Including amino, alkyl amino, arylamino, heterocyclic amino group, preferably Carbon number is 0~20, such as amino, N, N- dimethylaminos, N, N- diethylaminos, N- ethylaminos, anilino-, 1- pyrroles Cough up alkyl, piperidyl, morpholinyl etc.）, sulfophenyl（It is preferred that carbon number is 0~20, such as N, N- dimethyl methyl amido, N- benzene Base sulfophenyl etc.）, sulfamoyl（It is preferred that carbon number is 0~20, such as N, N- DimethylsuIfamoyl, N- phenyl sulfamoyls Base etc.）, acyloxy（It is preferred that carbon number is 1~20, such as acetyl group epoxide, benzoyl epoxide etc.）, carbamoyl （It is preferred that carbon number is 1~20, such as N, N- formyl-dimethylamino, N- phenylcarbamoyls etc.）, acyl amino（It is excellent It is 1~20 to select carbon number, such as acetyl-amino, Acryloyl amino, benzoyl-amido, nicotinoyl amido etc.）, cyano group, Hydroxyl, sulfydryl or halogen atom（Such as fluorine atom, chlorine atom, bromine atoms, iodine atom etc.）.

R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴' and R⁵' in the preferred alkyl of substituent, alkenyl, alkynyl, cycloalkyl, alcoxyl Base, aryloxy group, more preferably alkyl, cycloalkyl and alkoxy, further preferred alkyl and cycloalkyl.

R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴' and R⁵' on the basis of the position of hydroxyl positioned at ortho position group it is preferably following Formula（1）The group of expression.In addition, R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴' and R⁵' in be located at meta on the basis of the position of hydroxyl Group preferably 2 at least one be hydrogen atom, more preferably 2 are hydrogen atom.

Particularly preferred R⁵And R⁵' it is hydrogen atom.

Chemical formula 7

Formula（1）

Formula（1）In, R^aAnd R^bHydrogen atom is represented independently of one another or can have alkyl, alkenyl or the alkynes of substituent Base, R^aWith R^bIt can be mutually bonded to form ring.

R^aAnd R^bIn substituent can include R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴' and R⁵' substituent.

R^aAnd R^bIt is preferred that hydrogen atom, alkyl or alkenyl, more preferably hydrogen atom or alkyl, further preferred hydrogen atom or carbon Atomicity is 1~12 alkyl.

L is the linking group of divalent, the divalent that the carbon number for representing the connects chain of the phenyl ring for connecting both ends is more than 2 Aliphatic group.Wherein, the aliphatic group of divalent can be straight chain, branch or ring-type, can be that saturation can also be not Saturation（Wherein it is not arlydene）.In addition, when being ring-type, the ring is that monocyclic, condensed ring, bridge-type ring, loop coil are not related.

The L carbon number for being used to connect the connects chain of the phenyl ring at both ends is more than 2, and the carbon number of the connects chain is preferred For 2~25, more preferably 4~20, more preferably 6~15.

Wherein, the carbon number for the connects chain for the phenyl ring for connecting both ends refers to connect the phenyl ring at both ends by key Carbon number in connects chain, such as the carbon number of the connects chain of the phenyl ring for connecting both ends refer to alkylene for more than 2 Base ,-（CH₂）_n- situation, n be more than 2；In addition ,-CH（C₂H₅）- in, the carbon number of the connects chain is 1.Wherein, for even Connect the phenyl ring at both ends connects chain it is multiple in the presence of, represent most short connects chain.

Formula（I）In, the carbon atom being bonded with phenyl ring of L end is preferably sp³Carbon atom（Without unsaturated atom The carbon atom of key）, preferably tertiary or quaternary carbon atom（Carbon atom with 1 or without hydrogen atom）, wherein, preferred quaternary carbon atom （Carbon atom without hydrogen atom）.By the way that for such structure, the generation of the free radical on the carbon atom is inhibited, therefore It is preferred that.

The aliphatic group of the ring-type of the preferred divalents of L, the alkylidene connected by carbon-to-carbon triple bond.

As the ring of the divalent in the aliphatic group of the ring-type of divalent, preferably cyclohexane ring, tetrahydrochysene bicyclopentadiene ring and Adamantane ring.

As the alkylidene connected by carbon-to-carbon triple bond, preferably-alkylidene-（Ethynylene）_l- alkylidene-.Wherein, l Represent 1 or 2.More preferably-C（Rα）₂-（Ethynylene）_l-C（Rα）₂-, R α represent hydrogen atom or alkyl.The preferred alkyl of R α, spy Not preferred methyl.

Formula（I）The more preferably following formulas of the compound of expression（IA）Or（IB）The compound of expression, wherein, it is further excellent Gating formula（IA）The compound of expression, particularly preferred following formulas（IA-1）The compound of expression.

Chemical formula 8

Formula（IA）

Chemical formula 9

Formula（IB）

Chemical formula 10

Formula（IA-1）

Formula（IA）、（IB）、（IA-1）In, R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴’、R⁵’、R^a、R^bWith L and the formula（I） In R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴’、R⁵’、R^a、R^bScope identical with L implication, preferable is also identical.

Formula（I）The molecular weight of the compound of expression is preferably 200~1200, is more preferably 250~800, particularly preferably For 300~600.

When molecular weight is more than 200, due to being vaporized from film can be suppressed, therefore preferably.When for less than 1200 when, from From the viewpoint of suppression mist degree preferably.

Formula described below（I）The specific example of the compound of expression, but the present invention is not limited to these examples.

Chemical formula 11

Chemical formula 12

Chemical formula 13

Chemical formula 14

Chemical formula 15

Chemical formula 16

Wherein, Me represents methyl.

Formula（I）The compound of expression generally can be for example such as in Journal of Organic Chemistry, volume 60, Page 3612~3618（Nineteen ninety-five）, Angewandte der Chemie International Edition, volume 49,3684~ Page 3687（2009）, Journal of the American Chemical Society, volume 131, page 9914~9915 （2009）Or Tetrahedron Letters, volume 53, page 1567~1570（2012）Described in, by acid catalysis In the presence of agent, make amphyl with the compound containing 2 unsaturated bonds or the compound reaction containing 2 alcohol hydroxyl groups comes Obtain.As acid catalyst, Bronsted acid, lewis acid, ion exchange resin etc. can be used without particular limitation Solid acid etc..Although the unsaturated bond or hydroxyl that contain originally in may reacting and acid catalyst act on and generate cation kind, Generation transfer etc., so as to obtain the mixture of various structures, but it is also preferred that such product is directly used.

Formula（I）Content of the compound of expression in cellulose acylate is not particularly limited, relative to cellulose acyl The mass parts of compound 100, preferably 0.1~20 mass parts, more preferably 0.2~15 mass parts, particularly preferably 0.3~10 mass Part.

Can be by formula of more than two kinds（I）The compound of expression is used in combination, and now the content in cellulose acylate film is excellent Select its amount to it is above-mentioned be same scope.

When content is more than 0.1 mass parts, due to moisture permeability can be effectively reduced, therefore preferably.20 mass parts with When lower, from the viewpoint of mist degree is suppressed preferably.

The cellulose acylate ＞ of ＜ 2

Principal component of the cellulose acylate as film is used in the present invention.Here, in this specification, " principal component " is in conduct The composition of raw material is to refer to the composition in a kind of mode, and mass fraction highest composition is referred in for mode of more than two kinds. Cellulose acylate can use a kind, can also use two or more.Cellulose acylate can make acyl substituent for example by The cellulose acylate that acetyl group is separately formed, the cellulose acylated with a variety of different acyl substituents can also be used The mixture of thing or different cellulose acylates.

As the cellulose of the raw material of the cellulose acylate used in the present invention, there are cotton linter, wood pulp（Hardwood pulp, Softwood pulp）Deng can use the cellulose acylate obtained from any raw cellulose, can also be mixed according to different situations Use.On the detailed record of these raw celluloses, such as see that ball Ze, space field write, " プ ラ ス チ ッ Network Cai Liao Talk seats（17） Xian Victoria prime system Trees fat ", the new Wen societies of daily magazine industry（1970 Nian development rows）Huo Development Ming Association Hui Gong Open skill Reported public affairs skill designations 2001-1745 Number（The Page of 7 Page~8）, the cellulose described in these documents can be used.

In the present invention, the acyl group of cellulose acylate can be only a kind, can also use acyl group of more than two kinds.The present invention The middle cellulose acylate used is preferably with the acyl group that carbon number is 2~4 as substituent.When use acyl of more than two kinds It is one of preferably wherein acetyl group during base, as the acyl group that carbon number is 2~4, preferably propiono or bytyry.Utilize this A little cellulose acylates can make the excellent solution of dissolubility, particularly in chlorine-free organic solvent, can make good Solution.And then the solution that viscosity is low, filterability is good can be made.

First, the cellulose acylate preferably used in the present invention is recorded in detail.

The glucose unit for forming β -1,4 bondings of cellulose has free hydroxyl group at 2,3 and 6.Cellulose acyl Compound is part or all of polymer formed by acyl group acylation in these hydroxyls.

Acyl substitution represents the degree of the acylation of the hydroxyl of the cellulose positioned at 2,3 and 6, whole glucose lists For the hydroxyl of 2,3 and 6 of member when being acylated, total acyl substitution is 3, for example, all glucose units, only 6 it is complete When portion is acylated, total acyl substitution is 1.Similarly, in whole hydroxyls of whole glucose, in terms of each glucose unit, 6 Or any one whole in 2, when being acylated, total acyl substitution is also 1.

That is, the situation that whole hydroxyls in glucose molecule are all acylated is designated as 3 to represent acylated degree.

Total acyl substitution of the cellulose acylate used in the present invention（A）Preferably 1.5~3（1.5≤A≤3.0）、 More preferably 2.0~2.97, more preferably 2.5 less than 2.97, particularly preferably 2.70~2.95.

In addition, using only in cellulose acetate of the acetyl group as the acyl group of cellulose acylate, total degree of substitution with acetyl group （B）Preferably 2.0~3（2.0≤B≤3.0）, more preferably 2.0~2.97, more preferably 2.5 less than 2.97, Particularly preferably 2.70~2.95.

The acyl group that carbon number as the cellulose acylate used in the present invention is more than 2, can be aliphatic Acyl group can also be aromatic acyl group, be not particularly limited.These compounds are, for example, the alkyl oxycarbonyl base ester of cellulose, alkene Base carbonyl ester or aromatic carbonyl ester, aromatic alkyl carbonyl ester etc., can also each have further substituted group.Make For their preferable examples, acetyl group, propiono, bytyry, heptanoyl group, caproyl, caprylyl, capryl, ten can be included Diacyl, tridecanoyl base, myristoyl base, hexadecanoyl group, octadecanoyl, isobutyryl, pivaloyl group, cyclohexane carbo, oleoyl Base, benzoyl, naphthyl carbonyl, cinnamoyl etc..Wherein, more preferably acetyl group, propiono, bytyry, dodecanoyl, ten Eight acyl groups, pivaloyl group, oleoyl, benzoyl, naphthyl carbonyl, cinnamoyl etc., particularly preferably acetyl group, propiono, Bytyry（The carbon number of acyl group is 2~4 situation）, particularly preferably acetyl group（Cellulose acylate is acetate fiber The situation of element）.

In the acylation of cellulose, when using acid anhydrides or acyl chlorides as acylating agent, as the organic solvent of reaction dissolvent, make With organic acids such as acetic acid, dichloromethane etc..

As catalyst, when acylating agent is acid anhydrides, preferably using the protic catalyst such as sulfuric acid, when acylating agent is acyl chlorides （Such as CH₃CH₂COCl）When, preferably using alkali compounds.

The industrial preparative method of the mixed aliphatic ester of the most frequently used cellulose be by cellulose use contain with acetyl group and Aliphatic acid corresponding to other acyl groups（Acetic acid, propionic acid, valeric acid etc.）Or the method that the mixed organic acid composition of their acid anhydrides is acylated.

Cellulose acylate can for example be synthesized by the method described in Japanese Unexamined Patent Publication 10-45804 publications.

The film of the present invention is from the viewpoint of moisture permeability, the fiber containing 5~99 mass % preferably in total solid content Plain acylate, further preferably 20~99 mass %, particularly preferably contain 50~95 mass %.

The other additive ＞ of ＜ 3

Delay conditioning agent can also be added in the cellulose acylate film of the present invention（Postpone visualization reagent and delay depressant）, Or add polycondensation ester compounds（Polymer）, the polyester of polyalcohol, phthalic acid ester, phosphate etc. be used as plasticizer, enter And the additives such as ultra-violet absorber, antioxidant, delustering agent can also be added.

It should be noted that in present specification, in order to represent compound group, such as phosphate based compound Ground adds " being " and recorded, and in the above cases, its implication is identical with phosphate compound.

（Postpone depressant）

, can be using widely used phosphate based compound or except being used as cellulose acylated as delay depressant in the present invention The additive of thing film and the compound beyond known non-phosphate based compound.

Postpone depressant as macromolecule, may be selected from phosphoric acid polyester based polymer, styrenic and acrylic acid series The copolymer that polymer waits with them, preferably acrylic acid series polymeric compounds and styrenic.It is also preferable to containing at least A kind of polymer with negative intrinsic birefringence for being referred to as styrenic, acrylic acid series polymeric compounds.

As unless the low molecule amount delay depressant of the compound beyond the compound of phosphate system, can be included following Compound.These compounds can be that solid can also be grease.That is, to its fusing point or boiling point, there is no particular limitation.Example Such as the mixing of ultraviolet absorption material that fusing point or boiling point are less than 20 DEG C and more than 20 DEG C or being similarly deterioration preventing agent Mixing etc..In addition, as infrared absorbing dye, it is documented in such as Japanese Unexamined Patent Publication 2001-194522 publications.In addition, close , can be in Cellulose acylate solutions in the time of its addition（Rubber cement）Any time addition in production process, can also be in glue The increase process that is prepared of addition additive is starched after the last preparation section of preparation section to carry out.In addition, each raw material As long as addition can show its function, it is not particularly limited.

As unless the low molecule amount delay depressant of the compound beyond the compound of phosphate system, is not limited especially Fixed, its detailed content is documented in paragraph ［ 0066 ］~［ 0085 ］ of Japanese Unexamined Patent Publication 2007-272177 publications.

Formula described in paragraph ［ 0066 ］~［ 0085 ］ of Japanese Unexamined Patent Publication 2007-272177 publications（1）The change of expression Compound can be obtained as described in the publication by the condensation reaction of sulfonyl chloride derivatives and amine derivative.

Formula described in Japanese Unexamined Patent Publication 2007-272177 publications（2）The compound of expression can be by using condensation Agent（Such as dicyclohexylcarbodiimide（DCC）Deng）, the dehydration condensation or carboxylic acid chloride derivative of carboxylic acids and amine Obtained with the substitution reaction of amine derivative etc..

The delay depressant is from the viewpoint of suitable Nz coefficients are realized, more preferably Rth depressants.Delay reduces In agent, as Rth depressants, acrylic acid series polymeric compounds and styrenic, Japanese Unexamined Patent Publication 2007-272177 can be included Formula described in number publication（3）~（7）Low molecular compound of expression etc., wherein, preferably acrylic acid series polymeric compounds and benzene second Alkene based polymer, more preferably acrylic acid series polymeric compounds.

Postpone depressant relative to cellulose-based resin preferably with the addition of 0.01~30 mass % ratio, more preferably with 0.1~20 mass % ratio addition, particularly preferably added with 0.1~10 mass % ratio.By making addition be 30 matter Measure below %, it is possible to increase the compatibility with cellulose-based resin, suppress albefaction.When using delay depressant of more than two kinds, Its total amount is preferably within the above range.

（Postpone visualization reagent）

The cellulose acylate film of the present invention preferably comprises at least one kind of delay visualization reagent to show length of delay.

As delay visualization reagent, it is not particularly limited, the delay being made up of bar-shaped or discotic compound can be included and shown The compound of showing property of delay is shown in agent or above-mentioned non-phosphate based compound., can be excellent as bar-shaped or discotic compound Choosing uses the compound with least two aromatic rings as delay visualization reagent.

The content for the delay visualization reagent being made up of rod-shaped compound is relative to the component of polymer containing cellulose acylate 100 mass parts are preferably 0.1~30 mass parts, more preferably 0.5~20 mass parts.Postpone plate-like contained in visualization reagent Compound phase is preferably less than 3 mass parts, more preferably less than 2 mass parts for the mass parts of cellulose acylate 100, is particularly preferably Less than 1 mass parts.

Discotic compound is needing king-sized Rth due to being better than rod-shaped compound in terms of showing property of Rth delays Preferably used during delay.Delay visualization reagent of more than two kinds can also be used in combination.

Delay visualization reagent preferably has absorption maximum in 250~400nm wavelength region, and preferably real in visible region Without absorption in matter.

The details of delay visualization reagent is recorded in Japanese Laid-Open skill reports 2001-1745 page 49.

（Plasticizer（Hydrophobizers））

The cellulose acylate film of the present invention preferably comprises the polybasic esterification compound selected from polyalcohol（Hereinafter referred to as polyalcohol Ester system plasticizer.）, polycondensation ester compounds（Hereinafter referred to as contracting polyester plasticizer.）And carbohydrate（Hereinafter referred to as carbon aquation Compound derivative system plasticizer.）At least one of compound as plasticizer（Hydrophobizers）.

As plasticizer, preferably the glass transition temperature of cellulose acylate film is not being reduced as far as possible（Tg）In the case of Reduce moisture content.By using such plasticizer, the additive in hot and humid lower cellulose acylate film can be suppressed Spread to polarizer layer, so as to improve the deterioration of polarizer performance.

The plasticizer used in the present invention is described in detail below.

（Polyol ester system plasticizer）

For example following formulas of raw polyol of the polyol ester system plasticizer used in the present invention（c）It is shown.

Formula（c）

Rα-（OH）m

Formula（c）In, R α represent that the organic group of m valencys, m represent more than 2 positive integer.

As above-mentioned formula（c）In contained preferable polyalcohol, for example following compound can be included.But, originally Invention is not limited to these examples.

Ribitol, arabite, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2- propane diols, 1,3- third Glycol, DPG, tripropylene glycol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, dibutylene glycol, 1,2,4- fourths three Alcohol, 1,5-PD, 1,6- hexylene glycols, hexanetriol, galactitol, mannitol, 3- methylpentanes -1,3,5- triols, pinacol, D-sorbite, trimethylolpropane, trimethylolethane, xylitol etc..Particularly preferred triethylene glycol, tetraethylene glycol, dipropyl two Alcohol, tripropylene glycol, D-sorbite, trimethylolpropane, xylitol.

In polyol ester system plasticizer, the polyol ester for the polyalcohol that carbon number is more than 5 has preferably been used.It is especially excellent It is 5~20 to select carbon number.

Had no particular limits as the monocarboxylic acid used in the synthesis of polyol ester, known aliphatic can be used Monocarboxylic acid, alicyclic monocarboxylic acid, aromatic series monocarboxylic acid etc..When use alicyclic monocarboxylic acid, aromatic series monocarboxylic acid When, it is preferred from penetrability, the angle of retention is improved.

Monocarboxylic acid can include following compound, but the present invention is not limited to these.

As aliphatic monocarboxylic acid, preferably with the straight chain that carbon number is 1~32 or the aliphatic acid of side chain.Carbon atom Number more preferably 1~20, particularly preferably 1~10.When containing acetic acid, the compatibility increase with cellulose derivative, therefore It is preferred that it is also preferred that acetic acid and other monocarboxylic acids are used in mixed way.

As preferable above-mentioned aliphatic monocarboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, pungent can be included Acid, n-nonanoic acid, capric acid, 2- ethyl-hexanoics, hendecanoic acid, laurate, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, ten Seven alkanoic acids, stearic acid, nonadecylic acid, arachidic acid, behenic acid, tetracosanoic acid, hexacosoic acid, carboceric acid, montanic acid, honeybee Spend the saturated fatty acids such as acid, lacceroic acid, undecenoic acid, oleic acid, sorbic acid, linoleic acid, leukotrienes, arachidonic acid etc. no Saturated fatty acid etc..

As the example of preferable above-mentioned alicyclic monocarboxylic acid, can include ring valeric acid, cyclohexylenedinitrilotetraacetic acid, ring octanoic acid or it Derivative.

As the preferable above-mentioned monocarboxylic example of aromatic series, benzoic acid, methyl benzoic acid etc. can be included in benzene first The carboxylic acid of alkyl, diphenic acid, naphthoic acid, tetrahydro naphthoic acid etc. have been imported in the phenyl ring of acid has the aromatic series one of more than 2 phenyl ring First carboxylic acid or their derivative, but particularly preferred benzoic acid.

The molecular weight of polyol ester system plasticizer is not particularly limited, preferably 300~3000, more preferably 350~1500.It is preferred from the angle for suppressing to volatilize from film when molecular weight is more than 300, when molecular weight is less than 3000 When, it is preferred from the angle of penetrability and the compatibility of cellulose derivative.

The carboxylic acid used in the synthesis of polyol ester can be a kind, can also be mixing of more than two kinds.In addition, polyalcohol In hydroxyl can all be esterified, a part can also be remained in the form of hydroxyl.

The particular compound of polyol ester described below.

Chemical formula 17

Chemical formula 18

Chemical formula 19

Chemical formula 20

（Contracting polyester plasticizer）

The cellulose acylate film of the present invention preferably further contains contracting polyester plasticizer.By increasing containing contracting Polyester Modeling agent can obtain can obtain humidity stability, polarizer excellent in te pins of durability cellulose ester membrane effect.

Contracting polyester plasticizer is preferably by making following formulas（a）At least one kind of dicarboxylic acids and following formulas represented（b）Table At least one kind of glycol polycondensation for showing and obtain.

Formula（a）

HOC（=O）-X-CO₂H

Formula（b）

HO-Z-OH

Formula（a）、（b）In, X represents that the carbon number of the aliphatic group that the carbon number of divalent is 2~18 or divalent is 6 ~18 aromatic group, Z represent that the carbon number of divalent is 2~8 aliphatic group.Wherein, the carbon number of divalent be 2~ 8 aliphatic group can be that straight chain can also be branch.

Wherein, the carbon number of the divalent in X is that 2~18 aliphatic group can be that saturation can also be unsaturated , can be the chain of divalent or the aliphatic group of ring-type（Such as cycloalkylidene etc.）In any group.In addition, it is divalent Can be that straight-chain can also be branched during the aliphatic group of chain.The carbon number of the aliphatic group of divalent is more preferably For 2~12, more preferably 2~6.Wherein, the carbon number of divalent is the chain that 2~18 aliphatic group is preferably divalent Saturated aliphatic groups, more preferably chain alkylidene, more preferably straight-chain alkylidene.As carbon number For the aliphatic group of 2~18 chain, such as ethylidene, trimethylene, tetramethylene, pentamethylene, six Asias can be included Methyl, heptamethylene, eight methylene, decamethylene, ten dimethylenes, propylidene, 2- methyl trimethylenes, 2,2- dimethyl three Methylene, cyclopentylene, cyclohexylidene etc..

The carbon number of divalent in X is that 6~18 aromatic group can be the aromatic hydrocarbyl or 2 of divalent The aromatic heterocycle of valency.As the aromatic group of divalent, carbon number is preferably 6~15, more preferably 6~12.Close Aromatic rings in the aromatic hydrocarbyl of divalent, it can include such as phenyl ring, naphthalene nucleus, anthracene nucleus, cyclohexyl biphenyl, terphenyl ring.On Heteroaromatic in the aromatic heterocycle of divalent, preferably comprise at least one kind of conduct in oxygen atom, nitrogen-atoms or sulphur atom The heteroaromatic of ring atom.Heteroaromatic can include such as furans, pyrroles, thiophene, imidazoles, pyrazoles, pyridine, pyrrole Piperazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiadiazoles, oxazoline, oxazole, oxadiazoles, quinoline, isoquinoline Quinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzimidazole, benzoxazole, The heterocycles such as benzothiazole, BTA, the purine.Wherein, the preferred phenyl ring of aromatic rings in the aromatic hydrocarbyl of divalent, naphthalene nucleus, Cyclohexyl biphenyl, the preferred pyridine ring of heteroaromatic, triazine ring, quinoline ring in the aromatic heterocycle of divalent.

Z represents that the carbon number of divalent is 2~8 aliphatic group.The carbon number of divalent is 2~8 aliphatic group Can be saturation can also be it is undersaturated, can be the chain of divalent or the aliphatic group of ring-type（Such as cycloalkylidene Deng）In any group.In addition, when for the aliphatic group of the chain of divalent when, can be divalent straight-chain or point It is dendritic.The carbon number of the aliphatic group of divalent is more preferably 2~6, more preferably 2~4.Wherein, the carbon atom of divalent Number is that 2~8 aliphatic group is preferably the saturated aliphatic groups of the chain of divalent, is more preferably the alkylidene of chain, enters one Walk the alkylidene of preferred straight-chain.Carbon number be 2~8 chain alkylidene can include for example ethylidene, trimethylene, Tetramethylene, pentamethylene, hexa-methylene, heptamethylene, eight methylene, propylidene, 2- methyl trimethylenes, 2,2- dimethyl Trimethylene etc..

It should be noted that the cycloalkylidene as divalent, can include cyclopentylene, cyclohexylidene.

Contracting polyester plasticizer is preferably by the dicarboxylic acids with least one aromatic rings（Also referred to as aromatic dicarboxylic acid）With The aliphatic diol that at least one average carbon atom number is 2.5~8.0 obtains.In addition, it is also preferred that by aromatic dicarboxylic acid and extremely Lack a kind of mixture of aliphatic dicarboxylic acid, obtained with least one average carbon atom number for 2.5~8.0 aliphatic diol Arrive.

The calculating of the average carbon atom number of the dicarboxylic acid residue is based respectively on dicarboxylic acid residue and diol residue is carried out.

By the ratio of components of the dicarboxylic acid residue（Mole fraction）The value for forming carbon number and calculating is multiplied by as average Carbon number.For example, when being made up of each 50 moles of % of adipic acid residue and phthalic acid residue, average carbon atom number is 7.0。

In addition, the situation of the diol residue is similarly, the average carbon atom number of diol residue is by the group of diol residue Into than（Mole fraction）It is multiplied by the value for forming carbon number and calculating.Such as by 50 moles of % of glycol residue and 1,2- propane diols When 50 moles of % of residue are formed, average carbon atom number 2.5.

The number-average molecular weight of contracting polyester plasticizer is preferably 500~2000, is more preferably 600~1500, is further excellent Elect 700~1200 as.When the number-average molecular weight of polycondensation ester is more than 600, volatility step-down, height of the cellulose ester membrane in stretching The film failure caused by being vaporized or process pollution are inhibited under the conditions of temperature.

In addition, when the number-average molecular weight of polycondensation ester is less than 2000, uprised with the compatibility of cellulose esters, during film and plus Oozing out during hot-stretch is inhibited.

The number-average molecular weight of polycondensation ester can be measured by gel permeation chromatography, be evaluated.In addition, do not sealed for end , can also be by the amount of the hydroxyl of unit mass during the PEPA at end（Hereinafter also referred to hydroxyl value）Calculate.In the present invention, close In hydroxyl value, after by PEPA acetylation, measure neutralizes the amount of the potassium hydroxide needed for excessive acetic acid（mg）.

When the mixture of aromatic dicarboxylic acid and aliphatic dicarboxylic acid is used as into dicarboxylic acid component, preferred dicarboxylic composition Average carbon atom number be 5.5~10.0 dicarboxylic acids, more preferably 5.6~8.

When average carbon atom number is more than 5.5, the polarizer of excellent in te pins of durability can obtain.Average carbon atom number is less than 10 When, excellent in compatibility in cellulose esters and the generation oozed out can be suppressed in the film-forming process of cellulose ester membrane.

By formula（b）Included in the polycondensation ester that the diol compound of expression and dicarboxylic acids comprising aromatic dicarboxylic acid obtain Aromatic dicarboxylic acid residue.

In this specification, residue is the part-structure of polycondensation ester, represents the portion of the feature with the monomer for forming polycondensation ester Separation structure.Such as dicarboxylic acids HOC（=O）-X-CO₂The dicarboxylic acid residue that H is formed is-C（=O）-X-C（=O）-.The present invention The aromatic dicarboxylic acid residue ratio of the middle polycondensation ester used be preferably more than 40mol%, more preferably 40mol%~ 95mol%.

By making aromatic dicarboxylic acid residue ratio be more than 40mol%, can obtain showing sufficient optics respectively to different The cellulose ester membrane of property, the polarizer of excellent in te pins of durability can be obtained.In addition, when for below 95mol% when, with cellulose esters It is excellent in compatibility, can also in the film of cellulose ester membrane and heating stretching when suppress ooze out.

As the aromatic dicarboxylic acid of the synthesis available for contracting polyester plasticizer, can include such as phthalic acid, Terephthalic acid (TPA), M-phthalic acid, 1,5- naphthalenedicarboxylic acids, 1,4- naphthalenedicarboxylic acids, 1,8- naphthalenedicarboxylic acids, 2,8- naphthalenedicarboxylic acids or 2, 6- naphthalenedicarboxylic acids etc..Wherein, it is preferably phthalic acid, terephthalic acid (TPA), NDA, more preferably phthalic acid, right Phthalic acid, further preferred terephthalic acid (TPA).

The aromatic dicarboxylic acid residue in the aromatic dicarboxylic acid source used when in polycondensation ester formed with mixing.

That is, the aromatic dicarboxylic acid residue preferably comprises phthalic acid residue, terephthalic acid residue, M-phthalic acid It is at least one kind of, further preferably at least one kind of, further preferred in phthalic acid residue, terephthalic acid residue in residue Contain terephthalic acid residue.

By using terephthalic acid (TPA) as aromatic dicarboxylic acid in the synthesis of polycondensation ester, with the compatibility of cellulose esters more The fiber that the generation oozed out during film that is excellent, being further formed in cellulose ester membrane and when heating stretches also is inhibited Cellulose ester film.In addition, aromatic dicarboxylic acid can use a kind, can also use two or more.During using 2 kinds, preferably using adjacent benzene Dioctyl phthalate and terephthalic acid (TPA).

It is used in combination by this 2 kinds of aromatic dicarboxylic acids by phthalic acid and terephthalic acid (TPA), can be by the polycondensation under normal temperature Ester softens, and it is preferred to become easy angle from operability.

The content of terephthalic acid residue in the dicarboxylic acid residue of polycondensation ester is preferably 40mol%~100mol%.

By making terephthalic acid residue's ratio be more than 40mol%, can obtain showing sufficient optical anisotropy Cellulose ester membrane.

By formula（b）Included in the polycondensation ester that the diol compound of expression and dicarboxylic acids comprising aliphatic dicarboxylic acid obtain Aliphatic dicarboxylic acid residue.

The aliphatic dicarboxylic acid of synthesis contracting polyester plasticizer can include such as oxalic acid, malonic acid, butanedioic acid, Malaysia Acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid or 1,4- cyclohexane diacids Deng.

The aliphatic dicarboxylic acid residue in the aliphatic dicarboxylic acid source used when in polycondensation ester formed with synthesis.

The average carbon atom number of aliphatic dicarboxylic acid residue is 5.5~10.0, is more preferably 5.5~8.0, further preferably For 5.5~7.0.When the average carbon atom number of aliphatic dicarboxylic acid residue is less than 10.0, the heating damage of compound can be reduced Lose, can prevent the process caused by oozing out when cellulose acylate tablet is dried pollute caused by planar it is former Barrier.In addition, when the average carbon atom number of aliphatic dicarboxylic acid residue is more than 5.5, excellent in compatibility and polycondensation ester is difficult to occur Separate out, therefore preferably.

The aliphatic dicarboxylic acid residue when using 2 kinds, preferably comprises amber and specifically, it is preferable to comprising succinic acid residue Sour residue and adipic acid residue.

That is, the synthesis of polycondensation ester can use a kind of aliphatic dicarboxylic acid, can also use two or more, when using 2 kinds, It is preferred that use butanedioic acid and adipic acid.When the synthesis of polycondensation ester uses a kind of aliphatic dicarboxylic acid, preferably using butanedioic acid.From energy It is enough that the average carbon atom number of aliphatic dicarboxylic acid residue is adjusted to desired value and gone out with the angle of the compatibility of cellulose esters Hair is preferred.

In the present invention, the mixing in the formation of polycondensation ester preferably uses 2 kinds or 3 kinds of dicarboxylic acids.When using 2 kinds, preferably Aliphatic dicarboxylic acid and aromatic dicarboxylic acid respectively use a kind, during using 3 kinds, can use a kind of aliphatic dicarboxylic acid and 2 kinds of virtues Fragrant race's dicarboxylic acids, or 2 kinds of aliphatic dicarboxylic acids and a kind of aromatic dicarboxylic acid.The reason is that it can easily be accommodated dicarboxylic acid residue Average carbon atom number value and the content of aromatic dicarboxylic acid residue can be made to reach preferable scope, and can improve The durability of inclined device.

By formula（b）It is residual comprising glycol in the polycondensation ester that the diol compound of expression and dicarboxylic acids comprising dicarboxylic acids obtain Base.

In this specification, by formula（b）The diol compound of expression（HO-Z-OH）The diol residue of formation is-O-Z-O-.

As the glycol for synthesizing polycondensation ester, aromatic diol and aliphatic diol can be included, in of the invention, preferably At least synthesized using aliphatic diol.

Polycondensation ester preferably comprises the aliphatic diol residue that average carbon atom number is 2.5~7.0, be further preferably averaged carbon Atomicity is 2.5~4.0 aliphatic diol residue.

When the average carbon atom number of aliphatic diol residue is less than 7.0, is improved with the compatibility of cellulose esters, be not easy Ooze out, in addition, the loss on heating of compound is not easy to increase, it is difficult to process when occurring to be dried by cellulose acylate tablet Planar failure caused by pollution.In addition, when the average carbon atom number of aliphatic diol residue is more than 2.5, synthesis is easy.

It is excellent as the aliphatic diol for synthesizing contracting polyester plasticizer, preferably alkyl diol or ester ring type glycols Such as ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,2- butanediols, 1,3 butylene glycol, 2- methyl-1,3-propanediols, 1 are selected, 4- butanediols, 1,5- pentanediols, 2,2- dimethyl -1,3- propane diols（Neopentyl glycol）, 2,2- diethyl -1,3- propane diols（3, 3- dihydroxymethyl pentanes）, 2- normal-butyl -2- ethyl -1,3- propane diols（3,3- dihydroxymethyl heptane）, 3- methyl isophthalic acids, 5- penta 2 Alcohol, 1,6- hexylene glycols, 2,2,4- trimethyl -1,3- pentanediols, 2- ethyls -1,3- hexylene glycol, 2- methyl isophthalic acids, 8- ethohexadiols, 1, 9- nonanediols, 1,10- decanediols, 1,12- octacosanols, diethylene glycol, cyclohexanedimethanol etc..These glycol preferably with second Glycol forms one kind or two or more mixture and used together.

Aliphatic diol be more preferably it is at least one kind of in ethylene glycol, 1,2-PD and 1,3-PD, particularly preferably It is at least one kind of in ethylene glycol and 1,2- propane diols.When synthesizing polycondensation ester using 2 kinds of aliphatic diols, preferably using ethylene glycol With 1,2- propane diols.By using 1,2-PD or 1,3-PD, it can prevent polycondensation ester from crystallizing.

The diol compound used when can pass through mixing in the polycondensation ester adds diol component i.e. glycol in the polyester Residue.

That is, it is residual as diol residue to preferably comprise glycol residue, 1,2-PD residue and 1,3-PD for polycondensation ester It is at least one kind of in base, more preferably glycol residue or 1,2-PD residue.

Preferably comprised in the polycondensation ester in contained aliphatic diol residue glycol residue 10mol%~ 100mol%, further preferably 20mol%~100mol%.

The end of polycondensation ester can by it is uncapped and directly for glycol or carboxylic acid in the form of（I.e. polymer chain length end is-OH Or CO₂H）, monocarboxylic acid class or unary alcohol can also be made to react and implement so-called end-capped in addition.It should be noted that By the way that by the end-capped of polycondensation ester, following effects can be obtained：State at normal temperatures is not easy to be changed into solid shape, operability Become good, and humidity stability, the cellulose ester membrane of polarizer excellent in te pins of durability can be obtained.

As the monocarboxylic acid class for end-blocking, preferably acetic acid, propionic acid, butyric acid, benzoic acid etc..As one for end-blocking First alcohols, preferably methanol, ethanol, propyl alcohol, isopropanol, butanol, isobutanol etc., most preferably methanol.What the end of polycondensation ester used When the carbon number of monocarboxylic acid class is less than 7, go out from the loss on heating that can reduce compound, the viewpoint for suppressing planar failure Hair is preferred.

The end of polycondensation ester is further preferably uncapped and is directly diol residue, or by acetic acid or propionic acid or benzoic acid End-blocking.Whether two ends of polycondensation ester each whether there is the situation for implementing to block identical all not related.

When two ends of condensation product are uncapped, polycondensation ester is preferably PEPA.

One of mode as polycondensation ester, the carbon number that can include aliphatic diol residue are 2.5~8.0 and contracting The uncapped polycondensation ester in two ends of polyester.When two ends of polycondensation ester are blocked, preferably by being reacted with monocarboxylic acid to seal End.Now, two ends of the polycondensation ester turn into monocarboxylic acid residue.

In this specification, the monocarboxylic acid residue formed by monocarboxylic acid R β-COOH is R β-CO-.Two ends of polycondensation ester When being blocked by monocarboxylic acid, the monocarboxylic acid is preferably aliphatic monocarboxylic acid residue, and monocarboxylic acid residue is more preferably carbon Atomicity is less than 22 aliphatic monocarboxylic acid residue, and more preferably carbon number is less than 3 aliphatic unitary carboxylic Sour residue.Additionally, it is preferred that carbon number is more than 2 aliphatic monocarboxylic acid residue, particularly preferred carbon number is 2 fat Race's monocarboxylic acid residue.

One of mode as polycondensation ester, can include aliphatic diol residue carbon number be more than 2.5 and for 7.0 with Under, and the polycondensation ester that two ends of polycondensation ester are blocked by monocarboxylic acid residue.

When the carbon number for blocking the monocarboxylic acid residue of two ends of polycondensation ester is less than 3, volatility reduction, polycondensation Loss caused by the heating of ester will not increase, and can reduce the generation of process pollution or the generation of planar failure.

That is, it is former as the monocarboxylic acid class for end-blocking, preferred aliphat monocarboxylic acid, more preferably monocarboxylic carbon It is aliphatic monocarboxylic acid that subnumber is 2~22, the aliphatic monocarboxylic acid that more preferably carbon number is 2~3, especially excellent Select the aliphatic monocarboxylic acid residue that carbon number is 2.

Such as preferred acetic acid, propionic acid, butyric acid, benzoic acid and its derivative etc., more preferably acetic acid or propionic acid, most preferably second Acid.

Monocarboxylic acid for end-blocking can mix two or more.

It is preferred that two ends of polycondensation ester are blocked by acetic acid or propionic acid, most preferably blocked by acetic acid and two ends is turned into acetyl Base ester residue（Sometimes referred to as acetyl group residue）.

Specific example J-1~J-41 of polycondensation ester is listed in table 1 below, but the present invention is not limited to these examples.

Wherein, in the abbreviation of above-mentioned table 1, PA represent phthalic acid, TPA represent terephthalic acid (TPA), AA represent adipic acid, SA represents that butanedioic acid, 2,6-NPA represent 2,6- naphthalenedicarboxylic acids.

The synthesis of polycondensation ester can be by using the polyesterification reaction or ester exchange using glycol and dicarboxylic acids of conventional method Either method in the heat fusing condensation method of reaction or the Surface condensation method of these sour acyl chlorides and glycols is easily synthesized. It should be noted that the Knitting person of polycondensation Zhi villages well filial piety one " plastic drug そ reason Theory と ying use "（Co., Ltd. good fortune Books rooms, Showa 48 On March 1, the development row of first edition the 1st edition）In be documented, described compound can be used.

In the present invention, Japanese Unexamined Patent Publication 05-155809, Japanese Unexamined Patent Publication 05-155810, Japanese Unexamined Patent Publication can be used Flat No. 5-197073, Japanese Unexamined Patent Publication 2006-259494, Japanese Unexamined Patent Publication 07-330670, Japanese Unexamined Patent Publication 2006-342227 Number, the compound described in each publication of Japanese Unexamined Patent Publication 2007-003679 etc..

（Carbohydrate derivates system plasticizer）

The cellulose acylate film of the present invention preferably further contains carbohydrate derivates system plasticizer.By containing Carbohydrate derivates system plasticizer, can obtain can obtain humidity stability, the cellulose esters of polarizer excellent in te pins of durability The effect of film.

As carbohydrate derivates system plasticizer, preferably monose or the carbon hydrate containing 2~10 monosaccharide units The derivative of thing.

The monose or polysaccharide for preferably comprising carbohydrate derivates system plasticizer is characterised by, may replace in molecule Group（Such as hydroxyl, carboxyl, amino, sulfydryl etc.）It is substituted.The example of the structure formed as substituted, can be included Alkyl, aryl, acyl group etc..Taken in addition, ether structure, hydroxyl that hydroxyl is substituted and formed by alkyl or aryl can be included by acyl group Generation and the ester structure formed, the amide structure that is substituted and formed by amino or imide structure etc..

The example of carbohydrate as above-mentioned monose or containing 2~10 monosaccharide units, for example red moss can be included Sugar, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, fructose, mannose, gulose, Chinese mugwort Shut out sugar, galactolipin, talose, trehalose, isotrehalose, neotrehalose, mycosamine, kojibiose, nigerose, maltose, Maltitol, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, lactose amine, lactitol, lactulose, Melibiose, primeverose, rutinose, scillabiose, sucrose, Sucralose, turanose, vicianose, fiber triose, potato three Sugar, gentianose, Isomaltotriose, different panose, maltotriose, manninotriose, melezitose, panose, planteose, raffinose, eggplant Trisaccharide, umbelliferose, lycotetraose, maltotetraose, stachyose, maltopentaose, verbascose, MALTOHAXAOASE, alpha-cyclodextrin, β-ring Dextrin, gamma-cyclodextrin, δ-cyclodextrin, xylitol, D-sorbite etc..

Preferably ribose, arabinose, xylose, lyxose, glucose, fructose, mannose, galactolipin, trehalose, malt Sugar, cellobiose, lactose, sucrose, Sucralose, alpha-cyclodextrin, beta-schardinger dextrin, gamma-cyclodextrin, δ-cyclodextrin, xylitol, mountain Pears sugar alcohol, more preferably arabinose, xylose, glucose, fructose, mannose, galactolipin, maltose, cellobiose, sugarcane Sugar, beta-schardinger dextrin, gamma-cyclodextrin, particularly preferably xylose, glucose, fructose, mannose, galactolipin, maltose, fiber two Sugar, sucrose, xylitol, D-sorbite.

In addition, the example of the substituent as carbohydrate derivates system plasticizer, can include alkyl（It is preferred that carbon is former Subnumber is 1~22, the alkyl that more preferably carbon number is 1~12, particularly preferred carbon number is 1~8, for example, methyl, ethyl, Propyl group, hydroxyethyl, hydroxypropyl, 2- cyano ethyls, benzyl etc.）, aryl（It is preferred that carbon number is 6~24, more preferably carbon is former The aryl that subnumber is 6~18, particularly preferred carbon number is 6~12, such as phenyl, naphthyl）, acyl group（It is preferred that carbon number is 1 ~22, the acyl group that more preferably carbon number is 2~12, particularly preferred carbon number is 2~8, such as acetyl group, propiono, fourth Acyl group, valeryl, caproyl, caprylyl, benzoyl, toluyl, phthalyl, naphthoyl etc.）.In addition, make To be substituted the preferable structure to be formed by amino, amide structure can be included（It is preferred that carbon number is 1~22, more preferably carbon The acid amides that atomicity is 2~12, particularly preferred carbon number is 2~8, such as formamide, acetamide etc.）, imide structure（It is excellent To select carbon number be 4~22, the acid imide that more preferably carbon number is 4~12, particularly preferred carbon number is 4~8, such as amber Amber acid imide, phthalimide etc.）.

Wherein, further preferred substituent is alkyl, aryl or acyl group, particularly preferably acyl group.

As the preferable example of carbohydrate derivates system plasticizer, following plasticizer can be included.But, originally Workable carbohydrate derivates system plasticizer is not limited to these in invention.

It is preferred that xylose tetraacetate, alpha-glucose pentaacetate, fructose pentaacetate, Mannose pentaacetate, galactolipin five Acetic acid esters, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, D-sorbite six Acetic acid esters, the propionic ester of xylose four, glucose pentapropiopanoate, the propionic ester of fructose five, the propionic ester of mannose five, the propionic acid of galactolipin five Ester, the propionic ester of maltose eight, the propionic ester of cellobiose eight, sucrose octapropanoate, the propionic ester of xylitol five, the propionic acid of D-sorbite six Ester, the butyrate of xylose four, Glucose Pentabutyrate, the butyrate of fructose five, the butyrate of mannose five, the butyrate of galactolipin five, wheat Eight butyrates of bud sugar, the butyrate of cellobiose eight, the butyrate of sucrose eight, the butyrate of xylitol five, the butyrate of D-sorbite six, wood Sugared four benzoic ethers, the benzoic ether of glucose five, the benzoic ether of fructose five, the benzoic ether of mannose five, the benzoic acid of galactolipin five Ester, the benzoic ether of maltose eight, the benzoic ether of cellobiose eight, the benzoic ether of sucrose eight, the benzoic ether of xylitol five, sorbose Benzoic ether of alcohol six etc..

Further preferred xylose tetraacetate, alpha-glucose pentaacetate, fructose pentaacetate, Mannose pentaacetate, half Lactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, sorb The acetic acid esters of sugar alcohol six, the propionic ester of xylose four, glucose pentapropiopanoate, the propionic ester of fructose five, the propionic ester of mannose five, galactolipin five Propionic ester, the propionic ester of maltose eight, the propionic ester of cellobiose eight, sucrose octapropanoate, the propionic ester of xylitol five, D-sorbite six Propionic ester, the benzoic ether of xylose four, the benzoic ether of glucose five, the benzoic ether of fructose five, the benzoic ether of mannose five, galactolipin Five benzoic ethers, the benzoic ether of maltose eight, the benzoic ether of cellobiose eight, the benzoic ether of sucrose eight, the benzoic acid of xylitol five Ester, the benzoic ether of D-sorbite six etc..

Particularly preferred maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, the propionic ester of xylose four, Portugal Five propionic esters of grape sugar, the propionic ester of fructose five, the propionic ester of mannose five, the propionic ester of galactolipin five, the propionic ester of maltose eight, fiber two Sugared eight propionic esters, sucrose octapropanoate, the benzoic ether of xylose four, the benzoic ether of glucose five, the benzoic ether of fructose five, mannose Five benzoic ethers, the benzoic ether of galactolipin five, the benzoic ether of maltose eight, the benzoic ether of cellobiose eight, the benzoic acid of sucrose eight Ester, the benzoic ether of xylitol five, the benzoic ether of D-sorbite six etc..

Carbohydrate derivates system plasticizer preferably has pyranose structure or furanose structure.

As the carbohydrate derivates used in the present invention, particularly preferred compound shown below.But, this hair Workable carbohydrate derivates are not limited to these in bright.

It should be noted that in following structural formula, R separately represents arbitrary substituent, and multiple R can be with identical Can also be different.

It is will have 8 hydroxyls in table 2 below~5, such as in table 2（R is hydrogen atom）Derivative with 2 kinds of acylating agents The acylated derivative formed, one in the R that will be imported by 2 kinds of acylating agents be expressed as that " substituent 1 ", another R are expressed as " substituent 2 ", substitution value represent the number in all 8 hydroxyls.

Total R number is 5 in table 3, in table 4 and 5 is 8.Here, " phenyl acetyl " expression-C (=O)-CH₂- C₆H₅。

Chemical formula 21

Chemical formula 22

Chemical formula 23

Chemical formula 24

Carbohydrate derivates can be used as commercially available product to be obtained from Co., Ltd.'s Tokyo chemical conversion system, Aldrich etc., in addition Commercially available carbohydrate can pass through known esterification（Such as the side described in Japanese Unexamined Patent Publication 8-245678 publications Method）It is easily synthesized.

The content of these plasticizer is 1~20 mass % preferably with respect to cellulose acylate.When for more than 1 mass % When, be readily available polarizer durability improvement effect, and when for below 20 mass % when, ooze out and be inhibited.Enter one Preferable content is walked as 2~15 mass %, particularly preferably 5~15 mass %.

On the opportunity being added to these plasticizer in cellulose acylate film, as long as add at the time point of film Add, be then not particularly limited.For example, can be in the time point addition that cellulose acylate synthesizes, can also be when prepared by rubber cement Mixed with cellulose acylate.

（Other additives）

As other additives, known antioxidant, ultra-violet absorber, delustering agent etc. can be added.

They are illustrated below.

（Antioxidant）

In the present invention, known antioxidant, such as 2,6- di-t-butyl-can be added in Cellulose acylate solutions 4- sylvans, 4,4'- thiobis-（The 6- tert-butyl group -3- sylvans）, 1,1'- it is double（4- hydroxy phenyls）Hexamethylene, 2,2'- methylenes Base is double（4- ethyl -6- tert-butyl phenols）, 2,5- di-t-butyls hydroquinones, ［ the 3- of pentaerythrite-four（3,5- di-t-butyl -s 4- Hydroxy phenyl）Propionic ester ］ etc. phenol system or hydroquinones system antioxidant.In addition it is also preferred that addition three（4- methoxyl groups -3,5- two Phenyl）Phosphite ester, three（Nonyl phenyl）Phosphite ester, three（2,4- di-t-butyl phenyl）It is phosphite ester, double（Bis--uncles of 2,6- Butyl -4- aminomethyl phenyls）It is pentaerythritol diphosphites, double（2,4- di-t-butyl phenyl）Pentaerythritol diphosphites etc. Phosphorous antioxidant.The addition of antioxidant is relative to the mass parts of cellulose-based resin 100 0.05~5.0 mass of preferred addition Part.

（Ultra-violet absorber）

Can be with the present invention from the viewpoint of the deterioration for preventing polarizer or liquid crystal etc., in Cellulose acylate solutions Add ultra-violet absorber.It is excellent and good from the absorbability of below wavelength 370nm ultraviolet as ultra-violet absorber From the viewpoint of good liquid crystal display, preferably using the few ultra-violet absorber of the absorption of more than wavelength 400nm visible ray. The ultra-violet absorber preferably used in the present invention can include such as hindered phenol series compound, dihydroxy benaophenonel system chemical combination Thing, BTA based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, nickel Complex salt based compound etc..

Hindered phenol series compound can include 2,6- di-t-butyl -s the paracresol, (3- of pentaerythrite-four（3,5- bis--tertiary fourth Base -4- hydroxy phenyls）Propionic ester), N, N'- hexamethylene bis（3,5- di-t-butyl -4- hydroxy-hydrocineamides）、1,3, 5- trimethyls -2,4,6- three（3,5- di-t-butyl -4- hydroxybenzyls）Benzene, three-（3,5- di-t-butyl -4- hydroxybenzyls）- Isocyanuric acid ester etc..

BTA based compound can include 2-（2 '-hydroxyl -5 '-aminomethyl phenyl）BTA, 2,2- di-2-ethylhexylphosphine oxides 〔4-（1,1,3,3- tetramethyl butyls）-6-（2H- BTA -2- bases）Phenol),（2,4- pairs-（N-octylthio）-6-（4- Hydroxyl -3,5- di-t-butyl anilino-s）- 1,3,5- triazines, triethylene glycol-bis- (3-（The 3- tert-butyl group -5- methyl -4- hydroxy benzenes Base）Propionic ester), N, N'- hexamethylene bis（3,5- di-t-butyl -4- hydroxy-hydrocineamides）, 1,3,5- trimethyl -2, 4,6- tri-（3,5- di-t-butyl -4- hydroxybenzyls）Benzene, 2-（2'- hydroxyl -3 ', 5'- di-t-butyl phenyl）- 5- chloro benzos Triazole, 2-（2'- hydroxyl -3 ', 5'- bis--tertiary pentyl phenyl）- 5- chlorinated benzotriazoles, 2,6- di-t-butyl -s paracresol, season penta (the 3- of tetrol-four（3,5- di-t-butyl -4- hydroxy phenyls）Propionic ester) etc..

The addition of these ultraviolet preventing agents in optical film entirety in terms of mass ratio be preferably 1ppm~1.0%, More preferably 10~1000ppm.

（Delustering agent）

From the viewpoint of film slickness and stable manufacture, cellulose acylate film of the invention can also add delustring Agent.Delustering agent can be the delustering agent of inorganic compound or the delustering agent of organic compound.

The delustering agent of inorganic compound preferably comprises the inorganic compound of silicon（Such as silica, burn till calcium silicates, water and Calcium silicates, alumina silicate, magnesium silicate etc.）, titanium oxide, zinc oxide, aluminum oxide, barium monoxide, zirconium oxide, strontium oxide strontia, antimony oxide, oxidation Tin, tin-antiomony oxide, calcium carbonate, talcum, clay, kaolin and calcium phosphate etc. are burnt till, further preferably silicon is inorganization Compound or zirconium oxide, due to the turbidity of cellulose acylate film can be reduced, therefore particularly preferably use silica.

The particulate of silica can use for example with AEROSIL R972, R974, R812,200,300, R202, OX50、TT600（Above by Japanese AEROSIL Co. Ltd. systems）Etc. the commercially available product of trade name.The particulate of zirconium oxide can use Such as with AEROSIL R976 and R811（Above by Japanese AEROSIL Co. Ltd. systems）The particulate commercially available etc. trade name.

The delustering agent preference of the organic compound such as polymer such as organic siliconresin, fluororesin and acrylic resin, especially It is preferred that organic siliconresin.In organic siliconresin, particularly preferably there is the resin of three-dimensional network structure, can use for example with TOSPEARL103, TOSPEARL105, TOSPEARL108, TOSPEARL120, TOSPEARL145, TOSPEARL3120 and TOSPEARL240（Above by Toshiba's Silicone Co. Ltd. systems）Etc. the commercially available product of trade name.

When these delustering agents are added in Cellulose acylate solutions, its method is not particularly limited, as long as can Obtaining desired Cellulose acylate solutions, then any method all has no problem.For example, can by cellulose acylate with it is molten The stage addition additive of agent mixing, can also add addition after mixed solution has been made with cellulose acylate and solvent Thing.

In addition it can also use and preposition additive process mix, so-called is added before it will be cast to rubber cement, lead to Online setting screw is crossed to be kneaded to be mixed.And specifically, it is preferable to the static mixer of in-line mixing machine etc., in addition, conduct In-line mixing machine, such as preferably Static Mixer SWJ（Blender Hi-Mixer in Toray silent oscillation pipes）（Toray Engineering systems）Deng in-line mixing machine.

It should be noted that on online addition, in order to eliminate cohesion of density unevenness, particle etc., Japanese Unexamined Patent Publication 2003- Following methods have been recorded in No. 053752 publication：In the manufacture method of cellulose acylate film, by using will be with main original The distance L for expecting the front end of the addition nozzle of the annex solution mixing of the different compositions of rubber cement and the top portion of in-line mixing machine is main material Less than 5 times with bore d, to eliminate the cohesion of density unevenness, matting agent particles etc..As further preferred mode, note Carried the annex solution supply nozzle for making compositions different from main material rubber cement front end opening and in-line mixing machine top portion it Between distance（L）For the internal diameter of supply nozzle front end opening（d）Less than 10 times, and in-line mixing machine for static state without stirred type Blender in blender or dynamic agitation type pipe in pipe.More particularly, disclosed cellulose acylate film main material rubber cement/online The flow-rate ratio of annex solution is 10/1~500/1, is preferably 50/1~200/1.In addition, oozed out less with additive and there is no interlayer Peeling and slickness is good, the transparency is excellent phase retardation film be target Japanese Unexamined Patent Publication 2003-014933 public affairs Also describe as adding additivated method, can be added in dissolution kettle in report, can also be in dissolution kettle~common curtain coating mould Between by additive or additive is dissolved or the scattered solution formed is added in the rubber cement in liquor charging, due to the feelings of the latter Combination can be improved under condition, therefore is preferably provided with the mixed medias such as Static Mixer.

As long as delustering agent does not add in large quantities, the mist degree of film would not increase, so as to be actually used in LCD（Liquid crystal display） When, it is not susceptible to the unfavorable condition that contrast reduces, produces bright spot etc..It is as long as in addition, not very few, it becomes possible to realize above-mentioned smooth Property, marresistance.From these viewpoints, relative to cellulose acylate, particularly preferably with 0.05~1.0 mass % ratio Contain.

In total solid content, the summation of the composition of cellulose acylate, plasticizer and other additives is 100 matter Measure %.

The composition and physical property ＞ of the cellulose acylate films of ＜ 4

（The Rotating fields of film）

The cellulose acylate film of the present invention can be individual layer or more than 2 layers of layered product.

When the cellulose acylate film of the present invention is more than 2 layers of layered product, preferably 2 Rotating fields or 3-tier architecture are more excellent Elect 3-tier architecture as.During 3-tier architecture, film of the invention preferably has and the metal branch when being manufactured by solution film-forming The layer that support body connects（Hereinafter also referred to intermediate layer or top layer B）And the Air Interface of the metal support opposite side Layer（Hereinafter also referred to air surface or top layer A）And 1 layer of sandwich layer sandwiched therebetween（Hereinafter also referred to basic unit）.That is, film of the invention Preferably this 3-tier architecture of top layer B/ sandwich layers/top layer A.

It should be noted that top layer A and top layer B are also collectively referred to as top layer.

The acyl substitution of cellulose acylate in each layer of the cellulose acylate film of the present invention can also may be used with homogeneous To be mixed multiple fiber element acylate in one layer, but from the viewpoint of the regulation of optical characteristics, in preferably each layer The acyl substitution of cellulose acylate is all certain.In addition, when the cellulose acylate film of the present invention is 3-tier architecture, from system From the viewpoint of causing this, contained cellulose acylate uses acyl substitution identical fiber preferably in the superficial layer on two sides Plain acylate.

（Modulus of elasticity）

The practical sufficient modulus of elasticity of film display of the present invention.The scope of modulus of elasticity is not particularly limited, from manufacture From the viewpoint of adaptability and operability, preferably 1.0GPa~5.0GPa, more preferably 2.0GPa~4.5GPa.The present invention's Formula（I）The compound of expression is by being added in cellulose acylate, so as to by the way that film hydrophobization is improved into elasticity to have The effect of modulus, this point and advantages of the present invention.

（Photoelastic coefficient）

The absolute value of the photoelastic coefficient of the film of the present invention is preferably 8.0 × 10^-12m²/ below N, more preferably 6 × 10^{- 12}m²/ below N, more preferably 5 × 10^-12m²/ below N.By reducing the photoelastic coefficient of resin film, by the resin film When being assembled into liquid crystal display device as polaroid protective film, it can suppress uneven in hot and humid lower generation.Photoelastic coefficient Unless otherwise specified, to determine the value calculated by the following method.

The lower limit of modulus of photoelasticity is not particularly limited, but is preferably 0.1 × 10 in practical^-12m²/ more than N.

Film is cut into 3.5cm × 12cm, uses ellipsometer（M150 ［ trade name ］, Japan Spectroscopy Corporation）Measure is without lotus Re under weight, each loading of 250g, 500g, 1000g, 1500g, changed by Re and calculated relative to the slope of the straight line of stress, So as to determine photoelastic coefficient.

（Moisture content）

The moisture content of resin film can be evaluated by determining the equilibrium moisture content under certain humiture.Equilibrium moisture content After being placed 24 hours under the humiture, the amount of moisture of the sample of balance is reached by Karl Fischer methods measure, will Amount of moisture（g）Divided by sample mass（g）And the value calculated.

Moisture content under the film of the present invention is 80% in 25 DEG C, relative humidity is preferably below 5 mass %, more preferably 4 Below quality %, it is further preferably no larger than 3 mass %.By reducing the moisture content of film, protected using resin film as polarizer When film is assembled into liquid crystal display device, it is possible to increase the display performance of the liquid crystal display device under hot and humid.Under moisture content Limit value is not particularly limited, but is more than 0.1 mass % in practice.

（Moisture permeability）

The moisture permeability of resin film can the moisture permeability test based on JIS Z0208（Kapp Method）, by temperature be 40 DEG C, Relative humidity is the quality of the water vapour passed through in being determined 24 hours in 90%RH atmosphere from sample and is converted into every 1m²Sample Value during area is evaluated.

The moisture permeability of the resin film of the present invention is preferably 500~2000g/m²My god, more preferably 900~1300g/m²· My god, particularly preferably 1000~1200g/m²My god.

（Mist degree）

The mist degree of the cellulose acylate film of the present invention is preferably less than 1%, is more preferably less than 0.7%, particularly preferably For less than 0.5%.By making mist degree for below above-mentioned higher limit, the transparency with film further increases, becomes easier to use The advantages of making optical film.Mist degree is as long as no specified otherwise, then to be determined by the method used in following Example to calculate Value.The lower limit of mist degree is not particularly limited, but is more than 0.001% in practice.

（Thickness）

The average film thickness of the cellulose acylate film of the present invention is preferably 10~100 μm, more preferably 15~80 μm, enters one Step is preferably 20~70 μm.Operability raising during by for more than 20 μm, preparing the film of tablet shape, therefore preferably.It is in addition, logical Cross as less than 70 μm, be easy to tackle humidity change, effectively further play the improvement of the present invention.

In addition, the cellulose acylate film tool of the present invention haves three layers during the stepped construction of the above, the thickness of the sandwich layer is preferred For 3~70 μm, more preferably 5~60 μm.When the film of the present invention has the stepped construction for the above that haves three layers, the top layer on film two sides（Top layer A and top layer B）Thickness be more preferably 0.5~20 μm, be particularly preferably 0.5~10 μm, most preferably 0.5~3 μm.

（Film is wide）

The wide film of the cellulose acylate film of the present invention is preferably 700~3000mm, more preferably 1000~2800mm, spy You Xuanwei not 1300~2500mm.

The manufacture method ＞ of the cellulose acylate films of ＜ 5

The cellulose acylate film of the present invention is preferably manufactured by solvent cast method.On make use of the fibre of solvent cast method The Production Example of plain acylate film is tieed up, may be referred to U.S. Patent No. 2336310, U.S. Patent No. 2367603, United States Patent (USP) No. 2492078, U.S. Patent No. 2492977, U.S. Patent No. 2492978, U.S. Patent No. 2607704, the U.S. Each specification, British Patent No. 640731 and the British Patent No. of patent the 2739069th and U.S. Patent No. 2739070 Each specification and Japanese Patent Publication 45-4554 of No. 736892, Japanese Patent Publication 49-5614, Japanese Unexamined Patent Application 60- No. 176834, each publication such as Japanese Unexamined Patent Application 60-203430 and Japanese Unexamined Patent Application 62-115035.In addition, the cellulose Acylate film can be handled with drawn.On the method and condition of stretch processing, such as Japanese Unexamined Patent Application 62- may be referred to No. 115035, Japanese Unexamined Patent Publication 4-152125, Japanese Unexamined Patent Publication 4-284211, Japanese Unexamined Patent Publication 4-298310, Japan Each publications such as Unexamined Patent 11-48271.

（Casting method）

As the casting method of solution, there is the rubber cement that will be prepared equably to be expressed into from compression molding in metal support Method, rubber cement being revolved using the method for wing, with reverse with scraper regulation thickness by temporary transient curtain coating in metal support Turn roller be adjusted using method of reverse roll coaters etc., preferably by the method for compression molding.Compression molding have clothes hanger type, T mould types etc., they are preferably used.In addition, in addition to the method enumerated here, can also be incited somebody to action by previously known The various methods of cellulosic triacetate solution curtain coating film are implemented, by considering the difference of the boiling point of solvent for use etc. On the basis of set each condition, the effect same with the content described in each publication can be obtained.

Common curtain coating

The formation of the cellulose acylate film of the present invention is preferably using common curtain coating method, the tape casting, rubbing method etc. are laminated successively The tape casting, from the viewpoint of stable manufacture and reducing production cost, particularly preferred common curtain coating method simultaneously.

When by common curtain coating method and the tape casting is manufactured successively, first, the cellulose acetate solution of each layer is prepared（Glue Slurry）.Common curtain coating method（Multilayer is cast simultaneously）For following the tape castings：In curtain coating supporter（Band or roller）On, from by each layer （It can be 3 layers or more than 3 layers）Respective curtain coating rubber cement is from the curtain coating die head extruded by different slit etc. simultaneously by glue Slurry extrusion, each layer are cast, stripped at the appropriate time from supporter simultaneously, and drying shapes film.Shown in Fig. 2 using common curtain coating Die head 3, the state that is cast is extruded into for totally 3 layers in top layer simultaneously with rubber cement 1 and sandwich layer with rubber cement 2 with supporter 4 in curtain coating Sectional view.

The tape casting is following the tape castings successively：Its main points is first to use the 1st layer of curtain coating on curtain coating supporter Rubber cement is extruded from curtain coating with die head, is cast, and is dried or without drying, thereon by the 2nd layer of curtain coating rubber cement from Curtain coating is extruded with die head, is cast；Rubber cement is cast successively if necessary, is laminated until more than the 3rd layer, in due course from Supporter strips, and drying shapes film.Rubbing method is usually following methods：The film of sandwich layer is configured to by solution film-forming method Film, the coating fluid for being coated on top layer is prepared, using appropriate coating machine, one or two sides simultaneously will coating on film successively Liquid coating, dry, be configured to the film of stepped construction.

As the metal support annularly run used in manufacture cellulose acylate film, plated using surface by chromium The roller of mirror finish is carried out or the stainless steel band of mirror finish has been carried out by surface grinding（It is referred to as band）.Institute The compression molding used can set 1 or more than 2 in the top of metal support.Preferably 1 or 2.Set more than 2 When, each mould of rubber cement amount being cast can be differently divided into various ratios, can also from multiple precise quantitative gear pumps with Respective ratio is by rubber cement liquor charging to mould.The rubber cement used in curtain coating（Resin solution）Temperature be preferably -10~55 DEG C, it is more excellent Elect 25~50 DEG C as.Now, the solution temperature of all process steps can be with identical, can also each operation difference.In the case of difference, only To be desired temperature before it will be cast.

In addition, the material of above-mentioned metal support is not particularly limited, but more preferably use SUS systems（Such as SUS316）.

（Peel off）

The manufacture method of the cellulose acylate film of the present invention is preferably comprised the rubber cement film from the metal support The process stripped.The method of stripping in the manufacture method of cellulose acylate film is had no particular limits, uses known side During method, fissility can be improved.

（Stretch processing）

Preferably comprised in the manufacture method of the cellulose acylate film of the present invention by the process of the film stretching after film.Fiber The draw direction of plain acylate film is preferably film conveyance direction and the direction orthogonal with conveyance direction（Transverse direction）In any side To, but from subsequent use from the viewpoint of the polarization machining process of the film, it is particularly preferably orthogonal with film conveyance direction Direction（Transverse direction）.

The method stretched along transverse direction is for example recorded in 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.When carrying out the stretching of length direction, such as the speed of the carrying roller of adjusting film, the coiling speed of film is faster than stripping for film Speed, so as to by film stretching.When carrying out the stretching of transverse direction, it can be removed in the case where keeping the width of film with stenter Send, can also slowly widen the width of stenter by film stretching.It can also be stretched after film drying using stretching-machine（It is excellent Choosing uses the uniaxial tension of long stretching-machine）.

When the cellulose acylate film of the present invention to be used as to the diaphragm of the polarizer, in order to suppress to be polarized from oblique Light leak during piece is, it is necessary to which slow axis of the axis of homology of the polarizer with resin film of the invention in face is abreast configured.Continuously The axis of homology of the polarizer of the wound membrane shape of manufacture is generally parallel with the width of wound membrane, therefore for rising the wound membrane shape The diaphragm that inclined device is formed with by the cellulose acylate film of wound membrane shape is continuously bonded, it is necessary in the face of the diaphragm of wound membrane shape Slow axis is parallel with the width of film.It is therefore preferable that more stretched than width.In addition, stretch processing can be Carried out during 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% of transverse direction, more preferably 5~80%, particularly preferably 5~40% are drawn Stretch.In addition, stretch processing can also be carried out during film making process, the blank after being film-made and batching can also be drawn Stretch processing.In the former case, can be stretched in the state of containing residual solvent amount, preferably according to residual solvent amount =（Remain the film quality after volatile ingredient quality/heating）× 100% is stretched for 0.05~50% mode.Especially It is preferred that carry out 5~80% stretchings in the state of being 0.05~5% in residual solvent amount.Wherein, it is non-stretched to stretch 0%.

（Dry）

In the manufacture method of the cellulose acylate film of the present invention from the viewpoint of showing property of delay, preferably comprise fibre Tie up the process of plain acylate film drying and by dried resin film of the invention in glass transition temperature（Tg）- 10 DEG C with On temperature under the process that is stretched.

The drying of the rubber cement in metal support in the manufacture of the cellulose acylate film of the present invention generally has from metal Supporter（Roller or band）Face side, tablet i.e. in the metal support surface blowing hot-air method, from roller Or the back side blowing hot-air of band method, make to control the liquid of temperature from the opposite side in the rubber cement of band or roller curtain coating face I.e. rear-face contact, by heat transfer by roller or band heating in rear surface liquid heat transfer method of control surface temperature etc., it is excellent Select rear surface liquid heat exchange pattern.As long as the boiling point of the surface temperature of the metal support before curtain coating solvent used in rubber cement Can be then any temperature below.But in order to promote drying, and in order that it loses flowability in metal support, It is preferably set to the temperature of 1~10 DEG C of the low boiling point of the solvent minimum than boiling point in used solvent.It should be noted that Will curtain coating rubber cement cooling, without dryly stripping in the case of, not limited to this.

On the regulation of film thickness, in order to reach desired thickness, can adjust solid component concentration contained in rubber cement, The slit gap of the die head of mould, the extrusion pressure extruded from mould, metal support speed etc..

On the length of so obtained cellulose acylate film, preferably carried out in a manner of every 1 roller is 100~10000m Batch, more preferably 500~7000m, more preferably 1000~6000m.When batching, preferably assign and rolling at least one end Flower, the width of annular knurl be preferably 3mm~50mm, more preferably 5mm~30mm, it is highly preferred be 0.5~500 μm, more preferably 1 ~200 μm.It unilateral can be embossed can also bilateral embossing.

When as big picture with the optical compensation films of liquid crystal display device, preferably for example make a width of 1470mm of film with On, it is formed.In addition, the present invention polaroid protective film in not only include be cut into can direct-assembling enter liquid crystal display dress The film of the diaphragm mode for the size put, in addition to the film by way of continuous production is fabricated to strip and wound into rolls. The polaroid protective film of latter means can with the state take care of, conveyance etc., when actual assembled enters liquid crystal display device or with Polarizer etc. uses after being cut into desired size when being bonded.Furthermore it is also possible to by being prepared as the poly- of strip that grow up After polarizer of the compositions such as vinyl alcohol film etc. is directly bonded with strip, when actual assembled enters liquid crystal display device, it is cut into Used after desired size.As a mode of the optical compensation films of wound into rolls, can include be wound into a roll it is a length of The mode of more than 2500m web-like.

＜ ＜ polarizer ＞ ＞

The polarizer of the present invention at least has the cellulose acylate film of the polarizer and the present invention.

The polarizer of the present invention preferably has the polarizer and the film of the invention in the one or two sides of the polarizer. The polarizer has the iodine system polarizer, the dyestuff system polarizer and the polyenoid system polarizer using dichroic dye.The iodine system polarizer and dye The material system polarizer manufactures usually using polyvinyl alcohol mesentery.The cellulose acylate film of the present invention is used as polaroid protective film When, the preparation method of polarizer is not particularly limited, usual way can be used to make.There are following methods：To what is obtained Cellulose acylate film carries out basic treatment, and polyvinyl alcohol film is immersed in iodine solution and stretched, in the polarizer of making Two sides be bonded using fully saponified polyvinyl alcohol water solution.Basic treatment can also be replaced, implements such as Japanese Unexamined Patent Publication Easy bond processing described in 6-94915 publications, Japanese Unexamined Patent Publication 6-118232 publications.As for film process will to be protected The bonding agent that face is bonded with the polarizer, can include the polyethenol series bonding agent such as polyvinyl alcohol, polyvinyl butyral resin, Ethene base system latex such as butyl acrylate etc..

The mode that the cellulose acylate film of the present invention is fitted on the polarizer is preferably according to the axis of homology for making the polarizer The mode substantially orthogonal with the slow axis of the cellulose acylate film of the present invention is bonded.It is excellent in the liquid crystal display device of the present invention Select the axis of homology and the slow axis of the cellulose acylate film of the present invention of polarizer substantially orthogonal.Wherein, it is substantially orthogonal to refer to The principal refractive index nx of the cellulose acylate film of present invention direction and the direction of the axis of homology of polarizer are with 90 ° ± 10 ° of angle Degree is intersecting, preferably with 90 ° ± 5 ° of angle of intersection, more preferably with 90 ° ± 1 ° of angle of intersection.By within the above range, energy Enough light leaks further reduced under polarizer cross Nicols.

The present invention polarizer not only include be cut into can direct-assembling enter liquid crystal display device size diaphragm side The polarizer of formula, in addition to by way of continuous production is fabricated to strip and wound into rolls（Such as roll up a length of 2500m with Upper or more than 3900m mode）Polarizer.In order to be preferably for big picture liquid crystal display device, the width of polarizer More than 1470mm.On the specific composition of the polarizer of the present invention, can be formed without particular limitation using known, such as The composition described in Fig. 6 of Japanese Unexamined Patent Publication 2008-262161 publications can be used.

＜ ＜ liquid crystal display device ＞ ＞

The liquid crystal display device of the present invention has liquid crystal cells and the polarizer of the present invention.

The present invention liquid crystal display device be IPS, OCB or VA pattern liquid crystal display device, its have liquid crystal cells and A pair of polarizers in the both sides of the liquid crystal cells are configured, wherein, at least one polarization for the present invention in the polarizer Piece.The Inner Constitution of typical liquid crystal display device is shown in Fig. 1., can as the specific composition of the liquid crystal display device of the present invention Known form is used without particular limitation.In addition, also preferably use Fig. 2 of Japanese Unexamined Patent Publication 2008-262161 publications Described in composition.

Embodiment

Enumerate embodiment below further specifically to illustrate the present invention, but these embodiments are not to the present invention Being defined property is explained.

（Synthesis example 1）

2,6- dimethyl benzenes are added in the glass system flask of the 300ml with thermometer, backflow cooling tube and mixer Phenol 49g（0.4 mole）, limonene 6.7g（0.05 mole）With the Amberlyst as catalyst（R）15H4.8g.By in flask Temperature be warming up to 100 DEG C, heating stirring 5 hours.Thereafter, room temperature, filtering are cooled to, insoluble component is washed with ethyl acetate. Heating under reduced pressure is carried out to obtained solution, solvent and unreacted 2,6- xylenols is evaporated, is generated and remained by column chromatography Thing, obtain the example compound as reaction product（A-1）14g（Yield is 73%）.Wherein, will¹H-NMR is composed and Journal Of Organic Chemistry, volume 60, page 3612~3618（Nineteen ninety-five）Described in data compare, thereby confirm that here The product arrived is with following 3 kinds of mixtures for principal component.

Chemical formula 25

（Synthesis example 2）

2,6- dimethyl benzenes are added in the glass system flask of the 200ml with thermometer, backflow cooling tube and mixer Phenol 18.3g（0.15 mole）, 1,3- adamantane glycol 3.15g（0.018 mole）, dichloromethane 60mL.Trifluoro is added thereto Methanesulfonic acid 1.83mL, it is stirred at room temperature 5 hours.Water 40mL, liquid separation are added, aqueous phase is removed, adds magnesium sulfate, makes it dry It is dry, then filtered, solvent under reduced pressure is evaporated.Dichloromethane 50mL is added thereto to be dissolved, and adds acetic acid thereto The mixed liquor of ethyl ester/hexane（1/1（V/v））50mL, the solid being filtrated to get, is dried, and obtains the example chemical combination of the present invention Thing（A-51）.

On except above-mentioned example compound（A-51）Formula of the invention in addition（I）The compound of expression, it can pass through The method synthesis similar with above-mentioned synthesis example 1 and synthesis example 2.

Embodiment 1, comparative example 1

（1）The film of cellulose acylate film

（The preparation of cellulose acylate）

Prepare the cellulose acylate that degree of substitution with acetyl group is 2.87.It is carried out as follows：Add the sulfuric acid as catalyst （It is 7.8 mass parts relative to the mass parts of cellulose 100）, the carboxylic acid of the raw material as acyl substituent is added, is entered at 40 DEG C Row acylation reaction.In addition, after acylated, cured at 40 DEG C.And then the low molecular weight compositions of the cellulose acylate are used Acetone washing removes.

（The preparation of top layer rubber cement）

The preparation of Cellulose acylate solutions

Following compositions are put into blending tank, stirs, dissolve each composition, prepare Cellulose acylate solutions.

Wherein, the first industrial chemistry company system MONOPET（Registration mark）SB be sucrose benzoic ether, Eastman Chemical company systems SAIB-100 is the acetic acid and isobutyrate of sucrose.

The preparation of Mat agent solution

Following compositions are put into dispersion machine, stirs, dissolve each composition, prepare Mat agent solution.

The preparation of ultraviolet absorbent solution

Following compositions are put into blending tank, heated while stirring, each composition is dissolved, it is molten to prepare ultra-violet absorber Liquid.

Chemical formula 26

After the above-mentioned mass parts of Mat agent solution 1.3 and the mass parts of ultraviolet absorbent solution 3.4 are filtered respectively, using Line mixer mixes, and then adds the mass parts of Cellulose acylate solutions 95.3, is mixed using in-line mixing machine, prepares top layer and uses Solution.

（The preparation of basic unit's rubber cement）

The preparation of Cellulose acylate solutions

Following compositions are put into blending tank, stirs, dissolve each composition, prepare basic unit's rubber cement.

（Curtain coating）

It is by basic unit's rubber cement produced above and same with 3 layers of rubber cement for the top layer of its both sides using roller casting device When be equably cast to the curtain coating supporter of stainless steel from curtain coating mouth（It is -9 DEG C to support temperature）.In the rubber cement of each layer Residual solvent amount be about 70 mass % in the state of strip, the both ends of the width of film are fixed with pin stenter, Residual solvent amount is dried simultaneously to be stretched in the state of 3~5 mass %, at 1.28 times along transverse direction progress.Thereafter, lead to Cross between the roller of annealing device and transport, be further dried, obtain the cellulose acylate film 101 compared.Obtained fiber The thickness of plain acylate film 101 is 60 μm, width 1480mm.

Instead of the example compound A-7 in above-mentioned cellulose acylate film 101, by the species and content of compound as hereinafter Record in table 6 is changed, and in addition, in the same manner as cellulose acylate film 101, manufactures the cellulose of the present invention respectively Acylate film 102~115 and the cellulose acylate film c11~c14 compared.

In addition, in above-mentioned cellulose acylate film 110, by obtained cellulose acylate film according to thickness reach 40 μm, The mode that width reaches 1480mm is cast, dried, and obtains the cellulose acylate film 116 of the present invention.Instead of the cellulose acylated Example compound A-1 in thing film 116 seen, the record in the species of compound such as table 6 hereinafter is changed, in addition, In the same manner as cellulose acylate film 116, the cellulose acylate film 117 and 118 of the present invention is manufactured respectively and is compared Cellulose acylate film c15.

Similarly, in above-mentioned cellulose acylate film 110, obtained cellulose acylate film is reached into 25 μ according to thickness M, width reach 1480mm mode be cast, dry, obtain the present invention cellulose acylate film 119.Instead of the cellulose acyl Example compound A-1 in compound film 119, the record in the species of compound such as table 6 hereinafter is changed, in addition, In the same manner as cellulose acylate film 119, the cellulose acylate film 120 and 121 of the present invention is manufactured respectively and is compared Cellulose acylate film c16.

In addition, instead of the MONOPET in above-mentioned cellulose acylate film 101（Registration mark）SB and SAIB-100, addition Contracting polyester plasticizer is following polycondensation polymers（A）12 mass parts, and then example compound A-7 is replaced, by the kind of compound Record in class and content such as table 6 hereinafter is changed, and in addition, in the same manner as cellulose acylate film 101, is manufactured respectively The cellulose acylate film 201~203 of the present invention and the cellulose acylate film c21~c23 compared.

Polycondensation polymer（A）：The polyester being made up of adipic acid and ethylene glycol（End is hydroxyl）（Number-average molecular weight= 1000）

The evaluation of the yellow coloring of film is carried out to each cellulose acylate film.

In addition, as reference data, the measure of moisture permeability is carried out.

Obtained result is collected and is shown in following table 6.

It should be noted that these cellulose acylate films are hereinafter also referred to as polaroid protective film.

(evaluation)

（The evaluation of moisture permeability）

Moisture permeability test based on JIS Z0208（Kapp Method）, in the atmosphere that temperature is 40 DEG C, relative humidity is 90%RH In, the quality for the water vapour that measure passes through in 24 hours from the cellulose acylate film determined simultaneously is converted into 1m²During Area of Sample Value, evaluated according to following benchmark.

A：Moisture permeability is less than 1100g/m²My god

B：Moisture permeability is 1100~1200g/m²My god

C：Moisture permeability is more than 1200g/m²My god

（Film through when colour（Light）Evaluation）

Super Xenon Weather Meter are used to each polaroid protective film of above-mentioned making（Suga testing machine strains Formula commercial firm SX75）, it is 150W/m in radiation illumination², Black panel temperature is 63 DEG C, relative humidity is 50%RH condition Under, carry out 72 hours light irradiations.Thereafter, form and aspect b is determined using the spectrophotometer UV3150 of Shimadzu Seisakusho Ltd.^*.As form and aspect b^* Value to negative value side increase when, the blueness increase in transmitted light, when to when increasing on the occasion of side, yellow increase.

Evaluation is carried out according to following benchmark.

A：The b of every 1^*For less than 0.8

B：The b of every 1^*More than 0.8 and below 1.2

C：The b of every 1^*More than 1.2

Obtained result is collected and is shown in following table 6.

Embodiment 2, comparative example 2

（2）The preparation of polarizer

(saponification process of polaroid protective film)

By each cellulose acylate film i.e. polaroid protective film made in embodiment 1 2.3mol/L sodium hydroxide water Impregnated 3 minutes in solution, at 55 DEG C.Washed in the washing bath of room temperature, with 0.05mol/L sulfuric acid at 30 DEG C With.Washed again in the washing bath of room temperature, then with 100 DEG C of heated-air drying.In this way, each polaroid protective film is carried out The saponification process on surface.Wherein, the polarizer is polarized using conventional as described in ＜ ＜ polarizer ＞ ＞ parts above Device.

(preparation of polarizer)

Iodine absorption is set to make the polarizer on the polyvinyl alcohol film of drawn.

Manufacture in embodiment 1 and the polaroid protective film 101 through above-mentioned saponification process are pasted with polyethenol series bonding agent Close the one side of the polarizer.Commercially available cellulosic triacetate film（Fujitac TD80UF, Fuji Photo Film Co., Ltd.'s system） Same saponification process is carried out, with polyethenol series bonding agent with being fitted with the polaroid protective film 101 1 through saponification process On the face of the polarizer of the opposite side in side, fitting has carried out the above-mentioned commercially available cellulosic triacetate film of saponification process.

Now, the axis of homology of the polarizer is made with being made in embodiment 1 and having carried out the polaroid protective film of saponification process Slow axis is orthogonally configured.In addition, the axis of homology for the polarizer and having carried out the commercially available cellulose iii second of saponification process The slow axis of acid esters film, also configured according to orthogonal mode.

So it is prepared for the polarizer 101 of the present invention.

For polaroid protective film 102~121,201~203 and the polaroid protective film c11~c16, the c21 that compare~ 23, also carry out the making of saponification process and polarizer as described above respectively, so as to made the present invention polarizer 102~ 121st, 201~203 polarizer c11~c16 for, comparing, c21~23.

（The evaluation of polarizer durability）

Polarizer endurancing is that polarizer is being fitted on glass by adhesive and is making the cellulose of the present invention Acylate film is to be carried out as follows under the form of Air Interface side.

Prepare 2 samples that polarizer has been bonded on glass（About 5cm × 5cm）.In monolithic quadrature transmissivity measure, make The cellulose acylate film side of the invention of the sample is set towards light source, is measured.2 samples are determined respectively, will Orthogonal transmission of its average value as the polarizer of the present invention.The orthogonal transmission of polarizer is using Japan's light splitting strain formula meeting Society automatic polarization film measure device VAP-7070, it is measured in the range of 380nm~780nm, and using under 410nm Measured value.Thereafter, under the conditions of corresponding with the thickness of film, through when preserve after with same method determine orthogonal transmission. Obtain through when front and rear orthogonal transmission change, as polarizer durability, evaluated according to following benchmark.

It should be noted that the scope that the relative humidity in the environment of non-damping is 0~20%RH.The result that will be obtained It is shown in following table 6.

（Through when condition）

Sample 101~115,201~203, c11~c14 and c21~c23：

80 DEG C, relative humidity be 90%RH in the environment of, 168 hours and 336 hours samples 116~118 and c15：

80 DEG C, relative humidity be 90%RH in the environment of, 120 hours and 240 hours samples 119~121 and c16：

60 DEG C, relative humidity be 95%RH in the environment of, 500 hours and 1000 hours A：Through when front and rear orthogonal transmission Change be less than 0.6%

B：Through when front and rear orthogonal transmission change turn to 0.6~1.0%

C：Through when front and rear orthogonal transmission change more than 1.0%

The result is collected and is recorded in table 6 below.

Wherein, H-1~H-3 in table 6 is following compound.

Chemical formula 27

It was found from the result of above-mentioned table 6, the formula containing the present invention（I）The cellulose acyl of the invention of the compound of expression Compound film be polaroid protective film can effectively suppress through when in the polarizer deterioration, through when coloring it is few.Wherein, polarize The moisture permeability of piece diaphragm 101~115,201~203 is low.

On the other hand, the cellulose acylate film of the comparison containing above-mentioned amphyl relatively is polarizer protection Film c11, c12, c13, c21 and c22 suppress the deterioration of polarizer in which can not take into account compared with the polaroid protective film of the present invention With suppress through when colour.In addition, the formula of the present invention was not both contained（I）The compound of expression does not contain the phenol compared yet and derived The cellulose acylate film of the comparison of thing is polaroid protective film c14~c16, c23 and the cellulose acylate film of the present invention I.e. polaroid protective film is compared, also poor in terms of polarizer durability.

The result is shown, by using the polarizer for the cellulose acylate film for employing the present invention, can be made as above The liquid crystal display device of shown excellent properties.

Although with the present invention is described together with embodiments thereof, applicant think as long as no particularly refer to Fixed, then any specific part illustrated is not limitation of the invention, as long as not violating shown in appended claims The spirit and scope of invention, then the explanation of wide scope should be carried out to it.

The application is advocated using the patent application Japanese Patent Application 2012-210217 submitted in Japan on the 24th of September in 2012 as base The priority of plinth, its by referring to by its content include and be used as this specification record a part.

Claims (17)

1. a kind of cellulose acylate film, it contains at least one kind of and cellulose acylated in the compound that following logical formula (I)s represent Thing；

Logical formula (I)

In logical formula (I), R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴' and R⁵' hydrogen atom or substituent are represented independently of one another；Wherein, R¹Or R³In any one and R¹' or R³' in any one represent hydroxyl；R²And R²' represent what following formulas (1) represented independently of one another Group；In addition, R³For hydroxyl when, R⁴Represent the group that following formulas (1) represent, R³' when being hydroxyl, R⁴' represent following formulas (1) group represented；L is the aliphatic group of the ring-type of divalent or the alkylidene connected by carbon-to-carbon triple bond；

Formula (1)

In formula (1), R^aAnd R^bHydrogen atom is represented independently of one another or can have alkyl, alkenyl or the alkynyl of substituent, R^aWith R^bIt can be mutually bonded to form ring.

2. cellulose acylate film according to claim 1, wherein, the compound that the logical formula (I) represents is following logical The compound that formula (IA) or (IB) are represented；

Formula (IA)

Formula (IB)

In formula (IA), (IB), R¹、R³、R⁴、R⁵、R¹’、R³’、R⁴’、R⁵’、R^a、R^bWith the R in L and the logical formula (I)¹、R³、R⁴、 R⁵、R¹’、R³’、R⁴’、R⁵’、R^a、R^bIt is identical with L implication.

3. cellulose acylate film according to claim 1 or 2, wherein, the compound of the logical formula (I) or (IA) expression The compound represented for following formulas (IA-1)；

Formula (IA-1)

In formula (IA-1), R^a、R^bWith the R in L and the logical formula (I)^a、R^bIt is identical with L implication.

4. cellulose acylate film according to claim 1 or 2, wherein, the company for being used to connect the phenyl ring at both ends of the L The carbon number of chain link is 4~20.

5. cellulose acylate film according to claim 1 or 2, wherein, the L is the aliphatic group of the ring-type of divalent.

6. cellulose acylate film according to claim 1 or 2, wherein, the R^aAnd R^bBe each independently hydrogen atom or Carbon number is 1~12 alkyl.

7. according to the cellulose acylate film of claim 1 or 2, wherein, the R^aAnd R^bIt is hydrogen atom.

8. cellulose acylate film according to claim 1 or 2, wherein, the acyl substitution of the cellulose acylate (A) following formula is met；

1.5≤A≤3.0。

9. cellulose acylate film according to claim 1 or 2, wherein, the acyl group of the cellulose acylate is acetyl Base, and degree of substitution with acetyl group (B) meets following formula；

2.0≤B≤3.0。

10. cellulose acylate film according to claim 1 or 2, its also further containing in polycondensation ester compounds extremely Few a kind is used as plasticizer.

11. cellulose acylate film according to claim 10, wherein, the polycondensation ester compounds are by that following will lead to Obtained from least one kind of glycol polycondensation that at least one kind of dicarboxylic acids and following formulas (b) that formula (a) represents represent；

Formula (a)

HOC (=O)-X-CO₂H

Formula (b)

HO-Z-OH

In formula (a), (b), X represents that the carbon number of the aliphatic group that the carbon number of divalent is 2~18 or divalent is 6~18 Aromatic group, Z represent divalent carbon number be 2~8 aliphatic group.

12. cellulose acylate film according to claim 10, wherein, the number-average molecular weight of the polycondensation ester compounds is 500~2000.

13. cellulose acylate film according to claim 10, wherein, the end of the polycondensation ester compounds is blocked.

14. cellulose acylate film according to claim 1 or 2, it is also containing monose or by 2~10 monosaccharide unit structures Into carbohydrate at least one kind of be used as plasticizer.

15. cellulose acylate film according to claim 14, wherein, the carbohydrate is by alkyl, aryl or acyl Base substitutes.

16. a kind of polarizer, it at least with the cellulose acylate film any one of claim 1~15 and is polarized Device.

17. a kind of liquid crystal display device, it at least has the polarizer and liquid crystal cells described in claim 16.