CN101124250A

CN101124250A - Cellulose acylate grains and method for producing the same, cellulose acylate film and method for producing the same, polarizer, optical compensatory film, antireflection film and liquid-crystal displ

Info

Publication number: CN101124250A
Application number: CNA2006800055597A
Authority: CN
Inventors: 樋口聪; 松藤明博; 吉田哲也; 后藤靖友; 桥本齐和
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2005-12-21
Filing date: 2006-12-21
Publication date: 2008-02-13

Abstract

Cellulose acylate grains having a heat quantity of crystalline fusion of at most 10 J/g. A film prepared by melt-casting the grains is free from the problem of yellowing when built in liquid-crystal display devices.

Description

Cellulose acylate pellet and manufacture method thereof, cellulose acylate film and manufacture method thereof, polarizer, optical compensating film, anti-reflection film and liquid crystal indicator

Technical field

The present invention relates to cellulose acylate pellet, cellulose acylate film and their manufacture method.The invention still further relates to the polarizer, optical compensating film, anti-reflection film and the liquid crystal indicator that comprise cellulose acylate film with excellent optical property.

Background technology

Up to now, in the manufacturing of the cellulose acylate film that the liquid crystal image display unit is used, be to use solution-casting method basically; be included in dissolving cellulos acylate in the organic solvent that contains chlorine such as the methylene dichloride; it is carried out curtain coating on base material, and be dried, thereby form film.Methylene dichloride is a kind of organic solvent that contains chlorine; it is advantageously used for the solvent that cellulose acylate is used; therefore because it is a kind of good solvent for cellulose acylate, and have lower boiling (about 40 ℃), have and in film forming step and drying step, be easy to the evaporable advantage.

Yet in recent years, from the viewpoint of environment protection, the strong request inhibition contains the release of organic solvent He other organic solvents of chlorine.Therefore, attempted some countermeasures, be used for suppressing as much as possible the release of organic solvent, for example, used the closed system of more strict control, be enough to prevent that organic solvent from leaking from it; Perhaps may lead into absorption column, before being discharged in the outside air, absorb at organic solvent from the organic solvent that the film forming system is leaked; Perhaps use the flame organic solvent; Perhaps decompose with electron beam.Yet,, can not prevent fully that still organic solvent from discharging, and requires further improvement even use these countermeasures.

Researched and developed in film forming method (referring to JP-A-2000-352620) under the situation with an organic solvent not, this is the fusion casting film-forming of cellulose acylate.The document claims, the carbochain of the ester group in the plain acylate of elongated fibres, thus reduce the fusing point of polymkeric substance, be easy to carry out the fusion casting film-forming of polymkeric substance like this.Particularly, cellulose ethanoate is become cellulose propionate.

Summary of the invention

We, present inventor just, trial uses the film according to the fusion curtain coating film manufacturing of patent documentation 1 to form polarizer, and attempt polarizer is combined in the liquid crystal indicator (LCD), but we know now, when this liquid crystal indicator of life-time service, its problem is that flavescence increases.For example, we know, when liquid crystal indicator being carried out duration when testing for the forced aging corresponding to its actual use of its weather resistance time (for example, carrying out 1000 hours in 80 ℃), remarkable flavescence take place.Flavescence reduces the commodity value of liquid crystal indicator, therefore, must research and develop the film that does not have the flavescence problem.

Because above-mentioned prior art problem, we, just the present inventor makes further research, and with the film that provides when being combined into liquid crystal indicator in and can flavescence during long-time use, and is provided for film forming particle.

We, present inventor just, serious analysis liquid crystal indicator the reason of flavescence may take place when using for a long time, consequently, the aged chemical transformation may take place and cause flavescence in the degradation production that generates during the fusion film forming.Based on this discovery, we have successfully reduced the crystallization of the cellulose acylate pellet that uses in the fusion casting film-forming and have solved the flavescence problem.Therefore, the present invention includes following formation.

[1] a kind of cellulose acylate pellet, its crystallization fusion (crystalline fusion) heat is at most 10J/g.Because cellulose acylate pellet of the present invention has low-crystallinity, therefore fusion in the forcing machine of kneading at short notice.When cellulose acylate pellet of the present invention is used for fusion curtain coating film process, can reduce the required heat of molten resin, thereby the thermolysis that can prevent resin causes weather stain.The cellulose acylate film that uses cellulose acylate pellet of the present invention to make when it being combined into liquid crystal indicator and long-time the use, can prevent its flavescence fully.

[2] as [1] described cellulose acylate pellet, wherein the quantity of needle-like impurity is 50/mg at the most.

[3] as [1] or [2] described cellulose acylate pellet, its sulphate groups mass contg is that 0ppm is extremely less than 200ppm.

[4] as each described cellulose acylate pellet of [1]-[3], wherein the ratio of (basic metal molal quantity and group II metal molal quantity sum)/(sulfate groups molal quantity) is 0.3-3.0.

[5] as [4] described cellulose acylate pellet, wherein said group II metal is a calcium.

[6] as each described cellulose acylate pellet of [1]-[5], it satisfies following formula (S-1)-(S-3):

(S-1)2.6≤X+Y≤3.0，

(S-2)0≤X≤1.8，

(S-3)1.0≤Y≤3.0；

Wherein X represents the substitution value of ethanoyl to the Mierocrystalline cellulose hydroxyl; Y represents propionyl, butyryl radicals, pentanoyl and the caproyl total substitution value to the Mierocrystalline cellulose hydroxyl.

[7] as each described cellulose acylate pellet of [1]-[6], it is a pellet.

[8] make the method for cellulose acylate pellet, it is included in twin screw and kneads in the forcing machine with the screw speed of 50-300rpm and the cellulose acylate resin of kneading under the resin of 2-9MPa of the kneading-pressure of kneading.

[9] as the method for [8] described manufacturing cellulose acylate pellet, it is included in 160 ℃-220 ℃ described cellulose acylate resins and with its granulation kneaded and extrude.

[10], wherein knead the interior pressure of forcing machine for being lower than 1 normal atmosphere with described resin granulation by controlling described twin screw as the method for [8] or [9] described manufacturing cellulose acylate pellet.

[11], wherein knead in the forcing machine described resin granulation rare gas element being introduced described twin screw as the method for each described manufacturing cellulose acylate pellet of [8]-[10].

[12] as the method for each described manufacturing cellulose acylate pellet of [9]-[11], it comprises the pellet that grinding forms through granulation.

[13], described cellulose acylate and the carbonate that is selected from least a metal in sodium, potassium, magnesium and the calcium, supercarbonate (hydrogencarbonate), oxyhydroxide or oxide compound reaction are neutralized to knead as the method for each described manufacturing cellulose acylate pellet of [8]-[12].

[14] make the method for cellulose acylate pellet, it comprise by SP value for dissolving cellulos acylate in the solvent of 7-10 to prepare cellulose acylate solution, solidify described cellulose acylate then.

[15] as the method for [14] described manufacturing cellulose acylate pellet, the solvent of wherein said SP value 7-10 is that the SP value is the ketone solvent of 7-10 for the ester solvent of 7-10, halogenated hydrocarbon solvent or the SP value that the SP value is 7-10.

[16] as the method for [14] or [15] described manufacturing cellulose acylate pellet, wherein realize described curing to remove described solvent by the described cellulose acylate solution of drying.

[17] as the method for [14] or [15] described manufacturing cellulose acylate pellet, wherein, described cellulose acylate solution realizes described curing so that described cellulose acylate is precipitated by being introduced in the poor solvent.

[18] make the method for cellulose acylate film, it comprises each described cellulose acylate pellet fusion curtain coating of [1]-[7] is become film.

[19] as the method for [18] described manufacturing cellulose acylate film, wherein under the line pressure of 3kg/cm-100kg/cm, form described film by the use touch roll.

[20] as the method for [18] described manufacturing cellulose acylate film, wherein under the contact pressure of 0.3MPa-3MPa, form described film by the use touch roll.

[21] as the method for each described manufacturing cellulose acylate film of [18]-[20], it also is included at least one direction with the cellulose acylate film stretching 1%-300% that forms.

[22] a kind of cellulose acylate film, it is made according to each described manufacture method of [18]-[21].

[23] a kind of cellulose acylate film, it is formed by each described cellulose acylate pellet of [1]-[7], and its residual solvent content is 0.01 quality % at the most.

[24] a kind of polarizer, it comprises polarization film and at least one [22] or [23] described cellulose acylate film that closes layer by layer thereon.

[25] a kind of optical compensating film, it comprises the base material of [22] or [23] described cellulose acylate film as it.

[26] a kind of anti-reflection film, it comprises the base material of [22] or [23] described cellulose acylate film as it.

[27] a kind of liquid crystal indicator, it comprises at least a in [24] described polarizer, [25] described optical compensating film and [26] described anti-reflection film.

The method of making cellulose acylate pellet of the present invention can be included in before the neutralization activated cellulose, acylated cellulose and/or use sulfuric acid cleaned.

When cellulose acylate film of the present invention is combined in the liquid crystal indicator and use for a long time, can prevent its flavescence.Therefore, the cellulose acylate film utmost point of the present invention is suitable for polarizer, optical compensating film and anti-reflection film.According to the manufacture method of cellulose acylate pellet of the present invention, can make cellulose acylate film with simplified way.

Description of drawings

Fig. 1 is a synoptic diagram of implementing the sketch map of an embodiment of the film forming device of fusion curtain coating of the present invention.In this accompanying drawing, the 101st, the forcing machine of kneading, the 102nd, toothed gear pump, the 103rd, strainer; the 104th, mould, the 105th, touch roll, the 106th, curtain coating cooling drum, the 107th, cellulose acylate; the 108th, the machine direction stretch district, the 109th, crisscross drawing zone, the 110th, batch the district.

Embodiment

Describe cellulose acylate pellet, cellulose acylate film, their manufacture method and their application below in detail.

In this manual, term " particle " is broadly to comprise size 0.01mm ³-100000mm ³About the notion of any and each particulate matter.

Equally also in this manual, term " pellet " is the notion in " particle " scope, and this is meant size 1mm ³-500mm ³About particulate matter.

That puts down in writing below can be at representative embodiment more of the present invention to the explanation of constitutive requirements of the present invention, yet, the invention is not restricted to this.In this manual, the numerical range of expressing with term " number-another number " refers in the last number of this scope lower limit of indication and indicates scope between the back number of this range limit.

Suppress flavescence:

In the present invention, the cellulose acylate pellet of making the cellulose acylate film use has following feature, prevents the film flavescence that forms during with also long-time use the in being combined into liquid crystal indicator.In addition, make the method for cellulose acylate pellet and the method for manufacturing cellulose acylate film and also have following feature.They are described below in regular turn.

(1) characteristic of cellulose acylate pellet:

As mentioned above, in the present invention, for preventing film flavescence when cellulose acylate film is combined in the liquid crystal indicator and use for a long time, the crystallization fusion heat cellulose acylate pellet of 10J/g at the most is used to make cellulose acylate film.The crystallization fusion heat of cellulose acylate pellet is 0J/g-7J/g more preferably, more more preferably 0J/g-5J/g.Have the cellulose acylate pellet of the present invention of the brilliant fusion heat of brief summary by use, particle can be in fusion curtain coating film process Flashmelt.Compare with existing method, discovery can significantly prevent the resin thermolysis as the flavescence major cause.

In the present invention, the summation from the thermal absorption peak area of DSC (dsc) obtains the crystallization melting heat.When not detecting absorption peak, the crystallization melting heat is expressed as 0 (J/g).

Preferably, the number of the needle-like impurity in the cellulose acylate pellet of the present invention is 50/mg at the most, more preferably 0-40/mg, more preferably 0-30/mg again.When needle-like impurity was present in the particle, they were as nuclear, and promotion their crystallizations on every side in particle.Therefore, when needs in the fusion casting film-forming fusion they the time, they may be thermal decomposited and improve weather stain.Especially, place the strainer (usually, it places kneads between forcing machine and the mould) of fusion curtain coating film deposition system to have big dead band, thereby resin melt may stay in therebetween and thermolysis take place and cause weather stain.When using above-mentioned cellulose acylate pellet with less metering pin shape impurity, can more effectively prevent thermolysis.

The reason of needle-like impurity is a unreacted Mierocrystalline cellulose still residual after the Mierocrystalline cellulose acidylate.Therefore, be to reduce the quantity of needle-like impurity, preferred use activates the method for the raw cellulose that acidylate uses in advance, for example, and by making its swelling, so that used acylating agent (carboxylic acid anhydride) can soak into it fully; And/or the Mierocrystalline cellulose that filters acidylate by filter paper or filter cloth is placed in the poor solvent so that the sedimentary method of cellulose acylate then therefrom to remove needle-like impurity.

Preferably, the sulphate groups mass contg of cellulose acylate pellet of the present invention be 0ppm-less than 200ppm, more preferably 10ppm-160ppm, more preferably 20ppm-120ppm again.Residual sulfate groups as herein described is the sulfate groups that exists with the form of bonding sulfuric acid (bound sulfuric acid), nonbonding sulfuric acid, salt, ester or their title complex in cellulose acylate; The sulphate groups mass contg refers to the total content of these sulfate groups.Sulfate groups in the cellulose acylate is can form sulfuric ester with cellulosic hydroxyl bonding because be used as the sulfuric acid of acylation catalyst; or can be caught with the form of its free sulfuric acid or its salt, ester or title complex wherein by cellulose acylate; and they can not be removed in washing step, but stay in the polymkeric substance.Can prepare the cellulose acylate pellet of sulphate groups mass contg by the plain acylate of suitable washing the fibre in preparation process less than 200ppm.Residual sulfate groups can be used the residual hydroxy groups esterification of cellulose acylate, but because the strong hydrogen bonding bonding, cellulose acylate pellet is easy to be brought together, and promotes its crystallization.Therefore, when particle in fusion curtain coating film process during fusion, their can thermolysis and increase weather stain.Therefore, the sulphate groups mass contg need be controlled to less than 200ppm, may be thereby can prevent effectively as the formation of the thermal decomposition product of cellulose acylate weather stain reason.

Preferably, cellulose acylate pellet of the present invention contains basic metal and group II metal element.A kind of or the combination that can contain separately in polymkeric substance in these contains multiple.Preferably, in the process of making cellulose acylate, add these compounds, more preferably add in the washing step after the cellulose acylate manufacturing.Preferred basic metal and group II metal element are magnesium, calcium and strontium; More preferably magnesium and calcium; Calcium more preferably.Preferably, basic metal and group II metal element add with its alkaline compound, for example, and metal carbonate, alkali metal bicarbonate salt, metal hydroxides or metal oxide.More preferably hydroxide compound or weak acid formula salt compound; Hydroxide compound more preferably again.Wherein, particularly preferably be magnesium or calcium carbonate, supercarbonate, oxyhydroxide and oxide compound; Calcium hydroxide more preferably.

Add basic metal and/or the group II metal above-mentioned sulfuric acid that neutralizes effectively.Consequently, can more effectively prevent formation as the thermal decomposition product of cellulose acylate weather stain reason.In cellulose acylate pellet of the present invention, the ratio of (basic metal molal quantity and group II metal molal quantity sum)/(sulfate groups molal quantity) is preferably 0.3-3.0, more preferably 0.4-2.5, more preferably 0.5-2.0 again.

The weight average degree of polymerization of the cellulose acylate in the cellulose acylate pellet of the present invention is preferably 250-500, more preferably 330-480, more preferably 350-450 again.When use had the cellulose acylate of this low polymerization degree, its melt viscosity can be little in the fusion casting film-forming, to promote the fusion casting film-forming of expection.Consequently, must not increase to the melt temperature in the membrane process, therefore, can more effectively prevent formation as the thermal decomposition product of cellulose acylate weather stain reason.In addition, low-molecular weight polymer can prevent crystal formation, and therefore reduces the crystal amount in the particle effectively.The polymerization degree can prolong and reduce along with increase of acidylate temperature and reaction times, and therefore, by control acidylate temperature and time, cellulose acylate used herein can have the controllable required polymerization degree.

Preferably, cellulose acylate pellet of the present invention has the substitution value that satisfies following formula (S-1)-(S-3), more preferably satisfies following formula (S-4)-(S-6), more preferably satisfies following formula (S-7)-(S-9) again.The substitution value (composition) that has here to be limited can suppress crystal formation in the particle.Particularly; in cellulose acylate pellet of the present invention; make propionyl, butyryl radicals, pentanoyl and caproyl mix coexistence with ethanoyl, thereby particulate molecule systematicness is destroyed and can prevent crystal formation in the mode of combination than ethanoyl more volume.Be added to the amount of the acylating agent (acid anhydrides) of reaction system by control, can control substitution value.

(2-1) make particle by scorification:

Cellulose acylate pellet of the present invention can be by the step manufacturing (scorification) of the plain acylate resin of fused fiber.Especially, when making pellet, use scorification.

Particularly, can be by in twin screw is kneaded forcing machine, making cellulose acylate pellet of the present invention with the screw speed of 50-300rpm and the cellulose acylate resin of under the resin-pressure of kneading of 2-9MPa, kneading.Screw speed is 80-250rpm more preferably, more more preferably 100-230rpm.Resin-more preferably the 2-8MPa of pressure that kneads, more preferably 3-6MPa again.

When applying to it when pressing in this, the cellulose acylate resin, or be the raw material that particle is used, can be full of used twin screw extruder.Consequently, the resin of can more effectively kneading, and fusion crystal more fully prevent thermolysis simultaneously.Usually, do not apply interior pressure to resin-molten system.Yet if do not exert pressure to it, twin screw extruder can form the space around the screw rod therein so, can shear resin consumingly in described space, and resin is easy to take place thermolysis thus.This can be the reason of weather stain after the film forming.Exit by the forcing machine of kneading at used twin screw provides pressure controlled valve, can realize pressure-controlling.Usually, under the rotating speed of 40rpm at the most, use the twin screw forcing machine of kneading, but in the present invention, preferably use forcing machine under these conditions.Therefore, the residence time in twin screw extruder can be shortened, and thermolysis can be more effectively prevented.Increase shearing force by high rotating speed and can promote the crystalline fusion.

Preferably in kneading forcing machine, twin screw under 160 ℃-220 ℃ temperature, carries out granulation, and more preferably 170 ℃-215 ℃, more preferably 180 ℃-210 ℃ again.Usually, under 230 ℃ or higher high temperature, be melt into film resin, but in the present invention, preferably fused raw material cellulose acylate resin under described low temperature.In above-mentioned screw speed scope and interior pressure scope, can the molten resin crystal, and this temperature range is enough in the present invention.Consequently, can more effectively prevent to cause the thermolysis of weather stain.

In the present invention, used twin screw knead the interior pressure of forcing machine preferably remain below 1 normal atmosphere, more preferably the 0-0.8 normal atmosphere, more more preferably under the 0.1-0.6 normal atmosphere, make the resin granulation.Use vacuum pump to make the twin screw forcing machine exhaust of kneading, the pressure that can obtain to reduce by being located at the knead ventilation opening in the district of kneading of forcing machine or funnel of twin screw.

As the case may be, rare gas element can be introduced the twin screw forcing machine of kneading, make that the oxygen concn in the forcing machine is preferably 0-18% in granulating, more preferably 0.5-16%, more preferably 1-14% again.In this case, rare gas or nitrogen can be used as rare gas element, and it introduces the twin screw forcing machine of kneading by being located at the knead ventilation opening in district or funnel of forcing machine.

Pressure reduces and the rare gas element injection can be carried out independently, or can make up simultaneously as the preferred embodiment of granulation and to carry out.

Zhi Bei cellulose acylate pellet is applicable in follow-up film forming step by using single screw extrusion machine to carry out film forming in a manner described.Single screw extrusion machine can obtain the constant resin melt and extrude in time per unit, and can prevent the film thickness fluctuation.

When grinding, Zhi Bei cellulose acylate pellet can be the cellulose acylate pellet that has than small particle size in a manner described.The particle that obtains also can be used for film forming.(2-2) make particle by dissolution method:

Cellulose acylate pellet of the present invention can be by the process manufacturing (dissolution method) of dissolving cellulos acylate resin.Particularly, be dissolving cellulos acylate resin in the solvent of 7-10 in the SP value, then it is solidified to prepare cellulose acylate pellet of the present invention.The SP value is 7.5-9.7 more preferably, more more preferably 8.0-9.5.The definition of SP value (solubility parameter) described here and be determined in the following measuring method part and will describe in detail.The SP value be 7-10 solvent preferably the SP value be the ketone solvent of 7-10 for the ester solvent of 7-10, SP value for halogenated hydrocarbon solvent or the SP value of 7-10.The example of preferred solvent comprises acetone, methyl ethyl ketone, metacetone, ethyl acetate, butylacetate and methylene dichloride.Wherein, more preferably acetone, methyl ethyl ketone, ethyl acetate, butylacetate and methylene dichloride.

The concentration of the cellulose acylate solution that obtains after the dissolving is preferably 1 quality %-40 quality %, more preferably 3 quality %-35 quality %, more preferably 5 quality %-30 quality % again.Solvent temperature is preferably 10 ℃-50 ℃, more preferably 15 ℃-40 ℃.

With evaporating solvent (drying means), or place poor solvent to precipitate (intermediate processing) solution by drying solution, can realize solidifying.Poor solvent is the mixed solvent of water or water and lower alcohol (for example, methyl alcohol, ethanol, propyl alcohol) preferably.

When cellulose acylate was dissolved in the solvent with above-mentioned SP value, solvent had suitable affinity to cellulose acylate, prevented that therefore the cellulose acylate gathering from forming crystal.Therefore, the crystallization fusion heat of the cellulose acylate pellet that makes can be controlled in the defined scope of the present invention.

Preferably, cellulose acylate pellet of the present invention is of a size of 1mm ³-100000mm ³, more preferably 2mm ³-50000mm ³, more preferably 3mm again ³-10000mm ³When using drying means, can grind the solidified cellulose acylate, to carry out size control.When using intermediate processing; can control the size that drops into the cellulose acylate solution droplets in the poor solvent; or can under high speed, stir the cellulose acylate solution that is added in the poor solvent, thus can reduce the size of cellulose acylate solution droplets, with the particle of control manufacturing.

The cellulose acylate pellet of Huo Deing is applicable to the film forming of using twin screw extruder to realize in follow-up fusion curtain coating film process in a manner described.In twin screw extruder, at molten resin when resin is used high shear force.Therefore, can prevent from twin screw extruder to form by the flake that fused cellulose acylate not causes.Preferably, can knead and drive twin screw with the screw speed of 50-300rpm and under the resin of the 10MPa-pressure of kneading of kneading at the most and knead that forcing machine is kneaded and fusion resin wherein.More preferably, screw speed is 80-250rpm, and the resin-pressure of kneading is 1MPa-9MPa; Again more preferably, screw speed is 100-230rpm.

When the combination of above-mentioned cellulose acylate pellet and single screw extrusion machine was compared with the combination of cellulose acylate pellet and twin screw extruder, from as the optical thin film viewpoint of the film thickness controllability of important factor more, the former was more preferred than the latter.

(3) by using touch roll to make cellulose acylate film:

In the present invention, from making cellulose acylate film by the cellulose acylate pellet of scorification or dissolution method manufacturing.

When the preparation cellulose acylate film, preferably use touch roll.Touch roll is the roller that places the film forming system, and it makes and can press from both sides between the roller and described touch roll for the treatment of the curtain coating resin melt thereon by the resin melt (molten resin) of mould from melt extruding machine.

The touch roll of described type can be included in the elastomer layer that forms on the metal shaft, and it is also covered by external jacket, and wherein dielectric liquid layer is filled out between elastomer layer and external jacket.The layer thickness of external jacket is preferably 0.05mm-7.0mm, more preferably 0.2mm-5.0mm.Preferably, casting roller and touch roll all have specular surface, and its arithmetical mean height Ra is 100nm at the most, more preferably 50nm at the most, more preferably 25nm at the most again.Particularly, for example, can adopt those that put down in writing among JP-A-11-314263, JP-A-2002-36332, JP-A-11-235747, JP-A-2004-216717, JP-A-2003-145609, the WO97/28950.

For this reason, because the thin external jacket inner filling of touch roll has fluid, thereby when keeping in touch with casting roller, touch roll is applied to when pressure on it is pushed, and recoverable deformation can take place.Therefore,, touch roll contacts owing to facing each other with casting roller, so the dispersion of their pressure, and they can obtain low surface pressure.Therefore, in the film that is clipped between them, do not have residual strain, thereby can correct the surfaceness of film.Preferably, the line pressure of touch roll is 3kg/cm-100kg/cm, more preferably 5kg/cm-80kg/cm, more preferably 7kg/cm-60kg/cm again.Line pressure described here refers to the power on the touch roll of being applied to divided by the value of nib width gained.

Preferably, the power of pressing contact roller is defined by the contact pressure that is applied thereto.Contact pressure refers to the value of the area gained that keeps in touch each other divided by touch roll and casting roller with the power of pressing contact roller.In the present invention, the preferred 0.3MPa-3MPa of contact pressure, more preferably 0.5MPa-2.5MPa, more preferably 0.7MPa-2.0MPa again.

The temperature of touch roll and casting roller is preferably 60 ℃-160 ℃, and more preferably 70 ℃-150 ℃, more preferably 80 ℃-140 ℃ again.Liquid by making adjusting or steam can obtain the temperature control in the above-mentioned scope at the roller internal circulation.

When using the touch roll of described type, cool off film and therefore can more effectively prevent the film weather stain from casting roller and touch roll.When not having touch roll, only on a surface of casting roller, cool off the molten mass that comes out from mould, so speed of cooling is slow.Therefore, can promote the thermolysis of cellulose acylate, thereby make the film weather stain that obtains.Because the upper surface of casting roller always is exposed in the air, can lack thereby the film on the roller is exposed to the pyritous time, but the film on the roller can be easy to thermolysis.Therefore, under this condition, can cool off film fast with touch roll especially effectively.

Cellulose acylate:

The following describes the used cellulose acylate of the present invention.

For the manufacture method of the cellulose acylate that uses in the present invention, be suitable for the explanation among Hatsumei Kyokai Disclosure Bulletin (No.2001-1745, HatsumeiKyokai published in the March 15 calendar year 2001) p7-12.Add-on described here is scaled the quality % with respect to cellulose acylate.

Raw material:

Make raw fibre cellulosic material that cellulose acylate uses and preferably come from a kind of in hardwood pulp, softwood pulp, the cotton linter.

Activation:

Before acidylate, preferably use activator (being used for activation) to handle the raw fibre cellulosic material.The preferred acetate of activator, propionic acid, butyric acid, more preferably acetate.The preferred 5%-10000% of the add-on of activator, more preferably 10%-2000%, more preferably 30%-1000% again.The adding method of promoting agent can be selected from spraying, drip and use or dipping.Soak time preferred 20 minutes-72 hours, more preferably 20 minutes-12 hours.Preferred 0 ℃-90 ℃ of activation temperature, more preferably 20 ℃-60 ℃.When needed, can use its amount with activator is acylation catalyst such as the sulfuric acid of 0.1 quality %-10 quality %.

Activation can reduce the amount of above-mentioned needle-like impurity in the Mierocrystalline cellulose.Particularly, when the higher and soak time of activation temperature is longer, can reduce the amount of needle-like impurity to a greater degree.

Acidylate:

Preferably, Mierocrystalline cellulose reacts with carboxylic acid anhydride under the existence of Broensted acid that is used as catalyzer or Lewis acid (referring to Dictionary of Physic and Chemistry, the 5th edition, 2000), thus the hydroxyl of acylated cellulose.

Rise owing to the reaction heat in the acidylate makes temperature for control, preferably cool off acylating agent in advance.Preferred-50 ℃ to 50 ℃ of acidylate temperature is more preferably-30 ℃ to 40 ℃, more more preferably-20 ℃ to 35 ℃.Preferred-50 ℃ or higher of minimum response temperature, more preferably-30 ℃ or higher, more more preferably-20 ℃ or higher.Preferred 0.5 hour-24 hours acidylate time, more preferably 1 hour-12 hours, more preferably 1.5 hours-10 hours again.

For obtaining cellulosic mixing acylate, for example, can use Mierocrystalline cellulose with all as the dissimilar carboxylic acid anhydride reaction of two kinds of acylating agent, wherein two kinds of carboxylic acid anhydride are as the mixture or the method for adding in turn; Or use the method for the mixed acid anhydride (for example, blended diacetyl oxide/propionic anhydride) of two kinds of dissimilar carboxylic acids; Or make acid anhydrides (for example, acetate and the propionic anhydride) reaction of the different carboxylic acid in carboxylic acid and the reaction system form mixed acid anhydride (for example, blended diacetyl oxide/propionic anhydride), the method that itself and Mierocrystalline cellulose are further reacted; Or make earlier substitution value less than 3 cellulose acylate, then with acid anhydrides or carboxylic acid halides in the position of its residual hydroxy groups the method with its acidylate.

Has the cellulose acylate of big 6-substitution value about manufacturing, with reference to the explanation among JP-A-11-5851, JP-A-2002-212338 and the JP-A-2002-338601.

Acid anhydrides:

For carboxylic acid anhydride, carboxylic acid preferably has 2-22 carbon atom.More preferably diacetyl oxide, propionic anhydride, butyryl oxide.Preferably,, the normal acid anhydrides of 1.1-50 is added in the Mierocrystalline cellulose more preferably 1.2-30 equivalent, more preferably 1.5-10 equivalent again with respect to cellulosic hydroxyl.

Catalyzer:

Acylation catalyst is Broensted acid or Lewis acid preferably, more preferably sulfuric acid or perchloric acid; Its preferred add-on is 0.1-30 quality %, more preferably 1-15 quality %, more preferably 3-12 quality % again.

Solvent:

The acidylate solvent is carboxylic acid preferably, more preferably has the carboxylic acid of 2-7 carbon atom, more more preferably acetate, propionic acid, butyric acid.These solvents can mix use.

Reaction terminating agent:

After acidylate, preferably reaction terminating agent is added in the system.Reaction terminating agent can be can decompose acid anhydrides any, comprises for example water, alcohol (having 1-3 carbon atom), carboxylic acid (for example, acetate, propionic acid, butyric acid).Wherein, particularly preferably be the mixture of water and carboxylic acid (acetate).About the ratio of mixture of water in the mixture and carboxylic acid, the water yield is preferably 5 quality %-80 quality %, more preferably 10 quality %-60 quality %, more preferably 15 quality %-50 quality % again.

Neutralizing agent:

After stopping acidylate, neutralizing agent can be added in the system.The preferred example of neutralizing agent be ammonium, organic quaternary ammonium, basic metal, group II metal, 3-12 family metal or 13-15 family element carbonate, supercarbonate, with organic acid salt, oxyhydroxide or oxide compound.Particularly preferably be carbonate, supercarbonate, oxyhydroxide or the oxide compound of sodium, potassium, magnesium or calcium.

Partial hydrolysis:

Total substitution value of the cellulose acylate that obtains like this is near 3; but for obtaining having the ester of required substitution value; acylate can be in little amount of catalyst (usually; remaining acylation catalyst such as sulfuric acid) and the existence of water under, kept several minutes extremely several days at 20-90 ℃; thereby the partial hydrolysis ester bond, the acyl substituted degree with cellulose acylate is reduced to required degree like this.Thereafter, can with in the above-mentioned neutralizing agent and remaining catalyzer to stop partial hydrolysis.

Filter:

From acidylate to reppd any stage, can filtering mixt.Preferably, can be with the solvent cut system that is fit to before filtering.By filtering, can remove unreacted needle-like impurity.When removing needle-like impurity in advance by above-mentioned activation treatment, can more effectively filter, this embodiment is preferred.

Redeposition:

Cellulose acylate solution can mix with the water of carboxylic acid (for example, acetate, the propionic acid) aqueous solution, to carry out redeposition.Redeposition can be undertaken by continuous or intermittent mode.

Washing:

After redeposition, preferably wash acylate.Water or hot water can be used for washing.Can pass through pH, ionic concn or electroconductibility or determine the terminal point of washing by ultimate analysis.

Add basic metal, group II metal:

After washing, preferably above-mentioned basic metal or group II metal compound are added in the cellulose acylate.Described compound for example can be by following adding: with compound dissolution or be dispersed in solvent such as water in, be injected on the cellulose acylate then; Or be immersed in solution or the dispersion cellulose acylate and stirring, take out by filtering then.

Dry:

Preferably, at the plain acylate of 50-160 ℃ of dried fibres, make water-content 2 quality % at the most.

Cellulose acylate:

According to the cellulose acylate of above-mentioned manufacture method preparation be wherein with cellulosic β-1, the hydroxylic moiety of 2-position, 3-position and the 6-position of the glucose unit of 4-glucosides structure bonding or all by the polymkeric substance of acyl group esterification.In the cellulose acylate that the present invention uses, can be with two or more the dissimilar acyl moieties or the hydroxyl of substituted cellulose fully.

Preferably, cellulose acylate of the present invention satisfies following formula (S-1)-(S-3):

(S-1)2.6≤X+Y≤3.0，

(S-2)0≤X≤1.8，

(S-3)1.0≤Y≤3.0；

Wherein X represents the substitution value of ethanoyl to the Mierocrystalline cellulose hydroxyl; Y represents propionyl, butyryl radicals, pentanoyl and the caproyl total substitution value to the Mierocrystalline cellulose hydroxyl.When all hydroxyls of cellulosic 2-position, 3-position and 6-position during all by acyl substituted, substitution value is 3.

More preferably, cellulose acylate satisfies following formula (S-4)-(S-6):

(S-4)2.7≤X+Y≤3.0，

(S-5)0≤X≤1.2，

(S-6)1.5≤Y≤3。

Again more preferably, cellulose acylate satisfies following formula (S-7)-(S-9):

(S-7)2.8≤X+Y≤3.0，

(S-8)0≤X≤0.8，

(S-9)2.0≤Y≤3。

When X+Y is 2.6 or when bigger, the wetting ability of cellulose acylate is low, can more effectively dry acylate.

When X is 1.8 or more hour, the wetting ability of cellulose acylate is low, can more effectively dry acylate.

When Y is 1.0 or when bigger, the hydrophobicity of cellulose acylate is higher relatively, can dry effectively acylate.

Additive:

Thermo-stabilizer:

For further improving the thermostability of the cellulose acylate among the present invention, especially effectively add thermo-stabilizer.Especially, preferably add thermo-stabilizer, to keep the thermostability of cellulose acylate in the film process of fusion curtain coating at high temperature.Wherein, preferably add at least one phenol stabilizer of molecular weight at least 500 and be selected from the phosphite ester stabilizer of molecular weight at least 500 and the thioether stabilizers of molecular weight at least 500 at least a.

Any known phenol stabilizer of preferred use.A kind of preferred phenol stabilizer is a hindered phenol stabilizer.Particularly preferably, employed hindered phenol stabilizer has substituting group with the hydroxy phenyl position adjacent therein, wherein substituting group is more preferably and replaces or the alkyl of the unsubstituted 1-22 of a having carbon atom, more more preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, tert-pentyl, hexyl, octyl group, iso-octyl, 2-ethylhexyl.The stablizer that has hydroxy phenyl and phosphorous acid ester group in a molecule simultaneously also is preferred the use.

These are commercially available, and are for example sold by following manufacturers.Can obtain Irganox1076, Irganox1010, Irganox3113, Irganox245, Irganox1135, Irganox1330, Irganox259, Irganox565, Irganox1035, Irganox1098, Irganox1425WL from Ciba SpecialityChemicals.Can obtain Adekastab AO-50, Adekastab AO-60, AdekastabAO-20, Adekastab AO-70, Adekastab AO-80 from Asahi DenkaKogyo.Can obtain Sumilizer BP-76, Sumilizer BP-101, Sumilizer from SumitomoChemical.GA-80。Can obtain Seenox326M, Seenox336B from Sypro.

The phosphite ester stabilizer of molecular weight at least 500 is effectively as antioxidant, comprises the compound of putting down in writing among the compound of record in [0023]-[0039] of JP-A-2004-182979 for example and JP-A-51-70316, JP-A-10-306175, JP-A-57-78431, JP-A-54-157159 and the JP-A-55-13765.Other stablizers such as write up are at Hatsumei Kyokai Disclosure Bulletin (No.2001-1745, HatsumeiKyokai published in March 15 calendar year 2001), and those among the p17-22 also are suitable for, and can be selected from them.These also are commercially available.For example, can obtain Adekastab1178,2112, PEP-8, PEP-24G, PEP-36G, HP-10 from Asahi Denka Kogyo; With can obtain Sandostab P-EPQ from Clariant.

In the present invention, can use any known thioether stabilizers.For example, the commercially available Sumilizer TPL of Sumitomo Chemical, TPM, TPS, TDP; With can obtain Adekastab AO-412S from Asahi Denka Kogyo.

When using these stablizers; preferably with at least a phenol stabilizer and be selected from phosphite ester stabilizer and thioether stabilizers at least a being added in the cellulose acylate; add-on is respectively the 0.02-3 quality % of acylate, more preferably 0.05-1 quality %.The ratio of mixture of phenol stabilizer and phosphite ester stabilizer and/or thioether stabilizers is not concrete to be limited, but preferred 1/10-10/1 (quality), more preferably 1/5-5/1 (quality), more preferably 1/3-3/1 (quality) again, more preferably 1/3-2/1 (quality) again.

In the present invention, recommend to use the stablizer that in a molecule, has hydroxy phenyl and phosphorous acid ester group simultaneously.Its example is documented among the JP-A-10-273494.An example of this commercially available prod is Sumilizer GP (Sumitomo Chemical).

In addition, the long-chain fat family amine of putting down in writing in JP-A-61-63686, the compound of putting down in writing in JP-A-6-329830 with space hindered amine group, the hindered piperidine based stabilizer of putting down in writing in JP-A-7-90270 and the organic amine of putting down in writing in JP-A-7-278164 also are suitable for.

The preferred amine stabiliser that uses among the present invention is the commercially available prod Tinubin 765,144 of commercially available prod Adekastab LA-57, LA-52, LA-67, LA-62, LA-77 and the Ciba SpecialityChemicals of Asahi Denka.The ratio of employed amine and stablizer is generally about 0.01-25 weight %.

The UV absorption agent:

Cellulose acylate can contain the UV inhibitor.The UV inhibitor for example is documented among JP-A-60-235852, JP-A-3-199201, JP-A-5-1907073, JP-A-5-194789, JP-A-5-271471, JP-A-6-107854, JP-A-6-118233, JP-A-6-148430, JP-A-7-11056, JP-A-7-11055, JP-A-8-29619, JP-A-8-239509, the JP-A-2000-204173.The add-on of UV inhibitor is preferably the 0.01-2 quality % of the resin melt of preparation, more preferably 0.01-1.5 quality %.

Commercially available UV absorption agent such as following those also are suitable for.Commercially available benzotriazole compound is Tinubin P (Ciba Speciality Chemicals), Tinubin 234 (CibaSpeciality Chemicals), Tinubin 320 (Ciba Speciality Chemicals), Tinubin 326 (Ciba Speciality Chemicals), Tinubin 327 (CibaSpeciality Chemicals), Tinubin 328 (Ciba Speciality Chemicals), Sumisorb 340 (Sumitomo Chemical), Adekastab LA-31 (AsahiDenka Kogyo).Commercially available benzophenone UV absorption agent is Seesorb 100 (SyproChemical), Seesorb 101 (Sypro Chemical), Seesorb 101S (SyproChemical), Seesorb 102 (Sypro Chemical), Seesorb 103 (SyproChemical), Adekastab LA-51 (Asahi Denka Kogyo), Chemisorb 111 (Chemipro Chemical), Uvinul D-49 (BASF).Commercially available oxanilide (oxalicacid anilide) class UV absorption agent is Tinubin 312 (Ciba SpecialityChemicals), Tinubin 315 (Ciba Speciality Chemicals).Commercially available salicylic acid UV absorption agent is Seesorb 201 (Sypro Chemical), Seesorb 202 (SyproChemical); And commercially available cyanoacrylate UV absorption agent is Seesorb 501 (Sypro chemical), Uvinul N-539 (BASF).

Particulate:

In the present invention, particulate can be added in the cellulose acylate.Particulate comprises mineral compound particulate and organic compound particulate, and any can be that the present invention uses.Preferably, the average primary particle diameter of the particulate in the cellulose acylate of the present invention is 5nm-3 μ m, more preferably 5nm-2.5 μ m, more preferably 20nm-2.0 μ m again.The amount that particulate is added in the cellulose acylate can be the 0.005-1.0 quality % of acylate, more preferably 0.01-0.8 quality %, more preferably 0.02-0.4 quality % again.

Mineral compound comprises SiO ₂, ZnO, TiO ₂, SnO ₂, Al ₂O ₃, ZrO ₂, In ₂O ₃, MgO, BaO, MoO ₂, V ₂O ₅, talcum, calcined kaolin, calcining Calucium Silicate powder, hydrated calcium silicate, pure aluminium silicate, Magnesium Silicate q-agent and calcium phosphate.SiO preferably ₂, ZnO, TiO ₂, SnO ₂, Al ₂O ₃, ZrO ₂, In ₂O ₃, MgO, BaO, MoO ₂And V ₂O ₅In at least a; SiO more preferably ₂, TiO ₂, SnO ₂, Al ₂O ₃, ZrO ₂

As SiO ₂Particulate, operable commercially available prod for example are Aerosil R972, R972V, R974, R812,200,200V, 300, R202, OX50, TT600 (making by Nippon Aerosil).As ZrO ₂Particulate, operable commercially available prod for example are Aerosil R976 and R811 (making by Nippon Aerosil).In addition, Seahostar KE-E10, E30, E40, E50, E70, E150, W10, W30, W50, P10, P30, P50, P100, P150, P250 (making by Nippon Shokubai) also are suitable for.Silicon-dioxide microballon P-400,700 (Shokubai Kasei Kogyo) also is suitable for.SO-G1, SO-G2, SO-G3, SO-G4, SO-G5, SO-G6, SO-E1, SO-E2, SO-E3, SO-E4, SO-E5, SO-E6, SO-C1, SO-C2, SO-C3, SO-C4, SO-C5, SO-C6 (making by Admatechs) also are suitable for.In addition, the silicon-dioxide grain of Moritex (the water dispersion powdered is made) 8050,8070,8100,8150 also is suitable for.

As the organic compound particulate that uses in the present invention, preferably polymkeric substance such as silicone resin, fluoro-resin and acrylic resin; Silicone resin more preferably.Silicone resin preferably has tridimensional network.The commercially available prod is suitable for, as Tospearl103,105,108,120,145,3120 and 240 (making by Toshiba Silicone).

Preferably, employed mineral compound particulate is carried out surface treatment, thus they can be in cellulose acylate film stable existence.Further preferably use surface treatment inorganic particles afterwards.Surface treatment comprises the chemical surface treatment of using coupling agent, and physical surface treatment such as plasma discharge processing or Corona discharge Treatment.In the present invention, preferably use the surface treatment of coupling agent.Coupling agent is organic alkoxy-metallic compound (for example, silane coupling agent, titanium coupling agent) preferably.For can be as the inorganic particles of particulate (SiO particularly ₂Particle), it is effective especially using the processing of silane coupling agent.Not concrete qualification, the 0.005-5 quality % of the preferably inorganic particles of coupling agent, more preferably 0.01-3 quality %.

Softening agent:

When being added to softening agent in the cellulose acylate, can reduce the crystalline melt temperature (Tm) of acylate.The softening agent that uses among the present invention is not concrete to limit its molecular weight, but preferably has high molecular.For example, its molecular weight preferably at least 500, more preferably at least 550, more more preferably at least 600.About its kind, spendable softening agent comprises the fatty acid ester of phosphoric acid ester, alkyl phthalic acyl group alkyl oxyacetate, carboxylicesters, polyvalent alcohol.About its form, softening agent can be solid or oily matter.Therefore, not concrete its fusing point or the boiling point of limiting of softening agent.In the fusion casting film-forming, non-volatile plasticisers is particularly preferred.

Have the high-molecular weight softening agent even use, in the film forming trace volatilization to be arranged also for a long time, and can be deposited on the casting roller, its settling can be transferred on the surface of film of formation, therefore causes the surface imperfection of film.Therefore, it is most preferred not using softening agent.For this reason, can only use cellulose acylate with enough low melting viscosities.Particularly, can only use, more preferably the cellulose acylate of 1500Pas at the most at the following melt viscosity 2000Pas at the most of its melt temperature (230 ℃).The composition and the polymerization degree by controlling above-mentioned cellulose acylate can obtain this cellulose acylate.

Lubricant:

Lubricant can be added in the cellulose acylate of the present invention.The compound that lubricant is preferably fluorine-containing.Fluorine-containing compound can be the low-molecular weight compound or the polymer compound that can play lubricant.The polymkeric substance of putting down in writing in JP-A-2001-269564 can be used as polymeric lubricant.As fluorine-containing polymeric lubricant, the polymkeric substance that makes as the ethylenically unsaturated monomers that contains fluoroalkyl of neccessary composition by polymerization preferably.The ethylenically unsaturated monomers that contains fluoroalkyl that polymkeric substance is used can be any compound that has ethylenic unsaturated group and fluoroalkyl in molecule, not concrete the qualification.Fluorine-containing tensio-active agent also is suitable for, and nonionogenic tenside is particularly preferred.

The manufacturing of cellulose acylate film:

The following describes the method for making cellulose acylate film from cellulose acylate.In the present invention, preferably make film, wherein make the mixture fusion of cellulose acylate and additive, and form film according to fusion curtain coating film.When having residual solvent in the film that forms, can in dry film, carry out crystallization, consequently can reduce the shock strength of film.Therefore, in the present invention, the 0.01 weight % at the most of the amount of residual solvent in the film of Xing Chenging preferably, more preferably 0%.In not using the fusion curtain coating film of solvent, amount of residual solvent can be 0%.

Granulation:

In aforesaid method, with the cellulose acylate granulation.Can pass through cellulose mixture acylate and additive, and in solvent dissolving mixt, then by drying means or intermediate processing curing solution, and abrasive solid randomly, carry out granulation.When needed, can be by the following granulation of carrying out: mix and plain acylate of dried fibres and additive fusion and be extruded into line in twin screw is kneaded forcing machine then, cooling and curing and be granulated into pellet in water in a manner described.The pellet that obtains can grind to form littler particle.

Dry:

Before the fusion casting film-forming, dried particles preferably makes particulate water-content 0.1 quality % at the most, more preferably 0.01 quality % at the most.

For this reason, the preferred 40-180 of drying temperature ℃; The preferred 20-400m of dry air flow rates ³/ hr, more preferably 100-250m ³/ hr.Preferred 0 ℃ to-60 ℃ of the dew point of dry air is more preferably-20 ℃ to-40 ℃.

Melt extrude:

The supplying opening of exsiccant cellulose acylate resin (particle such as pellet) by the forcing machine of kneading supplied in its machine barrel.Cellulose acylate pellet can use separately or mix use with any other material.Single screw extrusion machine is preferred when the process resin pellet; But twin screw extruder is preferred when handling the resin particle for preparing with dissolution method.When the process resin mixture, can use in single screw rod or the twin screw extruder any.

The screw compression ratio of forcing machine kneaded is preferably 2.5-4.5, more preferably 3.0-4.0.L (spiro rod length)/D (screw diameter) is preferably 20-70, more preferably 24-50.The preferred 190-240 of extrusion temperature ℃.Preferably, the bucket of the forcing machine of molten resin heats by the heater unit that is divided into 3-20 part therein.

Preferably, melt temperature is 150 ℃-250 ℃, more preferably 160 ℃-240 ℃, and more preferably 170 ℃-235 ℃ again.In this case, preferably make the temperature of inlet side (funnel side) lower, and make the temperature of outlet side higher 10 ℃-60 ℃ than the temperature of inlet side.

Screw rod can be full flight screw, maddock screw rod or dalmage screw rod.

For preventing the resin oxidation, the internal atmosphere of the forcing machine of more preferably kneading is rare gas element (for example, nitrogen), or uses the forcing machine with ventilation opening and this forcing machine exhaust is made it to be in vacuum.

Filter:

In the outlet of forcing machine of kneading, preferably filter resin by spreader plate strainer (breaker platefilter).

Be secondary filter, blade type disk filter unit preferably is set after toothed gear pump.Filtration can be carried out in a stage or in a plurality of stage.Preferably, filtering accuracy is 3 μ m-15 μ m, more preferably 3 μ m-10 μ m.Preferably, filter material is stainless steel or ordinary steel, more preferably stainless steel.Strainer can be the structure of braiding or the structure of sintering metal, but the latter is preferred.

Toothed gear pump:

Be to improve thickness and precision (spraying fluctuation), preferably between forcing machine and the mould toothed gear pump is set kneading by reducing resin.Therefore, the fluctuation of the resin pressure at mould place is in ± 1%.

For improving the weight feed performance of toothed gear pump, further preferably change screw speed, thereby the pressure before the pinion pump is constant.The high precision gear wheel pump that comprises 3 or more a plurality of gears also is effective.Because the resistates in the toothed gear pump may cause the resin deterioration, the preferred design toothed gear pump makes that wherein the amount of resistates is as far as possible little.

The temperature variation of adapter that connects knead forcing machine and toothed gear pump and toothed gear pump and mould is preferably as far as possible little, to stablize extrusion pressure.For this reason, the preferred well heater of imbedding aluminium that uses.

Mould:

As long as be designed to can stop resin melt hardly therein, can use the mould of any general type, be coated with mould as T-mould, fish tail mould or clothes rack shape.T-mould and then before the T-mould can be provided with static mixer no problemly, to improve the homogeneity of resin temperature.Usually, the gap of T-mould outlet is preferably 1.0-5.0 times of film thickness, and more preferably 1.3-2 doubly.

Preferably, the die clearance can be controlled to the distance of 40-50mm, more preferably the distance of 25mm at the most.For reducing the film thickness fluctuation in the film forming, also effectively measure the film thickness of system downstream position, and feedback gained data are to carry out mold thickness control.

For providing as outer field functional layer, can use the multi-layer thin membrane formation device, have the film of two-layer or more multi-layered structure with manufacturing.

The residence time that enters the resin of kneading forcing machine and coming out by mould by supplying opening is 2 minutes-60 minutes, preferred 4 minutes-30 minutes.

Curtain coating:

The resin melt that cooling is extruded from mould as flap, and on the curtain coating cylinder, solidify to form film thereon.In this stage, preferably use static to apply (electrostatic charging) method, air knife method, air chamber method, vacuum nozzle method or touch roll method, with airtight contact the between enhanced film and the cylinder.Edge join (edge pinning) method (wherein only the two ends of film keep airtight contact) further preferably with cylinder.Wherein, particularly preferably be the touch roll method.

Preferably, use 1-8 curtain coating cylinder, more preferably 2-5 curtain coating cylinder cools off film gradually.Preferably, roller diameter is 50mm-5000mm, more preferably 150mm-1000mm.Distance between a plurality of these rollers, the i.e. preferred 0.3mm-300mm of distance on the surface-surface between them, more preferably 3mm-30mm.Preferred 60 ℃-160 ℃ of the temperature of curtain coating cylinder, more preferably 80 ℃-140 ℃.

Next, from curtain coating drum peel film,, batch then by nip rolls (nip rolls).The preferred 30 μ m-300 μ m of the thickness of the not tensile film that obtains like this, more preferably 40 μ m-200 μ m, more preferably 50 μ m-150 μ m again.

Batch:

Preferably, before batching, can prune the two ends of film.The raw material that can be used for film on the waste material under pruning utilizes again.As trimming tool, can use in rotary cutter, shear-blade or the cutter any.Its material can be any in carbon steel, stainless steel or the pottery.

Preferably, the tension force that batches film is 1kg/m-width-50kg/m-width, more preferably 3kg/m-width-20kg/m-width.About coiling tension, can batch film with constant-tension, but preferably batch with being tapered according to the winding roller diameter.

The stretch ratio of essential control film between nip rolls makes film can not receive than batching the bigger any tension force of qualification level in the line.

Before batching, can be at least one surface of film laminated any other film.

Preferably, the width of the film that batches is 1m-3m, more preferably 1.2m-2.5m.Preferably, the length of the film that batches is 1000m-8000m, more preferably 1500m-7000m, more preferably 2000m-6000m again.

Fig. 1 is the synoptic diagram of the sketch map that is used for the film forming device of fusion curtain coating that preferably uses of the present invention.In this accompanying drawing, the 101st, the forcing machine of kneading, the 102nd, toothed gear pump, the 103rd, strainer; the 104th, mould, the 105th, touch roll, the 106th, curtain coating cooling drum, the 107th, cellulose acylate; the 108th, the machine direction stretch district, the 109th, crisscross drawing zone, the 110th, batch the district.The following describes stretching.For not tensile film formation, after leaving curtain coating cooling drum 106, directly batch the film of formation, and not by drawing zone 108,109.

The physicals of tensile cellulose acylate film not:

Preferred its Re=0-20nm of the not tensile cellulose acylate film that obtains like this and Rth=0-80nm, more preferably Re=0-10nm and Rth=0-60nm.Re and Rth refer to interior delay of the face of film and thickness direction retardation respectively.By light being incided on the film, use KOBRA 21ADH (Oji ScientificInstruments manufacturing) measure R e in the film normal direction.Rth measures as follows: based on the delayed data that records at three different directions, be above-mentioned Re, in the direction of tilt with respect to the film normal direction+40 ° or-40 ° light is incided the length of delay of measuring on the film as tilting axis (turning axle) with slow axis, thereby calculate Rth.Preferably, the angle θ between the slow axis of the Re of film-direct of travel (machine direction) and film near 0 ° or+90 ° or-90 °.

Preferably, the total light transmittance of tensile cellulose acylate film is not 90%-100%.The mist degree of film is generally 0-1%, preferred 0-0.6%.

Preferably, the thickness offset of machine direction and crisscross film is 0%-3%, more preferably 0%-2%.

Preferably, the tensile modulus of film is 1.5kN/mm ²-3.5kN/mm ², more preferably 1.8kN/mm ²-2.6kN/mm ²The preferred 3%-300% of the elongation at break of film.

The Tg of film is preferably 95 ℃-145 ℃.The machine direction of film and crisscross on, 80 ℃ place 1 day after, the hot dimensional change of film all is preferably 0% to ± 1%, more preferably 0% to ± 0.3%.

The water vapour permeability of film is preferably 300g/m under 40 ℃ and the 90%RH ²My god-1000g/m ²My god, more preferably 500g/m ²My god-800g/m ²My god.The equivalent water-content of film is preferably 1 quality %-4 quality % under 25 ℃ and the 80%RH, more preferably 1.5 quality %-2.5 quality %.

The physicals of stretching and tensile cellulose acylate film:

Stretch:

The tensile film can not be stretched with the Re and the Rth of control film.

The preferred Tg-of draft temperature (Tg+50 ℃), more preferably (Tg+5 ℃)-(Tg+20 ℃).Preferably, the tensile stretch ratio is 1%-300%, more preferably 3%-200% at least one direction.More preferably, the stretch ratio of a direction is greater than other direction; The preferred 1%-30% of less stretch ratio of a direction, more preferably 3%-20%, the big preferred 30%-300% of stretch ratio, the more preferably 40%-150% of other direction.Can in a stage or a plurality of stage, obtain to stretch.Described stretch ratio can obtain according to following formula:

Stretch ratio (%)=100 * { (back length stretches)-(length before stretching) }/(length before stretching).

Can stretch by using nip rolls or tenter machine.Biaxial stretch-formed method when can also use described in JP-A-2000-37772, JP-A-2001-113591 and the JP-A-2002-103445.

The Re of tensile cellulose acylate film and Rth preferably satisfy following formula:

Rth≥Re，

200≥Re≥0，

500≥Rth≥30。

More preferably, the Re of tensile cellulose acylate film and Rth satisfy following formula:

Rth≥Re×1.2，

100≥Re≥20，

350≥Rth≥80。

In machine direction stretch, preferred 0 ± 3 ° of the angle θ that slow axis became of film-direct of travel (machine direction) and the Re of film, more preferably 0 ± 1 °.In crisscross stretching, described angle is preferably 90 ± 3 ° or-90 ± 3 °, more preferably 90 ± 1 ° or-90 ± 1 °.

The thickness of tensile cellulose acylate film is preferably 15 μ m-200 μ m, more preferably 40 μ m-140 μ m.The thickness offset of machine direction and crisscross film all is preferably 0%-3%, more preferably 0%-1%.

Physicals:

The physicals of tensile cellulose acylate film preferably falls in the following scope.

The tensile modulus of film is preferably 1.5kN/mm ²-3.0kN/mm ², more preferably 1.8kN/mm ²-2.6kN/mm ²

The elongation at break of film is preferably 3%-100%, more preferably 8%-50%.

The Tg of film is preferably 95 ℃-145 ℃, more preferably 105 ℃-135 ℃.

The machine direction of film and crisscross on, 80 ℃ place 1 day after, the hot dimensional change of film all is preferably 0% to ± 1%, more preferably 0% to ± 0.3%.

The water vapour permeability of film is preferably 300g/m under 40 ℃ and the 90%RH ²My god-1000g/m ²My god, more preferably 500g/m ²My god-800g/m ²My god.

The equivalent water-content of film is preferably 1 quality %-4 quality % under 25 ℃ and the 80%RH, more preferably 1.5 quality %-2.5 quality %.

The mist degree of film is preferably 0%-3%, more preferably 0%-1%.The total light transmittance of film is preferably 90%-100%.

The processing of cellulose acylate film:

Can in all sorts of ways and handle cellulose acylate film of the present invention, the following describes the certain preferred embodiments of described processing.

Surface treatment:

Cellulose acylate film can randomly carry out surface treatment, thereby plain acylate film of fortifying fibre and various functional layer (for example, undercoat (undercoat layer) and backing layer (back layer)) is bonding.Surface treatment for example is glow discharge processing, uviolizing processing, corona treatment, flame treating or acid or alkaline purification.Glow discharge described here is handled preferably 10 ^-3Low Temperature Plasma Treating under the air pressure of-20 Torr or the Cement Composite Treated by Plasma under the normal atmosphere.Plasma body-energizing gas in the Cement Composite Treated by Plasma refers to the gas of plasma exciatiaon under these conditions.Plasma body-energizing gas comprises that for example argon, helium, neon, krypton, xenon, nitrogen, carbonic acid gas, Chlorofluorocarbons (CFCs) (flons) reach their mixture as tetrafluoromethane.These gas write ups are at Hatsumei KyokaiDisclosure Bulletin (No.2001-1745, Hatsumei Kyokai published in March 15 calendar year 2001), among the p30-32.For the Cement Composite Treated by Plasma under the normal atmosphere that causes concern recently, preferably use at 10-1 the irradiation energy of 20-500KGy under the 000Kev, the more preferably irradiation energy of 20-300KGy under 30-500Kev.In above-mentioned processing, alkali soapization more preferably is extremely effective for the surface treatment of cellulose acylate film.

For alkali soapization, can thin film dippedly in saponification solution, maybe can be coated with film pending with saponification solution.In dipping method, can make film pass through 20-80 ℃ NaOH or the water-soluble liquid bath of KOH of pH10-14, lasted 0.1 minute-10 minutes, neutralization then washes with water and drying.

When carrying out alkali soap according to coating process, operable is dip coated method, coating method, extrusion coating method, excellent coating method and E-type coating process.The preferred solvent of selecting the alkali soap coating solution to use, make that the saponification solution comprise solvent can wetting well transparent support, wherein be coated with described solution, make solvent can not make the surface irregularity of transparent support, and keep support to have the excellent surface state to described support.Particularly, alcoholic solvent is preferred, and Virahol is particularly preferred.The aqueous solution of tensio-active agent also can be used as solvent.Alkali in the alkali soap coating solution is soluble alkali in above-mentioned solvent preferably.More preferably KOH or NaOH.The pH of saponification coating solution is preferably at least 10, and more preferably at least 12.About alkali saponified reaction conditions, the reaction times was preferably room temperature following 1 second-5 minutes, and more preferably 5 seconds-5 minutes, more preferably 20 seconds-3 minutes again.After the alkali soap processing, preferred water or the surface that is coated with the saponification solution of acid elution film, water further washs then.When needed, the coating saponification is handled and oriented film described later is removed processing and can be carried out continuously.In this way, can reduce the number of making the treatment step in the film.Particularly, for example, method for saponification is put down in writing in JP-A-2002-82226 and WO 02/46809.

Preferably, film of the present invention is provided with undercoat, is used to improve itself and thereon functional layer bonding to be formed.Undercoat can be formed on the film after above-mentioned surface treatment, or can directly be formed on the film and not through surface treatment.Internally coated details is put down in writing among the p32 Hatsumei Kyokai Disclosure Bulletin (No.2001-1745 is published in March 15 calendar year 2001 by Hatsumei Kyokai).

Surface treatment step and internally coated formation can be carried out separately or carry out with the final step combination in the film process.In addition, surface treatment step also can be carried out with the step that aftermentioned forms functional group.

The purposes of cellulose acylate film of the present invention:

Preferably, HatsumeiKyokai Disclosure Bulletin (No.2001-1745 is published in March 15 calendar year 2001 by Hatsumei Kyokai), the functional layer of putting down in writing among the p32-45 makes up cellulose acylate film of the present invention with in detail.Wherein, preferably film is provided with polarization layer (being used for polarizer), optical compensating layer (being used for optical compensating sheet) and anti-reflecting layer (being used for anti-reflection film).These are described below in regular turn.

(1) form polarization layer (structure polarizer):

Material:

At present, the method a kind of commonly used of making commercially available polarization film is included in dipping tensile polymkeric substance in the solution that contains iodine or dichroic dye in the bath, thereby iodine or dichroic dye are infiltrated in the binding agent.As polarization film, can use the polarization film of coating, typically for example make by Optiva Inc..Iodine and dichroic dye in the polarization film are orientated in binding agent, and show polarization property.Dichroic dye comprises azoic dyestuff, stibene dyestuff, pyrazolone dye, triphenhlmethane dye, quinoline dye, oxazine dye, thiazine dyes and anthraquinone dye.Preferably, dichroic dye is solvable in water.Also preferably, dichroic dye possess hydrophilic property substituting group (for example, sulfo group, amino, hydroxyl).For example, can use at Hatsumei Kyokai DisclosureBulletin (No.2001-1745 is published in March 15 calendar year 2001 by Hatsumei Kyokai), the compound of putting down in writing among the p58 is as dichroic dye.

The binding agent of using for polarization film, but the polymkeric substance and the crosslinked polymkeric substance of available linking agent of self-crosslinking can be used.These polymkeric substance can be used in combination.Binding agent comprises alkylmethacrylate polymer, styrol copolymer, polyolefine, polyvinyl alcohol, modified polyethylene alcohol, poly-(N hydroxymethyl acrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose and the polycarbonate described in [0022] of JP-A-8-338913 for example.In addition, silane coupling agent also can be used as described polymkeric substance.Wherein, water-soluble polymers (for example, poly-(N hydroxymethyl acrylamide), carboxymethyl cellulose, gel (gelatin), polyvinyl alcohol, modified polyethylene alcohol) is preferred; Gel, polyvinyl alcohol and modified polyethylene alcohol are preferred; Polyvinyl alcohol and modified polyethylene alcohol are most preferred.Particularly preferably, be used in combination two kinds of dissimilar polyvinyl alcohol or modified polyethylene alcohol with different polymerization degree.Preferably, the saponification deg of employed polyvinyl alcohol is 70-100%, more preferably 80-100%.Also preferably, the polymerization degree of polyvinyl alcohol is 100-5000.Modified polyethylene alcohol is put down in writing in JP-A-8-338913, JP-A-9-152509 and JP-A-9-316127.Can be used in combination two or more inhomogeneous polyvinyl alcohol and modified polyethylene alcohol.

Preferably, the following 10 μ m that are limited to of adhesive thickness.About its upper thickness limit,, preferably thinner from the viewpoint of the anti-light leak of the liquid crystal indicator that comprises it.Particularly, for example, preferably the thickness of polarization film is not more than the thickness (about 30 μ m) of at present commercially available polarizer, more preferably 25 μ m at the most, more preferably 20 μ m at the most again.

The binding agent of polarization film can be crosslinked.Polymkeric substance or monomer with crosslinking functionality can be added in the binding agent, perhaps can design binder polymer and make and itself have crosslinking functionality.By exposure, heating or change pH, can realize crosslinked, and the binding agent that obtains having crosslinked structure.Linking agent is at US issued patents No.23 again, record in 297.Boron compound (for example, boric acid, borax) also can be used as linking agent.Be added to cross-linked dosage in the binding agent and be preferably the 0.1-20 quality % of binding agent.In this scope, the orientation of polarizer and the humidity resistance of polarization film are all good.

After crosslinking reaction, preferably remaining unreacted cross-linked dosage is 1.0 quality % at the most in the polarization film, more preferably 0.5 quality % at the most.In this scope, polarization film has good weathering resistance.

Stretch:

Preferably, polarization film is stretched (according to stretching method) or rubs (according to rubbing manipulation), then with iodine or dichroic dye dyeing.

In stretching method, the preferred 2.5-30.0 of stretch ratio times, more preferably 3.0-10.0 doubly.Stretching can realize under drying regime in air.In contrast, stretching also can realize under wet condition by dipping film in water.Preferably, dry tensile stretch ratio is 2.5-5.0 times, and wet tensile stretch ratio is 3.0-10.0 times.Stretching can be carried out once or several times.When stretching several times, even film also can stretch more equably under high stretch ratio.Can be according to following method oriented film.

Before stretching, make the PVA films swell.The swelling capacity of film is 1.2-2.0 doubly (according to the swollen film and the mass ratio of swollen film not).Next, transmit film continuously, film is imported aqueous medium bathe in the dye bath of interior or importing dichroic substance solution by deflector roll.In bath, usually, at 15-50 ℃, oriented film under preferred 17-40 ℃ the bath temperature.By keeping films to stretch, and keep the transfer rate of latter stage nip rolls to be higher than the transfer rate of the nip rolls of last stage with the two pairs of nip rollss.Consider above-mentioned effect and advantage, tensile stretch ratio (length of tensile film/initial film length ratio-following identical) is preferably 1.2-3.5 doubly, and more preferably 1.5-3.0 doubly.Next, the tensile film is dried to polarization film at 50-90 ℃.

Laminated:

The saponified cellulose acylate film is laminated with the polarization film for preparing by stretching, thus constitute polarizer.Laminated the two the direction of preferred control makes the curtain coating direction of principal axis of cellulose acylate film intersect with the 45 and the tensile axis direction of polarizer.

Be not particularly limited, the tackiness agent of laminated usefulness can be the aqueous solution of PVA resin (comprising the PVA with any modification in acetoacetyl, sulfonic acid group, carboxyl and the oxyalkylene group) or boron compound.Wherein, PVA resin preferably.The thickness of bonding coat is preferably 0.01-10 μ m, more preferably 0.05-5 μ m after drying.

The transmittance of the polarizer that obtains like this is preferably higher, and its degree of polarization is also preferably higher.Particularly, for the light of wavelength 550nm, the transmissivity of polarizer is preferably 30-50%, more preferably 35-50%, most preferably 40-50%.For the light of wavelength 550nm, the preferred 90-100% of the degree of polarization of polarizer, more preferably 95-100%, most preferably 99-100%.

In addition, Gou Zao polarizer can close with λ/4 flaggies like this, forms circular polarizing disk.In this case, laminated they the two, make λ/slow axis of 4 plates and the absorption axes of polarizer angle at 45 intersect.In this, λ/4 plates are not particularly limited, but preferably its wavelength dependence (wavelength dependency) makes that the delay under the low wavelength is less.In addition, further preferably use and comprise λ/4 plates of absorption axes with respect to the optical anisotropic layer of the polarization film of 20-70 ° of machine direction inclination and liquid crystalline cpd.

(2) form optical compensating layer (structure optical compensating sheet):

Optical anisotropic layer is used for the liquid crystalline cpd of compensation liquid crystal cell when the black display of liquid crystal indicator, by forming oriented film on cellulose acylate film, forming optical anisotropic layer thereon then, constructs optical compensating sheet.

Oriented film:

Oriented film is located at and carried out on the above-mentioned surface-treated cellulose acylate film.Oriented film has the function that limits the liquid crystal molecular orientation direction.Yet if can make liquid crystalline cpd orientation and can former state fix its state of orientation, therefore the oriented film integrant that is not absolutely necessary can be omitted, and always not need so.In this case, only the optical anisotropic layer on the oriented film that has been fixed of state of orientation is transferred on the polarizer, constructs polarizer of the present invention.

For example can pass through friction treatment organic compound (preferred polymers), inclination vapour deposition mineral compound, form the microflute layer or (for example accumulate organic compound according to Langmuir-Blodgett method (LB film), ω-tricosanic acid, the two octadecyl methyl ammoniums of chlorination, methyl stearate), form oriented film.In addition, also have known other oriented films by giving electric field or magnetic field or can having the orientation function by rayed.

Oriented film preferably forms by the friction treatment polymkeric substance.In principle, the polymkeric substance that is used for oriented film has and plays the molecular structure that makes the liquid crystal molecular orientation effect.

Preferably, except making the liquid crystal molecular orientation effect, the polymkeric substance that uses among the present invention also has with the main chain bonded and contains crosslinking functionality () side chain for example, two keys perhaps is incorporated in the side chain and has the crosslinking functionality that makes the liquid crystal molecular orientation effect.

But the polymkeric substance that is used for oriented film can be the polymkeric substance or the crosslinked polymkeric substance of the enough linking agents of energy of self-crosslinking, maybe can be the combination of these two.The example of above-mentioned polymkeric substance is the alkylmethacrylate polymer described in the JP-A-8-338913 [0022], styrol copolymer, polyolefine, polyvinyl alcohol and modified polyethylene alcohol, poly-(N hydroxymethyl acrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose and polycarbonate.Silane coupling agent also can be used as described polymkeric substance less.Preferably, described polymkeric substance be water-soluble polymers (for example, poly-(N hydroxymethyl acrylamide), carboxymethyl cellulose, gel, polyvinyl alcohol, modified polyethylene alcohol), more preferably gel, polyvinyl alcohol and modified polyethylene alcohol, most preferably polyvinyl alcohol and modified polyethylene alcohol.Particularly preferably, be used in combination two kinds of dissimilar polyvinyl alcohol or modified polyethylene alcohol as described polymkeric substance with different polymerization degree.Preferably, the saponification deg of employed polyvinyl alcohol is 70-100%, more preferably 80-100%.Also preferably, the polymerization degree of polyvinyl alcohol is 100-5000.

Have the side chain that makes the liquid crystal molecular orientation effect and have hydrophobic group usually as functional group.Particularly, the type of functional group can be according to the essential state of orientation decision of liquid crystal molecule type that will be orientated and molecule.For example, the modification group of modified polyethylene alcohol can pass through in modification by copolymerization, chain transfer modification or the block polymerization modification introducing polymkeric substance.The example of modification group be the alkyl that replaces of hydrophilic radical (for example, hydroxy-acid group, sulfonic acid group, phosphonyl group, amino, ammonium group, amide group, thiol group), alkyl, fluorine atom, sulfide group, polymer-based group with 10-100 carbon atom (for example, undersaturated polymer-based group, epoxide group, the nitrogen heterocyclic propyl group) and alkoxysilyl (for example, tri-alkoxy, dialkoxy, monoalkoxy).The object lesson of described modified polyethylene alkylol cpd for example is documented in JP-A-2000-155216, and [0022]-[0145] and JP-A-2002-62426 is in [0018]-[0022].

When the side chain with crosslinking functionality combines with the main chain of oriented film polymkeric substance, perhaps when crosslinking functionality being introduced when having the side chain of the polymkeric substance that makes the liquid crystal molecular orientation effect, the polymkeric substance of oriented film can with the polyfunctional monomer copolymerization in the optical anisotropic layer.Consequently, not only between polyfunctional monomer, and between the oriented film polymkeric substance, even between polyfunctional monomer and oriented film polymkeric substance, all with the covalency pattern combination securely each other of bonding each other.Therefore, described crosslinking functionality is introduced the physical strength of obviously having improved the optical compensating sheet that obtains in the oriented film polymkeric substance.

Preferably, the crosslinking functionality of oriented film polymkeric substance contains polymerizable groups, as polyfunctional monomer.Particularly, for example, with reference at JP-A-2000-155216, those of record in [0080]-[0100].Except above-mentioned crosslinking functionality, the oriented film polymkeric substance also can be crosslinked with linking agent.

Linking agent for example comprises aldehyde, N-methylol compound, dioxane derivatives, can have active compound, active vinyl-compound, active halide compound, isoxazole and dialdehyde starch by activating its carboxyl.Can be used in combination two or more dissimilar linking agents.Particularly, for example, can use the compound of record in [0023]-[0024] at JP-A-2002-62426.The preferably aldehyde of hyperergy, more preferably glutaraldehyde.

Preferably, the cross-linked dosage that is added in the polymkeric substance is the 0.1-20 quality % of polymkeric substance, more preferably 0.5-1 5 quality %.Also preferably, remaining unreacted cross-linked dosage 1.0 quality % at the most in the oriented film, more preferably 0.5 quality % at the most.In with oriented film linking agent control to above-mentioned value the time, even even film uses in liquid crystal indicator for a long time and during long-time the placement, can guarantee that also film has good durability, can not become reticulation in high temperature and high humidity atmosphere.

Basically, by heating then and dry (so that carrying out crosslinked) as being orientated to the above-mentioned polymer-coated to the transparent support that contains linking agent of mould material, the such film that forms of friction can form oriented film then.By above-mentioned be applied to film forming material on the transparent support after, can carry out crosslinking reaction in any stage.When water-soluble polymers such as polyvinyl alcohol when being orientated to mould material, preferably the solvent used of coating solution is the mixed solvent that makes froth breaking organic solvent (for example, methyl alcohol) and water.The mass ratio of water/methyl alcohol is preferably 0/100-99/1, more preferably 0/100-91/9.This class mixed solvent can prevent to form bubble effectively in coating solution, consequently, can greatly reduce oriented film and even optical anisotropic layer in surface imperfection.

For forming oriented film, preferably use spin coating method, dip coated method, coating method, extrusion coating method, excellent coating method and method of roll coating.Particularly preferably be excellent coating method.Also preferably, dried film thickness is 0.1-10 μ m.Heat drying will be to carry out at 20-110 ℃.For full cross-linked, Heating temperature is preferably 60-100 ℃, more preferably 80-100 ℃.Can be 1 minute-36 hours time of drying, but preferred 1-30 minute.The preferred pH that limits coating solution makes it be suitable for used linking agent most.For example, when using glutaraldehyde, the pH of coating solution is preferably 4.5-5.5, and more preferably 5.

Oriented film is located on the transparent support or is located on the undercoat.By crosslinked above-mentioned polymer layer, the surface of friction layer then, can form oriented film.

For friction treatment, can use any method in the liquid crystal aligning processing that is widely used in LCD.Particularly, for example, by using paper, tulle (gauze), felt, rubber, nylon or trevira, thereby make thin film alignment in anticipated orientation on the surface of pre-determined direction friction orientation film.Usually, use to have the cloth of evenly planting hair with equal length and same thickness fiber, and with this cloth friction film surface several times.

On technical scale, contact with the film that in system, moves by the friction roller that makes rotation with polarization layer, operate.Preferably, the circularity of friction roller, cylindricity and deflection (degree of eccentricity) 30 μ m at the most respectively.Also preferably, the overlap joint angle (lapping angle) of film is 0.1-90 ° around the friction roller.Yet described in JP-A-8-160430, for stablizing friction treatment, film can 360 ° or wide-angle overlap joint more.Preferably, the film travelling speed is 1-100m/min.Sliding angle is 0-60 °, preferably selects the sliding angle that is fit in this scope.When described film was used for liquid crystal indicator, sliding angle was preferably 40-50 °, more preferably 45 °.

The thickness of the oriented film that obtains like this is preferably 0.1-10 μ m.

Next, the liquid crystal molecule of optical anisotropic layer is orientated on oriented film.Thereafter, when needed, the reaction of polyfunctional monomer in oriented film polymkeric substance and the optical anisotropic layer, or with the crosslinked oriented film polymkeric substance of linking agent.

The liquid crystal molecule that can be used in the optical anisotropic layer comprises rod shaped liquid crystal molecule and discotic liquid-crystalline molecules.Rod shaped liquid crystal molecule and discotic liquid-crystalline molecules can be high molecule liquid crystal or low molecular weight liquid crystal.In addition, they comprise the crosslinked low molecular weight liquid crystal that does not show liquid crystal liquid crystal property.

Rod shaped liquid crystal molecule:

Rod shaped liquid crystal molecule is the phenyl pyrimidine, phenyl pyrimidine, Ben Ji diox, tolane and the thiazolinyl phenylcyclohexane formonitrile HCN of alkoxyl group-replacement of azomethine, azoxy compound, cyanobiphenyl, cyanobenzene ester, benzoic ether, hexahydrobenzoic acid phenyl ester, cyano-phenyl hexanaphthene, cyano group-replacement preferably.

Rod shaped liquid crystal molecule comprises metal complexes.The liquid crystalline polymers that contains rod shaped liquid crystal molecule in its repeating unit also can be used as rod shaped liquid crystal molecule in the present invention.In other words, the used rod shaped liquid crystal molecule of the present invention can combine with (liquid crystal) polymkeric substance.

Rod shaped liquid crystal molecule is documented in Quarterly Journal of General Chemistry, Vol.22, and Liquid Crystal Chemistry (1994), the 4th, 7 and 11 chapters, the ChemicalSociety of Japan compiles; Liquid Crystal Devices Handbook, the 142 ^NdCommittee of the Nippon Academic Promotion compiles, in the 3rd chapter.

The degree of birefringence of rod shaped liquid crystal molecule is preferably 0.001-0.7.

Preferably, rod shaped liquid crystal molecule has polymerisable group, to fix their state of orientation.Polymerisable group is the unsaturated group or the cationoid polymerisation group of radical polymerization preferably.Polymer-based group and the polymeric liquid crystal compound mentioned in [0064]-[0086] particularly, for example, are arranged at JP-A-2002-62427.

Discotic liquid-crystalline molecules:

Discotic liquid-crystalline molecules comprises the research report that for example is documented in people such as C.Destrade, Mol.Cryst., Vol.71, the benzene derivative among the p111 (1981); Be documented in people's such as C.Destrade research report, MoI.Cryst., Vol.122, p141 (1985) and Physics lett.A, Vol.78, three indeno benzene (truxene) derivatives among the p82 (1990); Be documented in people's such as B.Kohne research report, Angew.Chem., Vol.96, the cyclohexane derivant among the p70 (1984); With the research report that is documented in people such as J.M.Lehn, J.Chem.Commun., people's such as p1794 (1985) and J.Zhang research report, J.Am.Chem.Soc, Vol.116, the azepine crown type (azacrown-type) among the p2655 (1994) is encircled greatly or the big ring of phenylacetylene.

Discotic liquid-crystalline molecules comprises following liquid crystalline cpd, wherein said liquid crystalline cpd molecule centronucleus by the benzoyloxy of straight chained alkyl, alkoxyl group or replacement as the radial replacement of side chain.Preferably the molecule of compound or molecule aggregates have rotational symmetry and certain orientation take place.Always do not need, when this discotic liquid-crystalline molecules formed optical anisotropic layer, the final compound that exists was a discotic liquid-crystalline molecules in optical anisotropic layer.For example, low molecule discotic liquid-crystalline molecules can have when being exposed to the group that heat or light time can react, and consequently, they obtain not having the macromolecular compound of liquid crystal through heat or photoresponse and polymerization or crosslinked.The preferred example of discotic liquid-crystalline molecules is documented among the JP-A-8-50206.In addition, the polymerization of discotic liquid-crystalline molecules is documented among the JP-A-8-27284.

For by the fixing discotic liquid-crystalline molecules of polymerization, must be with the disc centre of polymerisable group replacement discotic liquid-crystalline molecules.Preferably, polymerisable group combines with disc centre by linking group.Therefore, even this compounds also can remain on state of orientation after polymerization.For example, that can mention has at JP-A-2000-155216, the compound of record in [0151]-[0168].

In mixing orientation, the angle between main shaft of discotic liquid-crystalline molecules (disc face) and the polarization film face along with the distance of distance polarization film face along the increase of optical anisotropic layer depth direction and increase or reduce.Preferably, angle increases along with distance and reduces.It can be any pattern that increases continuously, reduces continuously, intermittently increases, intermittently reduces, comprises the variation that increases continuously and reduce continuously or comprise in changing the intermittence that increases and reduce that angle changes.Intermittently change and comprise that pitch angle wherein is in zone that the middle portion of thickness direction does not change.Angle can comprise the zone that does not have angle to change, as long as increase on the whole or reduce.Preferably, angle changes continuously.

Usually the material by suitably selecting discotic liquid-crystalline molecules or the material of oriented film, or, can control the main shaft mean direction of the discotic liquid-crystalline molecules of polarization film side by suitably selecting the friction treatment method.Usually the material of material by suitably selecting discotic liquid-crystalline molecules or the additive that uses with discotic liquid-crystalline molecules, main shaft (disc face) direction of discotic liquid-crystalline molecules that can control surface side (extraneous air side).The example of the additive that can use with discotic liquid-crystalline molecules comprises for example softening agent, tensio-active agent, polymerization single polymerization monomer and polymkeric substance.As mentioned above, by suitably selecting liquid crystal molecule and additive, also can control the main shaft intensity of variation of differently-oriented directivity.

Other components of optical anisotropic layer:

With above-mentioned liquid crystal molecule, softening agent, tensio-active agent, polymerization single polymerization monomer and other materials can be added in the optical anisotropic layer orientation of liquid crystal molecule in the homogeneity of filming with improvement, the intensity of film and the film.Preferably, additive has excellent compatibility with the liquid crystal molecule that constitutes optical anisotropic layer, and the tilt angle varied of liquid crystal molecule is had some influences, and orientation that can disturbing molecule.

Polymerization single polymerization monomer comprises compound free redical polymerization or cationically polymerizable.The monomer of multifunctional free redical polymerization preferably.In addition, further preferably can with those of the above-mentioned liquid crystalline cpd copolymerization that contains polymerizable groups.For example, that can mention has at JP-A-2002-296423, the compound of record in [0018]-[0020].The compound amount in the described layer of being added to is generally the 1-50 quality % of the discotic liquid-crystalline molecules in the described layer, but preferred 5-30 quality %.

Tensio-active agent can be any known tensio-active agent, but is preferably fluorine-containing compound.Particularly, for example, that can mention has at JP-A-2001-330725, the compound of record in [0028]-[0056].

Can be preferably the polymkeric substance that can change the pitch angle of discotic liquid-crystalline molecules with the polymkeric substance that discotic liquid-crystalline molecules uses.

The example of polymkeric substance is a cellulose ester.The preferred example of cellulose ester is put down in writing in [0178] at JP-A-2000-155216.In order not disturb the orientation of liquid crystal molecule in layer, be added to the 0.1-10 quality % that amount of polymers in the layer is preferably liquid crystal molecule, more preferably 0.1-8 quality %.

Preferably, the plate-like nematic liquid crystal phase/solid transformation temperature of discotic liquid-crystalline molecules is 70-300 ℃, more preferably 70-170 ℃.

The formation of optical anisotropic layer:

Contain the polymerization starter of liquid crystal molecule and optional existence described later and the coating solution of other optional compositions that exist by coating on oriented film, can form optical anisotropic layer.

The used solvent of preparation coating solution is preferably organic solvent.Representative examples of organic be acid amides (for example, N, dinethylformamide), sulfoxide (for example, dimethyl sulfoxide (DMSO)), heterogeneous ring compound (for example, pyridine), hydrocarbon are (for example, benzene, hexane), alkyl halide (for example, chloroform, methylene dichloride, tetrachloroethane), ester (for example, methyl acetate, butylacetate), ketone (for example, acetone, methyl ethyl ketone), ether (for example, tetrahydrofuran (THF), 1, the 2-glycol dimethyl ether).Wherein, preferably alkyl halide and ketone.Two or more organic solvents can be used in combination.

Coating solution can be coated on the oriented film by any currently known methods (for example, coiling rod coating, the coating of extrusion coated, direct intaglio plate, contrary intaglio plate coating, mould coating).

The thickness of optical anisotropic layer is preferably 0.1-20 μ m, more preferably 0.5-15 μ m, most preferably 1-10 μ m.

Fixing of the state of orientation of liquid crystal molecule:

The liquid crystal molecule of orientation can be fixed in the state of orientation former state.Preferably, fix by polymerization.Polymerization comprises the thermopolymerization of using thermal polymerization and the photopolymerization of using Photoepolymerizationinitiater initiater.Preferably photopolymerization.

Photoepolymerizationinitiater initiater for example comprises the alpha-carbonyl compound, and (USP 2,367,661,2,367,670), (USP 2 for acyloin ether, 448,828), the aromatic series acyloin compound (USP 2,722,512) of α-hydrocarbon-replacement, (USP 3 for the multinuclear naphtoquinone compounds, 046,127,2,951,758), (USP 3 in the combination of triarylimidazoles dimer and right-aminophenyl ketone, 549,367), acridine compound and compound phenazine (JP-A-60-105667, USP 4,239,850) He the oxadiazole compound (USP 4,212,970).

The add-on of Photoepolymerizationinitiater initiater is preferably the 0.01-20 quality % of coating solution solid substance, more preferably 0.5-5 quality %.

Preferably, the UV line is used for rayed polymerisable liquid crystal molecule.Preferably, irradiation energy is 20mJ/cm ²-50J/cm ², more preferably 20-5000mJ/cm ², more preferably 100-800mJ/cm again ²For promoting photopolymerization, can under heating, carry out rayed.

Protective layer can be located on the optical anisotropic layer

Preferably, optical compensating film can make up with polarization film.Particularly, above-mentioned optical anisotropic layer is coated on coating solution on the surface of polarization film, forms optical anisotropic layer thereon.Consequently, do not have polymeric film between polarization film and optical anisotropic layer, therefore obtain thin polarizer, wherein the stress that causes because of the polarization film dimensional change (strain * sectional area * elasticity) reduces.When polarizer of the present invention was installed to the large scale liquid crystal display unit, light leak problem and device demonstration high quality graphic can not take place.

Preferably, stretching polarization film and optical compensating layer, make between them the pitch angle corresponding to the machine direction of the axis of homology of two polarizers of liquid crystal cell both sides adherent that constitute LCD and liquid crystal cell or crisscross between angulation.Usually, the pitch angle is 45 °.Yet, in recent years,, researched and developed wherein not some devices of 45 ° always of pitch angle, and preferably draw direction changes in any required mode according to the design of LCD for transmission-type, reflection-type or transflective LCD.

(3) form anti-reflecting layer (being used for anti-reflection film):

Usually, by on transparent base, forming, construct anti-reflection film as the low-index layer of anti-trowel used for plastering layer and one deck at least (high refractive index layer or middle index layer) of refractive index ratio low-refraction floor height.

By for example forming multilayer film with chemical vapor deposition (CVD) or the laminated transparent film of physical vapor deposition (PVD) mode with mineral compound (for example, metal oxide) of different refractivity; Or according to sol-gel method use metallic compound such as metal oxide, form the film of colloidal metal oxide particle, carry out aftertreatment (for example, the irradiation of the UV among the JP-A-9-157855 then, or the Cement Composite Treated by Plasma among the JP-A-2002-327310), thus obtain film.

On the other hand, the various anti-reflection films of high productivity have been proposed, by being laminated in the film forming of dispersive inorganic particulate in the matrix.

Can further handle the anti-reflection film that makes according to above-mentioned coating process, make its outermost surface roughening and have anti-dazzle performance.

Cellulose acylate film of the present invention can be applied to any the above-mentioned type.Particularly preferably, described film is applied to (layer application type film) on the membrane structure of layer-coating system.

The layer structure of layer application type anti-reflection film:

Designed anti-reflection film have on base material form in order at least in the layer structure of index layer, high refractive index layer and low-index layer (outermost layer), it satisfies following index distribution.

The specific refractory power of the specific refractory power＞low-index layer of the specific refractory power＞transparent support of the specific refractory power of high refractive index layer＞middle index layer.

Between transparent support and middle index layer, hard coat can be set.In addition, specific refractory power hard coat, high refractive index layer and low-index layer during film can comprise.

For example can be with reference to JP-A-8-122504, JP-A-8-110401, JP-A-10-300902, JP-A-2002-243906, JP-A-2000-111706.

Each layer can have other functions.That for example, can mention has antifouling low-index layer and an antistatic high refractive index layer (for example, JP-A-10-206603, JP-A-2002-243906).

Preferably, the mist degree of anti-reflection film at the most 5%, more preferably at the most 3%.Also preferably, in the pencil hardness test according to JIS K5400 method, film strength is 1H at least, more preferably 2H at least, most preferably 3H at least.

High refractive index layer and middle index layer:

The high refractive index layer of anti-reflection film is formed by solidified film and matrix binding agent, and the solidified film contains the ultramicron of the mineral compound of high refractive index at least, and its median size is 100nm at the most.

The inorganic compound particles of high refractive index is that specific refractory power is at least those of 1.65, preferably at least 1.9.Inorganic compound particles for example is the particle that has the particle of any metal oxide among Ti, Zn, Sb, Sn, Zr, Ce, Ta, La and the In and contain the composite oxides of above-mentioned atoms metal.

For example, can use surface treatment agent (for example, silane coupling agent, JP-A-11-295503,, JP-A-11-153703, JP-A-2000-9908; Anionic compound or organo-metallic coupling agent JP-A-2001-310432) are handled ultramicron; Can use core-shell structure that the high refractive index particle constitutes ultramicron as core (for example, or be used in combination ultramicron and specific dispersant (for example, JP-A-11-153703, USP 6 JP-A-2001-166104),, 210,858 B1, JP-A-2002-2776069).

The material that forms matrix can be any known thermoplastic resin and curable resin film.

For material, further preferably at least a composition, it is selected from the composition that contains the polyfunctional compound, wherein this compound has group at least two free redical polymerizations and/or cationically polymerizable, and the composition or its part condensation product that comprise the organometallic compound that contains hydrolysable group.For this point, for example, with reference to the compound that is documented among JP-A-2000-47004, JP-A-2001-315242, JP-A-2001-31871 and the JP-A-2001-296401.

In addition, the curable film that forms by colloidal metal oxide and metal alkoxide compound compositions preferably, wherein colloidal metal oxide obtains from the hydrolytic condensate of metal alkoxide compound.For example, this film is documented among the JP-A-2001-293818.

The specific refractory power of high refractive index layer is 1.70-2.20 normally.The thickness of high refractive index layer is 5nm-10 μ m preferably, more preferably 10nm-1 μ m.

In the specific refractory power of index layer be controlled between the specific refractory power of the specific refractory power of low-index layer and high refractive index layer.The specific refractory power of middle index layer is 1.50-1.70 preferably.

Low-index layer

Low-index layer is laminated on the high refractive index layer in order.The specific refractory power of low-index layer can be 1.20-1.55 for example, but preferred 1.30-1.50.

Low-index layer preferably constitutes the outermost layer with good scuff resistance and good didirtresistance.For significantly strengthening the scuff resistance of this layer, be the surface of lubricated this layer effectively.For this point, for example, can use by adding conventional silicone compounds or fluorochemicals and form the method for thin layer.

The specific refractory power of fluorochemicals is 1.35-1.50 preferably, more preferably 1.36-1.47.Fluorochemicals preferably has the crosslinkable or the polymerisable functional group of the fluorine atom that contains 35-80 quality %.

For example, can use to be documented in JP-A-9-222503 [0018]-[0026]; JP-A-11-38202, [0019]-[0030]; JP-A-2001-40284, [0027]-[0028]; Compound among the JP-A-2000-284102.

The silicone resin compound preferably has polysiloxane structure, and wherein polymer chain contains curable functional group or polymerisable functional group, and forms the film with crosslinked structure.For example, it comprises reactive siloxane (for example, Silaplane by Chisso make) and at two ends by the end capped polysiloxane structure of silanol (for example, JP-A-11-258403).

Preferably, having the fluoropolymer of crosslinked or polymerisable group and/or the crosslinked or polyreaction of siloxane polymer carries out as follows: when coating contains the outermost coating composition of formation of polymerization starter and sensitizing agent or afterwards, and by carrying out crosslinked or polymerization with rayed or heating coating layer.

In addition, the curable film of sol-gel preferably, the silane coupling agent that it comprises organometallic compound such as silane coupling agent and has specific fluorine-containing alkyl, and wherein they carry out condensation reaction and cured film in the presence of catalyzer.

For example, that can mention has silane compound or its partial hydrolysis condenses (JP-A-58-142958, JP-A-58-147483, JP-A-58-147484, JP-A-9-157582, JP-A-11-106704) that contains Polyfluoroalkyl and has the silyl compound (JP-A-2000-117902, JP-A-2001-48590, JP-A-2002-53804) of fluorine-containing long chain alkyl group, poly-(perfluoroalkyl ethers) group.

As the additive outside the mentioned component, low-index layer can contain filler, and (for example, the median size of primary particle is the low-refraction mineral compound of 1-150am, as silicon-dioxide (silica) and fluorine-containing particle (magnesium fluoride, Calcium Fluoride (Fluorspan) and barium fluoride); Be documented in JP-A-11-3820, [0020]-[0038]) in organic particle), silane coupling agent, lubricant, tensio-active agent etc.

When low-index layer is below outermost layer, can form low-index layer (for example, vacuum evaporation method, spray method, ion plating method or plasma CVD method) by gas phase process.Yet preferably using can the low-cost coating process that forms low-index layer.

The thickness of low-index layer is 30-200nm preferably, more preferably 50-150nm, most preferably 60-120nm.

Hard coat:

For strengthening the physical strength at the transparent support anti-reflection film to be formed, hard coat can be formed on the surface of transparent support.Particularly preferably being hard coat is arranged between transparent support and the above-mentioned high refractive index layer.

But hard coat preferably forms by the compound generation crosslinking reaction or the polyreaction of light and/or thermofixation.Curable functional group is the functional group of photopolymerization preferably, and the organometallic compound that contains hydrolyzable functional group is the organoalkoxysilane based compound preferably.

The object lesson of these compounds is with above-mentioned described those are identical to high refractive index layer.

The object lesson that constitutes the component acid of hard coat for example is to be documented among JP-A-2002-144913, JP-A-2000-9908 and the WO 00/46617 those.

High refractive index layer also can serve as hard coat.In this case, preferably, add in the hard coat micropartical and fine dispersion using and forming the identical mode of high refractive index layer.

Hard coat can contain the particle that median size is 0.2-10 μ m, and also as the antiglare layer (below will illustrate) with anti-dazzle function.

Can compatibly design the thickness of hard coat according to purposes.The thickness preference of hard coat is 0.2-10 μ m in this way, more preferably 0.5-7 μ m.

In the pencil hardness test according to JIS K5400 method, the intensity of hard coat is 1H at least preferably, more preferably 2H at least, most preferably 3H at least.Further preferably, before according to the taper of JISK5400 method test and afterwards, the wearing and tearing of sample are as far as possible little.Forward scattering layer (front-scattering layer):

The forward scattering layer can be set, be used for when film is applied to liquid crystal indicator, improving the visual angle of upper and lower sides and left and right sides.Micropartical with different refractivity can disperse in hard coat, and the hard coat that obtains can be used as the forward scattering layer.

For this point, for example, with reference to JP-A-11-38208, wherein the forward scattering coefficient is specifically limited; JP-A-2000-199809, wherein transparent resin and atomic relative refractive index are limited to specified range; And JP-A-2002-107512, wherein haze value is limited at least 40%.

Other layers:

Except above-mentioned layer, film can also have bottom (primer layer), antistatic layer, undercoat, protective layer etc.

Coating process:

Each of anti-reflection film layer can form by various coating processes, for example dip coated, airblade coating, curtain coating, roller coat, the coating of coiling rod, intaglio plate coating, the coating of nick version or extrusion coated (USP 2,681,294).

Anti-dazzle function:

Anti-reflection film can have the anti-dazzle function of scattering ambient light.By making the film surface roughening, make it have anti-dazzle function.When anti-reflection film had anti-dazzle function, its mist degree was preferably 3-30%, more preferably 5-20%, most preferably 7-20%.

For making the anti-reflection film surface roughening, can use any method that wherein fully keeps coarse surface shape.For example, having of can mentioning micropartical is added in the low-index layer so that the method for the surface roughening of this layer (for example, JP-A-2000-271878); (0.1-50 quality %) relatively large particle (particle diameter 0.05-2 μ m) is added to the lower floor's (high refractive index layer under the low-index layer on a small quantity, in index layer or hard coat) in so that lower floor's surface roughening, and form low-index layer thereon, keep simultaneously lower floor surface shape method (for example, JP-A-2000-281410,, JP-A-2000-95893, JP-A-2001-100004, JP-A-2001-281407); And with the shape physical transfer of roughening to the lip-deep method of outermost layer (stain-proofing layer) (for example, handling) according to the embossing among JP-A-63-278839, JP-A-11-183710, the JP-A-2000-275401.

Liquid crystal indicator:

Cellulose acylate film of the present invention can be advantageously used in the liquid crystal indicator.Especially, cellulose acylate film of the present invention is effective when as the optical compensating sheet in the liquid crystal indicator.As under the situation of optical compensating sheet, polarizer (aftermentioned) is with become to make the former axis of homology by the film forming optical compensating sheet preferred disposition of cellulose acylate parallel or vertical with the latter's slow axis basically at film itself.The structure of such polarizer and optical compensating sheet is put down in writing in JP-A-10-48420.Liquid crystal indicator comprises: be loaded with between two electrode base boards the liquid crystal cell of liquid crystal, respectively two polarizers of liquid crystal cell both sides configurations and place liquid crystal cell and polarizer between at least one optical compensating sheet.

The following describes various types of liquid crystal indicators that cellulose acylate film of the present invention is suitable for.

The TN-mode LCD:

The TN-pattern is most frequently used in the colored TFT liquid crystal indicator, and is documented in many documents.The state of orientation of TN-mode display liquid crystal cell when black level is as follows: rod shaped liquid crystal molecule is erect at the element middle body, and keeps flat near device substrate.The OCB-mode LCD:

It is the liquid crystal cell of curved orientation pattern, wherein is orientated at the upper section of liquid crystal cell and the rod shaped liquid crystal molecule substantial reverse (symmetrically) of lower part.The liquid crystal indicator that comprises this curved orientation mode liquid crystal element is disclosed in USP 4,5 83, in 825 and 5,410,422.Because the upper section of liquid crystal cell and the rod shaped liquid crystal molecule symmetric orientation in the lower part, therefore the liquid crystal cell of this curved orientation pattern has from optical compensation function.Therefore, this liquid crystal mode is also referred to as OCB (optical compensation curved) liquid crystal mode.

State of orientation when showing about OCB-mode liquid crystal element black level, identical with TN-mode liquid crystal element, rod shaped liquid crystal molecule is erect at the element middle body, and keeps flat near device substrate.

The VA-mode LCD:

It is characterized in that, when not applying voltage, rod shaped liquid crystal molecule perpendicular orientation.VA-mode liquid crystal element comprises: the VA-mode liquid crystal element of (1) narrow sense, wherein do not applying rod shaped liquid crystal molecule perpendicular orientation under the voltage, but substantial horizontal orientation (JP-A-2-176625) when applying voltage, except that it, also comprise, (2) be used to enlarge multiple domain VA-pattern (MVA-pattern) liquid crystal cell (SID97 at visual angle, Digest of Tech.Papers (subscribing this), 28 (1997) 845), (3) liquid crystal cell of n-ASM pattern, wherein the rod shaped liquid crystal molecule perpendicular is orientated when not applying voltage, (Nippon Liquid Crystal Discussion Meeting subscribes this but be orientated to reverse the multiple domain mode when applying voltage, and (4) SURVAIVAL mode liquid crystal element (publicity in LCD International 98) p58-59 (1998)).Other liquid crystal indicators:

Based on above-mentioned identical consideration, the liquid crystal indicator of ECB-pattern and STN-pattern can be by optical compensation.

Analytical procedure and evaluation method:

The following describes the method for analyzing and estimating cellulose acylate pellet and cellulose acylate film.According to the data among the present invention of following method mensuration.

(1) crystallization melting heat:

The cellulose acylate pellet of 10-20mg of weighing, and put into sample disc.Use DSC (dsc), sample is heated to 250 ℃ with the speed of 10 ℃/min from room temperature, obtain the crystallization melting heat (J/g) of sample from the summation of 170 ℃-250 ℃ thermal absorption peak areas.In the present invention, when not detecting absorption peak, the crystallization melting heat is expressed as 0 (J/g).

(2) needle-like impurity:

Cellulose acylate pellet is dissolved in the methylene dichloride, and making its concentration is 20 quality %, and curtain coating solution forms the cellulose acylate film of thickness 100 μ m.Place on the polarizing microscope, observe down at 50 times.See that under cross-polarized light (cross-Nicol) state needle-like impurity is bright spot, the bright spot number of counting per unit weight sample.

(3) sulphate groups mass contg:

Measure the sulphate groups mass contg of cellulose acylate pellet according to ASTM D-817-96 method.

(4) basic metal amount and group II metal amount:

Nitric acid is added in the cellulose acylate pellet, uses the multiband ashing, be dissolved in the water then.According to the ICP-OES method, basic metal amount in the working sample and group II metal amount.

(5) weight average degree of polymerization (DPw):

Cellulose acylate is dissolved in prepares sample solution (0.5 quality %) among the THF.Under the following conditions, the weight-average molecular weight (Mw) by the GPC working sample.Use polystyrene (TSK-polystyrene standard, molecular weight 1050,5970,18100,37900,190000,706000) to draw working curve.With the molecular weight of the value Mw that obtains like this, obtain DPw divided by each segment (per one segment) that obtains from the substitution value of determining according to following method.

Post: TSK GEL Super HZ4000, TSK GEL Super HZ2000

TSK GEL Super HZM-M，TSK Guard Column Super

HZ-L

Column temperature: 40 ℃

Eluent: THF

Flow velocity: 1ml/min

Detector: RI

(6) the acyl substituted degree in the cellulose acylate:

According to ASTM D-817-91 method, with the cellulose acylate complete hydrolysis, free carboxy acid or its salt by gas-chromatography or liquid chromatography quantitative assay obtain obtain the acyl substituted degree in the sample.

(7) SP value:

Use is at J.Brandrup, E.H.Immergut and E.A.Grulke, " PolymerHandbook Fourth Edition ", VII/688-694 (1998), John Wiley﹠amp; Sons, the data of putting down in writing among the Inc..The data of not put down in writing in the following manner (298 ° K temperature under value).

According at J.H.Hildebrand, " Solubility of Nonelectrolytes ", 424-427 (1950), the method for putting down in writing among the Reinhold Publishing Co. obtains data according to following formula (1):

SP value (σ)=[(Δ H-RT)/VL] ^1/2(1)

Wherein σ represents solubility parameter; Δ H represents a vaporization heat; VL represents molecular volume; R represents gas law constant (1.986 cal/mol).

Δ H is according to the Hildebrand rule, based on the sample boiling point, presses the value under 298 ° of K temperature that following formula (2) calculates.About calculate the method for solubility parameter according to the Hildebrand rule, can use J.H.Hildebrand, " Solubility ofNonelectrolytes ", 424-427 (1950), the method for putting down in writing among the Reinhold Publishing Co..

ΔH298＝23.7Tb+0.020Tb ²-2950 (2)

The boiling point of Tb representative sample wherein.

Embodiment

Illustrate in greater detail the present invention below by embodiment and Comparative Examples.In following examples, the details of used material, consumption and ratio and processing and treating processes can suitably be improved or change, and can not exceed the spirit and scope of the present invention.Therefore, the invention is not restricted to following embodiment.

Embodiment A:

1. manufacturing cellulose acylate:

(1) make cellulose acetate propionate (embodiment 1-44,49):

A) activation:

The Mierocrystalline cellulose (slurry) of 80 mass parts and the acetate input of 33 mass parts are equipped with in the reactor of whipping appts and refrigerating unit, heat 4 hours with activated cellulose at 60 ℃.Change soak time has the embodiment 17-19 of different needle-like foreign matter contents with manufacturing cellulose acylate.

B) acidylate:

Mix diacetyl oxide, 540 mass parts propionic acid, the propionic anhydride of 558 mass parts and the sulfuric acid of 4 mass parts of 32 mass parts, and be cooled to-20 ℃, be added in the reactor.The control maximum temperature is 35 ℃ of esterified celluloses, and the viscosity of reaction liquid is the terminal point of reaction when arriving 910cP.The control reaction mixture, the temperature of reaction mixture is 15 ℃ when making terminal point.The water by mixing 133 mass parts and the acetate of 133 mass parts also are cooled to-5 ℃ of preparation feedback terminators, are added in the reaction mixture, make the temperature of reaction mixture not be higher than 23 ℃.Change the ratio of mixture of reactant, obtain the cellulose acylate of embodiment 39-44.

C) partial hydrolysis:

Reaction mixture stirred 2 hours at 60 ℃, carried out partial hydrolysis, used filter paper filtering then.Change churning time, obtain having the cellulose acylate of the embodiment 35-38 of different polymerization degree.

D) control sulfuric acid amount:

Next, with 77g (for sulfuric acid 2 equivalents) magnesium acetate 4-hydrate, the mixing solutions of 77g acetate and 77g water is added to (neutralization) in the reactor, stirs 2 hours (post-heating) at 60 ℃.Use filter paper filtering; Mix with acetic acid aqueous solution then, make the polymer compound redeposition that obtains, use 70-80 ℃ hot water repeated washing then.Change washing time, obtain the cellulose acylate of the different embodiment 20-29 of wherein remaining sulfuric acid amount.

E) add basic metal, group II metal:

After the dehydration, cellulose acylate is immersed in the aqueous solution of basic metal shown in the table 1 or group II metal compound, and stirred 30 minutes.Next, dehydration once more.60 ℃ of vacuum-dryings 12 hours.Change the kind of basic metal or group II metal compound and the concentration of its aqueous solution, obtain the M/S shown in the table 1, that is, and (basic metal molal quantity and group II metal molal quantity sum)/(sulfate groups molal quantity).

(2) make cellulose acetate butyrate etc. (embodiment 45-48):

A) activation:

The Mierocrystalline cellulose (cotton linter) of 200 mass parts and the acetate input of 100 mass parts are equipped with in the reactor of whipping appts and refrigerating unit, heat 4 hours with activated cellulose at 60 ℃.

B) acidylate:

Mix the acetate of 161 mass parts, the diacetyl oxide of 449 mass parts, the butyric acid of 742 mass parts, the butyryl oxide of 1349 mass parts and the sulfuric acid of 14 mass parts, and be cooled to-20 ℃, be added in the reactor.

C) partial hydrolysis:

The control maximum temperature is 30 ℃ of esterified celluloses, and the viscosity of reaction liquid is the terminal point of reaction when arriving 1050cP.The control reaction mixture, the temperature when making terminal point is 10 ℃.The water by mixing 297 mass parts and the acetate of 558 mass parts also are cooled to-5 ℃ of preparation feedback terminators, are added in the reaction mixture, make the temperature of reaction mixture not be higher than 23 ℃.

D) control sulfuric acid amount:

Reaction mixture stirred 2 hours 30 minutes at 60 ℃, carried out partial hydrolysis, used filter paper filtering then.It is mixed with acetic acid aqueous solution, make the polymer compound redeposition that obtains, use 70-80 ℃ hot water repeated washing then.

E) add basic metal, group II metal:

After the dehydration, cellulose acylate is immersed in the aqueous solution of basic metal shown in the table 1 or group II metal compound, and stirred 30 minutes.In this state, the concentration of the control aqueous solution obtains the M/S ratio shown in the table 1.Next, dehydration once more.70 ℃ of dryings, obtain cellulose acylate butyric ester (embodiment 45).

In making the aforesaid method of cellulose acylate, changing A) time in the activation is with control needle-like impurity level; Change B) acidylate and C) condition in the partial hydrolysis is with the molecular weight of control substitution value and polymkeric substance; Change D) the post-heating time in the sulfuric acid amount control is with the sulfuric acid amount in the control reaction system; And change E) add basic metal, the condition of the calcium hydroxide aqueous solution in the group II metal (kind, concentration) is with basic metal amount in the controlling polymers and group II metal amount.Therefore, can make different cellulose acylate (embodiment 46-48).

2. form the cellulose acylate pellet:

120 ℃ of dryings 3 hours, making water-content was 0.1 quality %, to the silicon dioxide granule that wherein adds 0.05 quality % (Aerosil R972V) with above-mentioned cellulose acylate.In addition, to wherein adding stablizer (the Sumilizer GP of Sumitomo Chemical, 0.3 quality %) and UV absorption agent (the Adekastab LA-31 of Asahi Denka Kogyo, 1 quality %).The mixture that obtains is dropped into twin screw knead in the funnel of forcing machine, and under the granulation condition shown in the table 1, knead therein.Knead its compression ratio of screw rod of forcing machine of twin screw is 3; The bucket diameter is 40mm; L/D=40; The rate of extrusion of forcing machine is 150kg/hr.After the fusion, cellulose acylate is extruded with the line of diameter 3mm, and in 10 ℃ water, solidified, be cut into the pellet of length 5mm then.With the pellet made like this 100 ℃ of dryings 10 minutes.

According to aforesaid method, the ratio of the crystallization fusion heat of analysis pellet, needle-like impurity, sulphate groups mass contg, (basic metal molal quantity and group II metal molal quantity sum)/(sulfate groups molal quantity) (the M/S ratio in the table 1), weight average degree of polymerization (DPw) and substitution value.Data are shown in table 1.

3. fusion casting film-forming:

With above-mentioned cellulose acylate pellet in 110 ℃ Vacuumdrier dry 2 hours, make residual moisture content 0.01 quality % at the most.Their are dropped in the funnel of being controlled at of twin screw extruder (Tg-10) ℃, under nitrogen atmosphere, knead and fusion.The first supplying opening temperature is 180 ℃; The compression zone temperature is 210 ℃; The second supplying opening temperature is 220 ℃.The compression ratio of full flight screw is 4; L (spiro rod length)/D (screw diameter) is 30.In the exit of forcing machine, filter resin melt by the spreader plate strainer, filter once more then by toothed gear pump, and by 4-μ m stainless steel blade type disc filter arrangement.

The resin melt that obtains is extruded by the T-mould of forcing machine, among the embodiment 1 that uses then at JP-A-11-235747 the record touch roll, under line pressure shown in the table 1, form film.The diameter of casting roller and touch roll is 400mm, is arranged on 120 ℃.After the casting roller stripping film, prune the two ends (each end be total width 3%) of film.At two ends annular knurl width 10mm and height 50 μ m, batch with speed 30m/min then.Its width of the film that batches like this is 1.5m, and length is 3000m.

The granulation pellet crystallization fusion of kneading

Table 1

Ethanoyl (X)	Cellulose acylate									Granulation				Granule performance					Film forming		Film is estimated
	Cellulose acylate									Granulation				Granule performance					Film forming		Film is estimated		Substitution value							Tg (℃)	Screw speed (rpm)	The resin pressure (MPa) of kneading	Knead temperature (℃)	Vacuum exhaust (pressure in kneading) (normal atmosphere)	Rare gas element	Residual oxygen (%)	Crystallization melting heat (J/P)	Needle-like impurity (/mg)	Sulfate groups (ppm)	M S ^*	M ^*Kind	The line pressure of touch roll (kg/ cm)	Thickness (μ m)	Weather stain (400 nm absorbancy)	Flavescence among the LCD	Embodiment 1
	Propionyl (Y1)	Butyryl radicals (Y2)	Pentanoyl (Y3)	Caproyl (Y4)	Y (Y1-Y4 sum)	X+ Y	Weight average degree of polymerization																Substitution value
	Propionyl (Y1)	Butyryl radicals (Y2)	Pentanoyl (Y3)	Caproyl (Y4)	Y (Y1-Y4 sum)	X+ Y	Weight average degree of polymerization	0.4	2.5		2.5	2.9	400	135	150	5	200	0.5	N2	5	0.2	0	80	0.6	Ca(OH) ₂	10	80	0.02	0																		Comparative Examples 1
0.4	2.5				2.5	2.9	400	0.4	2.5		2.5	2.9	400	135	150	5	200	0.5	N2	5	0.2	0	80	0.6	Ca(OH) ₂	10	80	0.02	0	135	100	1	190	0.3	He	3	15	0	80	0.6	Ca(OH) ₂	10	80	0.36	9	Embodiment 2	Comparative Examples 1
0.4	2.5				2.5	2.9	400	0.4	2.5		2.5	2.9	180	135	100	2	190	0.3	He	3	3	0	80	0.6	Ca(OH) ₂	10	80	0.09	3	135	100	1	190	0.3	He	3	15	0	80	0.6	Ca(OH) ₂	10	80	0.36	9	Embodiment 2	Embodiment 3
0.4	2.5				2.5	2.9	480	0.4	2.5		2.5	2.9	180	135	100	2	190	0.3	He	3	3	0	80	0.6	Ca(OH) ₂	10	80	0.09	3	135	100	9	190	0.3	He	3	4	0	80	0.6	Ca(OH) ₂	10	80	0.10	3	Comparative Examples 2	Embodiment 3
0.4	2.5				2.5	2.9	480	0.4	2.5		2.5	2.9	530	135	100	11	190	0.3	He	3	16	0	80	0.6	Ca(OH) ₂	10	80	0.38	9	135	100	9	190	0.3	He	3	4	0	80	0.6	Ca(OH) ₂	10	80	0.10	3	Comparative Examples 2	Comparative Examples 3
0.4	2.5				2.5	2.9	400	0.4	2.5		2.5	2.9	530	135	100	11	190	0.3	He	3	16	0	80	0.6	Ca(OH) ₂	10	80	0.38	9	135	40	5	190	0.3	He	3	12	0	80	0.6	Ca(OH) ₂	10	80	0.39	8	Embodiment 4	Comparative Examples 3
0.4	2.5				2.5	2.9	400	0.4	2.5		2.5	2.9	400	135	60	5	190	0.3	He	3	2	0	80	0.6	Ca(OH) ₂	10	80	0.11	3	135	40	5	190	0.3	He	3	12	0	80	0.6	Ca(OH) ₂	10	80	0.39	8	Embodiment 4	Embodiment 5
0.4	2.5				2.5	2.9	400	0.4	2.5		2.5	2.9	400	135	60	5	190	0.3	He	3	2	0	80	0.6	Ca(OH) ₂	10	80	0.11	3	135	280	5	190	0.3	He	3	3	0	80	0.6	Ca(OH) ₂	10	80	0.09	4	Comparative Examples 4	Embodiment 5
0.4	2.5				2.5	2.9	400	0.4	2.5		2.5	2.9	400	135	330	5	190	0.3	He	3	12	0	80	0.6	Ca(OH) ₂	10	80	0.33	8	135	280	5	190	0.3	He	3	3	0	80	0.6	Ca(OH) ₂	10	80	0.09	4	Comparative Examples 4	Embodiment 6
0.4	2.5				2.5	2.9	400	0.4	2.5		2.5	2.9	400	135	330	5	190	0.3	He	3	12	0	80	0.6	Ca(OH) ₂	10	80	0.33	8	135	150	5	150	0.5	Ar	10	5	0	80	0.6	Ca(OH) ₂	10	80	0.15	5	Embodiment 7	Embodiment 6
0.4	2.5				2.5	2.9	400	0.4	2.5		2.5	2.9	400	135	150	5	170	0.5	Ar	10	1	0	80	0.6	Ca(OH) ₂	10	80	0.06	2	135	150	5	150	0.5	Ar	10	5	0	80	0.6	Ca(OH) ₂	10	80	0.15	5	Embodiment 7

Table 1 (continuous 1)

Embodiment 8	0.4	2.5	2.5	2.9	400	135	150	5	220	0.5	Ar	10	1	0	80	0.6	Ca(OH) ₂	10	80	0.07	2
Embodiment 8	0.4	2.5	2.5	2.9	400	135	150	5	220	0.5	Ar	10	1	0	80	0.6	Ca(OH) ₂	10	80	0.07	2	Embodiment 9	0.4	2.5	2.5	2.9	400	135	150	5	230	0.5	Ar	10	5	0	80	0.6	Ca(OH) ₂	10	80	0.16	5
Embodiment 10	0.4	2.5	2.5	2.9	400	135	150	5	200	1	-	19	4	0	80	0.6	Ca(OH) ₂	10	80	0.15	5	Embodiment 9	0.4	2.5	2.5	2.9	400	135	150	5	230	0.5	Ar	10	5	0	80	0.6	Ca(OH) ₂	10	80	0.16	5
Embodiment 10	0.4	2.5	2.5	2.9	400	135	150	5	200	1	-	19	4	0	80	0.6	Ca(OH) ₂	10	80	0.15	5	Embodiment 11	0.4	2.5	2.5	2.9	400	135	150	5	200	0.9	-	17	2.5	0	80	0.6	Ca(OH) ₂	10	80	0.08	2
Embodiment 12	0.4	2.5	2.5	2.9	400	135	150	5	200	0	-	2	1.5	0	80	0.6	Ca(OH) ₂	10	80	0.06	2	Embodiment 11	0.4	2.5	2.5	2.9	400	135	150	5	200	0.9	-	17	2.5	0	80	0.6	Ca(OH) ₂	10	80	0.08	2
Embodiment 12	0.4	2.5	2.5	2.9	400	135	150	5	200	0	-	2	1.5	0	80	0.6	Ca(OH) ₂	10	80	0.06	2	Embodiment 13	0.4	2.5	2.5	2.9	400	135	150	5	200	1	N2	19	5	0	80	0.6	Ca(OH) ₂	10	80	0.16	5
Embodiment 14	0.4	2.5	2.5	2.9	400	135	150	5	200	1	N2	17	2.3	0	80	0.6	Ca(OH) ₂	10	80	0.09	2	Embodiment 13	0.4	2.5	2.5	2.9	400	135	150	5	200	1	N2	19	5	0	80	0.6	Ca(OH) ₂	10	80	0.16	5
Embodiment 14	0.4	2.5	2.5	2.9	400	135	150	5	200	1	N2	17	2.3	0	80	0.6	Ca(OH) ₂	10	80	0.09	2	Embodiment 15	0.4	2.5	2.5	2.9	400	135	150	5	200	1	N ₂	2	1	0	80	0.6	Ca(OH) ₂	10	80	0.07	2
Embodiment 16	0.4	2.5	2.5	2.9	400	135	150	5	200	0.9	N ₂	17	0.5	0	80	0.6	Ca(OH) ₂	10	80	0.03	0	Embodiment 15	0.4	2.5	2.5	2.9	400	135	150	5	200	1	N ₂	2	1	0	80	0.6	Ca(OH) ₂	10	80	0.07	2
Embodiment 16	0.4	2.5	2.5	2.9	400	135	150	5	200	0.9	N ₂	17	0.5	0	80	0.6	Ca(OH) ₂	10	80	0.03	0	Embodiment 17	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	6	60	80	0.6	Mg(OH) ₂	10	100	0.18	4
Embodiment 18	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	2	45	80	0.6	Mg(OH) ₂	10	100	0.11	1	Embodiment 17	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	6	60	80	0.6	Mg(OH) ₂	10	100	0.18	4
Embodiment 18	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	2	45	80	0.6	Mg(OH) ₂	10	100	0.11	1	Embodiment 19	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.8	20	80	0.6	Mg(OH) ₂	10	100	0.06	1
Embodiment 20	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	6	0	220	1.2	Ca(OH) ₂	10	80	0.15	5	Embodiment 19	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.8	20	80	0.6	Mg(OH) ₂	10	100	0.06	1
Embodiment 20	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	6	0	220	1.2	Ca(OH) ₂	10	80	0.15	5	Embodiment 21	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	2.2	0	180	1.2	Ca(OH) ₂	10	80	0.11	2
Embodiment 22	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	1.5	0	30	1.2	Ca(OH) ₂	10	80	0.08	1	Embodiment 21	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	2.2	0	180	1.2	Ca(OH) ₂	10	80	0.11	2
Embodiment 22	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	1.5	0	30	1.2	Ca(OH) ₂	10	80	0.08	1	Embodiment 23	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	1.5	0	0	1.2	Ca(OH) ₂	10	80	0.03	0
Embodiment 24	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	5	0	100	3.2	Ca(OH) ₂	10	80	0.14	5	Embodiment 23	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	1.5	0	0	1.2	Ca(OH) ₂	10	80	0.03	0
Embodiment 24	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	5	0	100	3.2	Ca(OH) ₂	10	80	0.14	5	Embodiment 25	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	2.3	0	100	2.8	Ca(OH) ₂	10	80	0.09	2
Embodiment 26	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	1.5	0	100	0.4	Ca(OH) ₂	10	80	0.05	1	Embodiment 25	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	2.3	0	100	2.8	Ca(OH) ₂	10	80	0.09	2
Embodiment 26	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	1.5	0	100	0.4	Ca(OH) ₂	10	80	0.05	1	Embodiment 27	0.4	25	25	2.9	400	135	150	5	200	0.5	N ₂	5	4.5	0	100	0.2	Ca(OH) ₂	10	80	0.15	4
Embodiment 28	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.6	0	180	2.8	Ca(OH) ₂	10	80	0.03	1	Embodiment 27	0.4	25	25	2.9	400	135	150	5	200	0.5	N ₂	5	4.5	0	100	0.2	Ca(OH) ₂	10	80	0.15	4
Embodiment 28	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.6	0	180	2.8	Ca(OH) ₂	10	80	0.03	1	Embodiment 29	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	2.8	0	220	3.2	Ca(OH) ₂	10	80	0.23	6
Embodiment 30	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.2	0	60	1.5	NaH(CO ₃)	Do not use	80	0.18	4	Embodiment 29	0.4	2.5	2.5	2.9	400	135	150	5	200	0.5	N ₂	5	2.8	0	220	3.2	Ca(OH) ₂	10	80	0.23	6

Table 1 (continuous 2)

Embodiment 31	0.4	2.5		2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.2	60	1.5	NaH(CO ₃)	2	80	0.14	2
Embodiment 31	0.4	2.5		2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.2	60	1.5	NaH(CO ₃)	2	80	0.14	2	Embodiment 32	0.4	2.5				2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.2	0	60	1.5	NaH(CO ₃)	4	80	0.05	1
Embodiment 33	0.4	25		2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.2	60	1.5	NaH(CO ₃)	90	80	0.05	1	Embodiment 32	0.4	2.5				2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.2	0	60	1.5	NaH(CO ₃)	4	80	0.05	1
Embodiment 33	0.4	25		2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.2	60	1.5	NaH(CO ₃)	90	80	0.05	1	Embodiment 34	0.4	2.5				2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.2	0	60	1.5	NaH(CO ₃)	120	80	0.12	2
Embodiment 35	0.4	2.5		2.5	2.9	220	133	150	5	200	0.5	N ₂	5	0.2	40	0.6	KH(CO ₃)	10	120	0.14	4	Embodiment 34	0.4	2.5				2.5	2.9	400	135	150	5	200	0.5	N ₂	5	0.2	0	60	1.5	NaH(CO ₃)	120	80	0.12	2
Embodiment 35	0.4	2.5		2.5	2.9	220	133	150	5	200	0.5	N ₂	5	0.2	40	0.6	KH(CO ₃)	10	120	0.14	4	Embodiment 36	0.4	25				2.5	2.9	260	134	150	5	200	0.5	N ₂	5	0.2	0	40	0.6	KH(CO ₃)	10	120	0.05	1
Embodiment 37	0.4	2.5		2.5	2.9	480	135	150	5	200	0.5	N ₂	5	0.2	40	0.6	KH(CO ₃)	10	120	0.04	2	Embodiment 36	0.4	25				2.5	2.9	260	134	150	5	200	0.5	N ₂	5	0.2	0	40	0.6	KH(CO ₃)	10	120	0.05	1
Embodiment 37	0.4	2.5		2.5	2.9	480	135	150	5	200	0.5	N ₂	5	0.2	40	0.6	KH(CO ₃)	10	120	0.04	2	Embodiment 38	0.4	2.5				2.5	2.9	530	136	150	5	200	0.5	N ₂	5	0.2	0	40	0.6	KH(CO ₃)	10	120	0.19	5
Embodiment 39	0.05	2.95		2.95	3.0	450	130	150	5	200	0.5	N ₂	5	0.2	150	2.2	Ca(OH)2	50	280	0.04	0	Embodiment 38	0.4	2.5				2.5	2.9	530	136	150	5	200	0.5	N ₂	5	0.2	0	40	0.6	KH(CO ₃)	10	120	0.19	5
Embodiment 39	0.05	2.95		2.95	3.0	450	130	150	5	200	0.5	N ₂	5	0.2	150	2.2	Ca(OH)2	50	280	0.04	0	Embodiment 40	0.8	2.0				2.0	2.8	450	130	150	5	200	0.5	N ₂	5	0.2	0	150	2.2	Ca(OH)2	50	280	0.08	1
Embodiment 41	1.6	1.2		1.2	2.8	450	140	150	5	200	0.5	N ₂	5	0.2	150	2.2	Ca(OH)2	50	280	0.10	2	Embodiment 40	0.8	2.0				2.0	2.8	450	130	150	5	200	0.5	N ₂	5	0.2	0	150	2.2	Ca(OH)2	50	280	0.08	1
Embodiment 41	1.6	1.2		1.2	2.8	450	140	150	5	200	0.5	N ₂	5	0.2	150	2.2	Ca(OH)2	50	280	0.10	2	Embodiment 42	2.0	0.8				0.8	2.8	450	145	150	5	200	0.5	N ₂	5	0.2	0	150	2.2	Ca(OH)2	50	280	0.18	4
Embodiment 43	0.6	2.0		2.0	2.6	450	132	150	5	200	0.5	N ₂	5	0.2	150	2.2	Ca(OH)2	50	280	0.06	2	Embodiment 42	2.0	0.8				0.8	2.8	450	145	150	5	200	0.5	N ₂	5	0.2	0	150	2.2	Ca(OH)2	50	280	0.18	4
Embodiment 43	0.6	2.0		2.0	2.6	450	132	150	5	200	0.5	N ₂	5	0.2	150	2.2	Ca(OH)2	50	280	0.06	2	Embodiment 44	0.4	2.0				2.0	2.4	450	135	150	5	200	0.5	N ₂	5	0.2	0	150	2.2	Ca(OH)2	50	200	0.19	4
Embodiment 45	1.5		1.2	1.2	2.7	450	135	150	5	200	0.5	N ₂	5	0.2	150	2.2	Ca(OH)2	50	30	0.10	1	Embodiment 44	0.4	2.0				2.0	2.4	450	135	150	5	200	0.5	N ₂	5	0.2	0	150	2.2	Ca(OH)2	50	200	0.19	4
Embodiment 45	1.5		1.2	1.2	2.7	450	135	150	5	200	0.5	N ₂	5	0.2	150	2.2	Ca(OH)2	50	30	0.10	1	Embodiment 46	1.0		1.7			1.7	2.7	450	130	150	5	200	0.5	N ₂	5	0.2	0	150	2.2	Ca(OH)2	50	30	0.06	1
Embodiment 47	0.4		2.5	2.5	2.9	450	125	150	5	200	0.5	N ₂	5	0.2	150	2.2	Ca(OH)2	50	30	0.05	1	Embodiment 46	1.0		1.7			1.7	2.7	450	130	150	5	200	0.5	N ₂	5	0.2	0	150	2.2	Ca(OH)2	50	30	0.06	1
Embodiment 47	0.4		2.5	2.5	2.9	450	125	150	5	200	0.5	N ₂	5	0.2	150	2.2	Ca(OH)2	50	30	0.05	1	Embodiment 48	1.0	1.2	0.2	0.2	0.2	1.8	2.8	450	95	150	5	200	0.5	N ₂	5	0.2	0	150	2.2	Ca(OH)2	50	30	0.12	2
Embodiment 49	0.2	2.5		2.5	2.7	270	140	150	5	200	0.5	N ₂	5	0	90	1	Ca(OH)2	30	80	0.03	0	Embodiment 48	1.0	1.2	0.2	0.2	0.2	1.8	2.8	450	95	150	5	200	0.5	N ₂	5	0.2	0	150	2.2	Ca(OH)2	50	30	0.12	2
Embodiment 49	0.2	2.5		2.5	2.7	270	140	150	5	200	0.5	N ₂	5	0	90	1	Ca(OH)2	30	80	0.03	0	Comparative Examples 5	0.2	2.5				2.5	2.7	200	140	30	0	240	1	-	21	20	350	350	0	-	Do not use	80	0.55	10

^*M: basic metal molal quantity and alkaline-earth metal molal quantity sum

S: sulfate groups molal quantity

4. form the tensile cellulose acylate film:

The tensile sheet does not stretch by following stretch ratio with 300%/min at Tg+10 ℃.Tg refers to the second-order transition temperature of each film, measures Tg by DSC with 10 ℃/min, and the baseline in 10 ℃/min DSC begins migration from low temperature side.

Use automatic double refraction meter (KOBRA-21ADH, Oji ScientificInstruments), under 25 ℃ and 60%RH, analyze the tensile film.The result of embodiment 1 is as follows, and other embodiment obtain equifinality.

Table 2

	MD-tensile stretch ratio (%)	CD-tensile stretch ratio (%)	RE (nm)	Rth (nm)
	MD-tensile stretch ratio (%)	CD-tensile stretch ratio (%)	RE (nm)	Rth (nm)	Tensile film not	0	0	0	0
Tensile film 1	300	0	200	100	Tensile film not	0	0	0	0
Tensile film 1	300	0	200	100	Tensile film 2	50	10	60	220
Tensile film 3	50	50	0	450	Tensile film 2	50	10	60	220
Tensile film 3	50	50	0	450	Tensile film 4	50	10	60	220
Tensile film 5	0	150	150	150	Tensile film 4	50	10	60	220

5. the high temperature ageing of tensile or tensile cellulose acylate film not:

Cellulose acylate film is cut into slices, under 80 ℃ and 10%RH aging 1000 hours (long-term aging).Next, measure the absorbancy under 400nm, it is converted into value (actual measurement absorbance * (100/ actual (real) thickness (the μ m)) of the film of thickness 100 μ m.This is the long-term aging flavescence degree of film afterwards, is shown in table 1 (wherein putting down in writing in weather stain one hurdle).

6. structure polarizer:

(1) saponification of cellulose acylate film:

The not tensile cellulose acylate film and the tensile acylate film of long-term aging are carried out saponification according to following process by dipping in saponification solution.When with the saponification solution coated thin film, obtain identical result.

(1-1) dipping saponification:

Preparation NaOH (1.5mol/L) aqueous solution is as saponification solution, 60 ℃ of adjustings.Cellulose acylate film is immersed in this solution 2 minutes.Next, be immersed in sulfuric acid (0.05mol/L) aqueous solution 30 seconds, bathe by water washing then.

(1-2) coating saponification:

The water of 20 mass parts is added in the Virahol of 80 mass parts, with KOH be dissolved in wherein to concentration be 1.5mol/L.60 ℃ of adjustings, used as saponification solution.Saponification solution is applied on 60 ℃ the cellulose acylate film, to 10g/m ²Degree, the saponification film is 1 minute thus.Next, by thereon with 10L/m ².min spray 50 ℃ hot wash 1 minute.

(2) preparation polarization film:

According to the embodiment 1 of JP-A-2001-141926, with film between two pairs of nip rollss with different peripheral speeds (peripheral speed) along machine direction stretch, with the polarization film of preparation thickness 20 μ m.

(3) laminated:

Use 3%PVA (Kuraray ' s PVA-117H) aqueous solution as tackiness agent; any in tensile or the tensile cellulose acylate film is not laminated with the polarization film that obtains like this and saponified, makes the polarization axle and the machine direction of cellulose acylate film intersect with 45 °.The polarizer of structure like this is installed on the 20-inch VA-mode LCD of Fig. 2-9 of JP-A-2000-154261, drives the complete white demonstration of this device.In this stage, the flavescence of visual assessment device panel the results are shown in table 1 (flavescence among the LCD).Each sample is with 10 full marks evaluations.There was not the sample of flavescence in 0 minute; Gave the sample of strong flavescence in 10 minutes.Realistic scale at the most 6, preferably at the most 4, more preferably at the most 2, more more preferably at the most 1, most preferably 0.

Film of the present invention all has good result.On the other hand, contrast film flavescence greatly.Especially, with the film (Comparative Examples of the embodiment 3-1 of JP-A-2000-352620

5) compare, corresponding film of the present invention (embodiment 49) is obviously better.

7. structure optical compensating film:

(1) tensile film not:

When not tensile cellulose acylate film of the present invention is used for first transparent support of JP-A-11-316378 embodiment 1, can make the good optical compensation film.

(2) tensile cellulose acylate film:

When replacing the liquid crystal layer application type cellulose acetate film of JP-A-11-316378 embodiment 1, can make the good optical compensation film with tensile cellulose acylate film of the present invention.Similarly, when replacing the liquid crystal layer application type cellulose acetate film of JP-A-7-333433 embodiment 1, can make good optical compensation filter membrane (filter film) with tensile cellulose acylate film of the present invention.

8. structure low refractive index film:

According to Hatsumei Kyokai Disclosure Bulletin (No.2001-1745; Hatsumei Kyokai published in March 15 calendar year 2001) embodiment 47; with tensile of the present invention or not the tensile cellulose acylate film be used to construct low refractive index film, and this film has the good optical performance.

9. structure liquid crystal indicator:

Above-mentioned polarizer of the present invention is used for liquid crystal indicator in JP-A-10-48420 embodiment 1 record; The oriented film of the optical anisotropic layer that contains discotic liquid-crystalline molecules of record and polyvinyl alcohol coating in JP-A-9-26572 embodiment 1; The 20-inch VA-mode LCD of JP-A-2000-154261 Fig. 2-9; 20-inch OCB-mode LCD with 2JP-A-2000-154261 Figure 10-15.Low refractive index film of the present invention is attached to the outmost surface layer of these liquid crystal indicators, visual valuation.All these all show good visibility.

The pellet that replaces embodiment 1-49 uses by these pellets are ground to form size 1-10mm ³And the cellulose acylate pellet of preparation, the method according to embodiment 1-49 prepares cellulose acylate film then.These cellulose acylate films also have good result, and are similar to the film that forms from the cellulose acylate pellet.

In addition, by making other films with embodiment 1 same way as, yet, add the softening agent Octyl adipate (embodiment 50) of 4 quality % or the softening agent 2 of the JP-A-2000-352620 formula 1 of 6 quality % (embodiment 51).The film of these films and embodiment 1 is made comparisons.Film with embodiment 1 aspect embodiment 50 and 51 the flavescence of film in crystallization melting heat, needle-like impurity, aged variable color and LCD is identical; But in embodiment 51, softening agent precipitates on casting roller after becoming film length 100m; In embodiment 52, softening agent precipitates on casting roller after forming film with length 1000m.These settlings cause that the spot on the film shifts.In embodiment 1, even after with length 10000m or bigger film forming, also do not observe the film spot.

Embodiment B:

The acetate of 0.1 mass parts and the propionic acid of 2.7 mass parts are sprayed on the Mierocrystalline cellulose (hardwood pulp) of 10 mass parts, at room temperature preserved then 1 hour.In addition, prepare the diacetyl oxide of 1.2 mass parts, the propionic anhydride of 61 mass parts and the vitriolic mixture of 0.7 mass parts, be cooled to-10 ℃, in reactor, mix then with top pretreated Mierocrystalline cellulose.After 30 minutes, outside temperature is risen to 30 ℃, make compound reaction 4 hours.25% acetic acid aqueous solution of 46 mass parts is added in the reactor, internal temperature is risen to 60 ℃, stirred 2 hours.The solution that passes through mixing magnesium acetate 4-hydrate, acetate and water (1/1/1 weight) preparation of 6.2 mass parts is added to wherein, stirred 30 minutes.Adding the strainer filtering reaction liquid of depressing by the sintering metal that keeps particle diameter 40 μ m, 10 μ m and 5 μ m, to remove impurity.The filtrate that obtains is mixed with 75% acetic acid aqueous solution, to be settled out cellulose acetate propionate, uses 70 ℃ of hot washes then, is 6-7 up to the pH of washing waste material.In addition, in 0.001% calcium hydroxide aqueous solution, stirred 0.5 hour, filter then.With the cellulose acetate propionate that obtains 70 ℃ of dryings. ¹H-NMR confirms, its degree of acetylation of the cellulose acetate propionate that obtains like this is 0.15, the propionyl degree is 2.5 5, weight-average molecular weight be 135000 and number-average molecular weight be 52000.

Change diacetyl oxide amount and the propionic anhydride amount be added in the reaction system, its degree of acetylation of the cellulose acetate propionate that obtains is 0.43, the propionyl degree is 2.40, weight-average molecular weight be 125000 and number-average molecular weight be 48000.

With embodiment 1 the same terms of embodiment A under carry out granulation, obtain pellet, its crystallization melting heat is 0.1J/g, the needle-like amount of impurities is 0/mg, the sulphate groups mass contg is 70ppm, M/S is 0.5, M is Ca (OH) ₂Use this pellet, press with embodiment 1 same way as and form film, yet the touch roll contact pressure is 1MPa.The film that test obtains like this, its weather stain is 0.01, and flavescence is 0 among the LCD, and promptly film has good performance.

Embodiment C:

(1) make cellulose acylate:

The acetate of 0.1 mass parts and the propionic acid of 2.7 mass parts are sprayed on the Mierocrystalline cellulose (hardwood pulp) of 10 mass parts, at room temperature preserve then.Change the shelf time, thereby press the amount that changes needle-like impurity shown in the table 3.In addition, prepare the diacetyl oxide of 1.2 mass parts, the propionic anhydride of 61 mass parts and the vitriolic mixture of 0.7 mass parts, be cooled to-10 ℃, in reactor, mix then with top pretreated Mierocrystalline cellulose.After 30 minutes, outside temperature is risen to 30 ℃, make compound reaction 4 hours (partial hydrolysis).25% acetic acid aqueous solution of 46 mass parts is added in the reactor, internal temperature is risen to 60 ℃, stirred 2 hours.The solution that passes through mixing magnesium acetate 4-hydrate, acetate and water (1/1/1 weight) preparation of 6.2 mass parts is added to wherein, stirred 30 minutes.Adding the strainer filtering reaction liquid of depressing by the sintering metal that keeps particle diameter 40 μ m, 10 μ m and 5 μ m, to remove impurity.The filtrate that obtains is mixed with 75% acetic acid aqueous solution, with precipitated cellulose acetate propionic ester, uses 70 ℃ of hot washes then, is 6-7 up to the pH of washing waste material.In addition, in 0.001% calcium hydroxide aqueous solution, stirred 0.5 hour, filter then.With the cellulose acetate propionate that obtains 70 ℃ of dryings. ¹H-NMR confirms, its degree of acetylation of the cellulose acetate propionate that obtains like this is 0.15, the propionyl degree is 2.55, weight average degree of polymerization be 420 and number-average degree of polymerization be 160.

Change the diacetyl oxide amount and the propionic anhydride amount that are added in the reaction system, the cellulose acylate that obtains has the different degree of acetylation shown in the table 3, propionyl degree and Butyrylation degree.In addition, change the time (when the time was longer, the polymerization degree of polymkeric substance descended) of partial hydrolysis, obtain the cellulose acylate shown in the table 3 with different weight average degree of polymerizations.

(2) form cellulose acylate pellet:

Cellulose acylate shown in the table 3 is dissolved in the solvent with the value of SP shown in the table 3, is the cellulose acylate solution of 10 quality % with preparation concentration.Handle according to following arbitrary method (table 3), obtain cellulose acylate pellet.

(i) intermediate processing:

The mixed solvent of acetate and water (acetic acid/water=1/1 weight) is as poor solvent.Cellulose acylate solution is added to wherein, changes the revolution (when the stirring revolution was big, particle diameter was less) that stirs blade, the cellulose acylate pellet that obtains having table 3 illustrated dimension.Filter, wash with water and drying.

(ii) drying means:

Cellulose acylate solution is inserted in the container (chamber), dry under the temperature higher 10 ℃ than solvent boiling point, make residual solvent reduce to 0.01 weight % at the most.Next, grind the cellulose acylate pellet that obtains having table 3 illustrated dimension.By the particle that control milling time and further screening are ground, realize the particulate size control.

(3) fusion casting film-forming:

With above-mentioned cellulose acylate pellet drying 2 hours in 110 ℃ drying machine (use dew point-20 ℃ air), residual moisture content is reduced to 0.01 quality % at the most.Their are dropped in the funnel of being controlled at of twin screw extruder (Tg-10) ℃, under air atmosphere, knead and fusion therein.The first supplying opening temperature is 180 ℃; The compression zone temperature is 220 ℃; The second supplying opening temperature is 230 ℃.Screw speed is 100rpm, and the resin pressure of kneading is 5MPa.In the exit of forcing machine, filter resin melt by the spreader plate strainer, filter once more then by toothed gear pump, and by 3-μ m stainless steel blade type disc filter arrangement.

The resin melt that obtains is extruded by the T-mould of forcing machine, among the embodiment 1 that uses then at JP-A-11-235747 the record touch roll, under line pressure shown in the table 3, form film.The diameter of casting roller and touch roll is 500mm.Be arranged on 120 ℃, centre by upstream side and be arranged on after 3 casting rollers of series connection that 125 ℃, downstream side are arranged on 115 ℃, prune the two ends (each end be total width 3%) of film.At two ends annular knurl width 10mm and height 30 μ m, batch with speed 30m/min then.Its width of the film that batches like this is 1.5m, and length is 3000m.

Table 3

	Cellulose acylate							The dissolving of cellulose acylate	The formation of cellulose acylate pellet		The performance of cellulose acylate pellet					Film forms		Film is estimated
	Cellulose acylate							The dissolving of cellulose acylate	The formation of cellulose acylate pellet		The performance of cellulose acylate pellet					Film forms		Film is estimated		Substitution value					Weight average degree of polymerization	Tg (℃)	Type of solvent	The SP value	Method	Particle size (mm ³)	Crystallization melting heat (J/g)	Needle-like impurity (/mg)	Sulfate groups (ppm)	M/ S ^*	M ^*Kind	Touch roll touch pressure (MPa)	Thickness (μ m)	Weather stain (400 nm absorbancy)	Flavescence among the L C D
	Ethanoyl (X)	Propionyl (Y1)	Butyryl radicals (Y2)	Y (Y1 and Y2 sum)	X+Y															Substitution value
	Ethanoyl (X)	Propionyl (Y1)	Butyryl radicals (Y2)	Y (Y1 and Y2 sum)	X+Y	Comparative Examples 101	0.15	2.55	2.55	2.70	420	137	Neopentane	6.3	The precipitator method	5	12	0	80	0.6	Ca(OH) ₂	1.0	80	0.39																9
Embodiment 101	0.15	2.55		2.55	2.70	Comparative Examples 101	0.15	2.55	2.55	2.70	420	137	Neopentane	6.3	The precipitator method	5	12	0	80	0.6	Ca(OH) ₂	1.0	80	0.39	420	137	Ether	7.4	The precipitator method	5	3	0	80	0.6	Ca(OH) ₂	1.0	80	0.15	4	9
Embodiment 101	0.15	2.55		2.55	2.70	Embodiment 102	0.15	2.55	2.55	2.70	420	137	Ethyl acetate	8.0	The precipitator method	5	1	0	80	0.6	Ca(OH) ₂	1.0	80	0.08	420	137	Ether	7.4	The precipitator method	5	3	0	80	0.6	Ca(OH) ₂	1.0	80	0.15	4	1
Embodiment 103	0.15	2.55		2.55	2.70	Embodiment 102	0.15	2.55	2.55	2.70	420	137	Ethyl acetate	8.0	The precipitator method	5	1	0	80	0.6	Ca(OH) ₂	1.0	80	0.08	420	137	Butylacetate	8.5	The precipitator method	5	1	0	80	0.6	Ca(OH) ₂	1.0	80	0.07	1	1
Embodiment 103	0.15	2.55		2.55	2.70	Embodiment 104	0.15	2.55	2.55	2.70	420	137	Methyl ethyl ketone	9.3	The precipitator method	5	1	0	80	0.6	Ca(OH) ₂	1.0	80	0.08	420	137	Butylacetate	8.5	The precipitator method	5	1	0	80	0.6	Ca(OH) ₂	1.0	80	0.07	1	1
Embodiment 105	0.15	2.55		2.55	2.70	Embodiment 104	0.15	2.55	2.55	2.70	420	137	Methyl ethyl ketone	9.3	The precipitator method	5	1	0	80	0.6	Ca(OH) ₂	1.0	80	0.08	420	137	Methylene dichloride	9.5	The precipitator method	5	1	0	80	0.6	Ca(OH) ₂	1.0	80	0.08	1	1
Embodiment 105	0.15	2.55		2.55	2.70	Embodiment 106	0.15	2.55	2.55	2.70	420	137	Acetone	9.9	The precipitator method	5	5	0	80	0.6	Ca(OH) ₂	1.0	80	0.18	420	137	Methylene dichloride	9.5	The precipitator method	5	1	0	80	0.6	Ca(OH) ₂	1.0	80	0.08	1	4
Comparative Examples 102	0.15	2.55		2.55	2.70	Embodiment 106	0.15	2.55	2.55	2.70	420	137	Acetone	9.9	The precipitator method	5	5	0	80	0.6	Ca(OH) ₂	1.0	80	0.18	530	137	Acetate	10.1	The precipitator method	5	15	0	80	0.6	Ca(OH) ₂	1.0	80	0.45	9	4
Comparative Examples 102	0.15	2.55		2.55	2.70	Comparative Examples 103	0.4	2.5	2.5	2.9	400	137	Neopentane	6.3	Desiccating method	100	12	0	40	0.8	Mg(OH) ₂	1.6	100	0.38	530	137	Acetate	10.1	The precipitator method	5	15	0	80	0.6	Ca(OH) ₂	1.0	80	0.45	9	9
Embodiment 107	0.4	2.5		2.5	2.9	Comparative Examples 103	0.4	2.5	2.5	2.9	400	137	Neopentane	6.3	Desiccating method	100	12	0	40	0.8	Mg(OH) ₂	1.6	100	0.38	400	137	Ether	7.4	Desiccating method	100	2	0	40	0.8	Mg(OH) ₂	1.6	100	0.14	4	9
Embodiment 107	0.4	2.5		2.5	2.9	Embodiment 108	0.4	2.5	2.5	2.9	400	137	Methylene dichloride	9.5	Desiccating method	100	1	0	40	0.8	Mg(OH) ₂	1.6	100	0.08	400	137	Ether	7.4	Desiccating method	100	2	0	40	0.8	Mg(OH) ₂	1.6	100	0.14	4	1

Table 3 (continuous 1)

Embodiment 109	0.4	2.5	2.5	2.9	400	137	Acetone	9.9	Desiccating method	100	3	0	40	0.8	Mg(OH) ₂	1.6	100	0.16	4
Embodiment 109	0.4	2.5	2.5	2.9	400	137	Acetone	9.9	Desiccating method	100	3	0	40	0.8	Mg(OH) ₂	1.6	100	0.16	4	Comparative Examples 104	0.4	2.5	2.5	2.9	400	137	Acetate	10.1	Desiccating method	100	14	0	40	0.8	Mg(OH) ₂	1.6	100	0.49	9
Embodiment 110	0.4	2.5	2.5	2.9	400	137	Ethyl acetate	8.0	The precipitator method	40	1	60	120	1.2	Mg(OH) ₂	1.4	280	0.21	4	Comparative Examples 104	0.4	2.5	2.5	2.9	400	137	Acetate	10.1	Desiccating method	100	14	0	40	0.8	Mg(OH) ₂	1.6	100	0.49	9
Embodiment 110	0.4	2.5	2.5	2.9	400	137	Ethyl acetate	8.0	The precipitator method	40	1	60	120	1.2	Mg(OH) ₂	1.4	280	0.21	4	Embodiment 111	0.4	2.5	2.5	2.9	400	137	Ethyl acetate	8.0	The precipitator method	40	1	45	120	1.2	Mg(OH) ₂	1.4	280	0.13	1
Embodiment 112	0.4	2.5	2.5	2.9	400	137	Ethyl acetate	8.0	The precipitator method	40	1	20	120	1.2	Mg(OH) ₂	1.4	280	0.08	1	Embodiment 111	0.4	2.5	2.5	2.9	400	137	Ethyl acetate	8.0	The precipitator method	40	1	45	120	1.2	Mg(OH) ₂	1.4	280	0.13	1
Embodiment 112	0.4	2.5	2.5	2.9	400	137	Ethyl acetate	8.0	The precipitator method	40	1	20	120	1.2	Mg(OH) ₂	1.4	280	0.08	1	Embodiment 113	0.4	2.5	2.5	2.9	400	137	Butylacetate	8.5	Desiccating method	8000	1	0	220	1.2	Ca(OH) ₂	0.8	40	0.16	5
Embodiment 114	0.4	2.5	2.5	2.9	400	137	Butylacetate	8.5	Desiccating method	8000	1	0	180	1.2	Ca(OH) ₂	0.8	40	0.10	2	Embodiment 113	0.4	2.5	2.5	2.9	400	137	Butylacetate	8.5	Desiccating method	8000	1	0	220	1.2	Ca(OH) ₂	0.8	40	0.16	5
Embodiment 114	0.4	2.5	2.5	2.9	400	137	Butylacetate	8.5	Desiccating method	8000	1	0	180	1.2	Ca(OH) ₂	0.8	40	0.10	2	Embodiment 115	0.4	2.5	2.5	2.9	400	137	Butylacetate	8.5	Desiccating method	8000	1	0	30	1.2	Ca(OH) ₂	0.8	40	0.07	1
Embodiment 116	0.4	2.5	2.5	2.9	400	137	Butylacetate	8.5	Desiccating method	8000	1	0	0	1.2	Ca(OH) ₂	0.8	40	0.07	0	Embodiment 115	0.4	2.5	2.5	2.9	400	137	Butylacetate	8.5	Desiccating method	8000	1	0	30	1.2	Ca(OH) ₂	0.8	40	0.07	1
Embodiment 116	0.4	2.5	2.5	2.9	400	137	Butylacetate	8.5	Desiccating method	8000	1	0	0	1.2	Ca(OH) ₂	0.8	40	0.07	0	Embodiment 117	0.4	2.5	2.5	2.9	400	137	Methylene dichloride	9.5	The precipitator method	2	1	0	100	3.2	Ca(OH) ₂	1.2	60	0.15	5
Embodiment 118	0.4	2.5	2.5	2.9	400	137	Methylene dichloride	9.5	The precipitator method	2	1	0	100	2.8	Ca(OH) ₂	1.2	60	0.08	2	Embodiment 117	0.4	2.5	2.5	2.9	400	137	Methylene dichloride	9.5	The precipitator method	2	1	0	100	3.2	Ca(OH) ₂	1.2	60	0.15	5
Embodiment 118	0.4	2.5	2.5	2.9	400	137	Methylene dichloride	9.5	The precipitator method	2	1	0	100	2.8	Ca(OH) ₂	1.2	60	0.08	2	Embodiment 119	0.4	2.5	2.5	2.9	400	137	Methylene dichloride	9.5	The precipitator method	2	1	0	100	0.4	Ca(OH) ₂	1.2	60	0.05	1
Embodiment 120	0.4	2.5	2.5	2.9	400	137	Methylene dichloride	9.5	The precipitator method	2	1	0	100	0.2	Ca(OH) ₂	1.2	60	0.16	5	Embodiment 119	0.4	2.5	2.5	2.9	400	137	Methylene dichloride	9.5	The precipitator method	2	1	0	100	0.4	Ca(OH) ₂	1.2	60	0.05	1
Embodiment 120	0.4	2.5	2.5	2.9	400	137	Methylene dichloride	9.5	The precipitator method	2	1	0	100	0.2	Ca(OH) ₂	1.2	60	0.16	5	Embodiment 121	0.4	2.5	2.5	2.9	400	137	Acetone	9.9	Desiccating method	1000	5	0	60	1.5	NaH(CO ₃)	Do not use	80	0.19	5
Embodiment 122	0.4	2.5	2.5	2.9	400	137	Acetone	9.9	Desiccating method	1000	5	0	60	1.5	NaH(CO ₃)	0.3	80	0.12	3	Embodiment 121	0.4	2.5	2.5	2.9	400	137	Acetone	9.9	Desiccating method	1000	5	0	60	1.5	NaH(CO ₃)	Do not use	80	0.19	5
Embodiment 122	0.4	2.5	2.5	2.9	400	137	Acetone	9.9	Desiccating method	1000	5	0	60	1.5	NaH(CO ₃)	0.3	80	0.12	3	Embodiment 123	0.4	2.5	2.5	2.9	400	137	Acetone	9.9	Desiccating method	1000	5	0	60	1.5	NaH (CO ₃)	3.0	80	0.05	1
Embodiment 124	0.4	2.5	2.5	2.9	400	137	Acetone	9.9	Desiccating method	1000	5	0	60	1.5	NaH(CO ₃)	4.0	80	0.13	3	Embodiment 123	0.4	2.5	2.5	2.9	400	137	Acetone	9.9	Desiccating method	1000	5	0	60	1.5	NaH (CO ₃)	3.0	80	0.05	1
Embodiment 124	0.4	2.5	2.5	2.9	400	137	Acetone	9.9	Desiccating method	1000	5	0	60	1.5	NaH(CO ₃)	4.0	80	0.13	3	Embodiment 125	0.4	2.5	2.5	2.9	220	135	Ethyl acetate	8.0	The precipitator method	80	3	0	40	0.6	KH(CO ₃)	1.8	120	0.15	4
Embodiment 126	0.4	2.5	2.5	2.9	260	137	Ethyl acetate	8.0	The precipitator method	80	1	0	40	0.6	KH(CO ₃)	1.8	120	0.08	1	Embodiment 125	0.4	2.5	2.5	2.9	220	135	Ethyl acetate	8.0	The precipitator method	80	3	0	40	0.6	KH(CO ₃)	1.8	120	0.15	4
Embodiment 126	0.4	2.5	2.5	2.9	260	137	Ethyl acetate	8.0	The precipitator method	80	1	0	40	0.6	KH(CO ₃)	1.8	120	0.08	1	Embodiment 127	0.4	2.5	2.5	2.9	480	137	Ethyl acetate	8.0	The precipitator method	80	1	0	40	0.6	KH(CO ₃)	1.8	120	0.07	2
Embodiment 128	0.4	2.5	2.5	2.9	530	137	Ethyl acetate	8.0	The precipitator method	80	3	0	40	0.6	KH(CO ₃)	1.8	120	0.18	5	Embodiment 127	0.4	2.5	2.5	2.9	480	137	Ethyl acetate	8.0	The precipitator method	80	1	0	40	0.6	KH(CO ₃)	1.8	120	0.07	2
Embodiment 128	0.4	2.5	2.5	2.9	530	137	Ethyl acetate	8.0	The precipitator method	80	3	0	40	0.6	KH(CO ₃)	1.8	120	0.18	5	Embodiment 129	0.05	2.95	2.95	3.0	450	138	Methylene dichloride	9.5	The precipitator method	50	2	0	150	2.2	Ca(OH) ₂	2.2	150	0.11	1

Table 3 (continuous 2)

Embodiment 130	0.8	2.0		2.0	2.8	450	130	Methylene dichloride	9.5	The precipitator method	50	1	150	2.2	Ca(OH) ₂	2.2	150	0.12	1
Embodiment 130	0.8	2.0		2.0	2.8	450	130	Methylene dichloride	9.5	The precipitator method	50	1	150	2.2	Ca(OH) ₂	2.2	150	0.12	1	Embodiment 131	1.6	1.2		1.2	2.8	450	140	Methylene dichloride	9.5	The precipitator method	50	2	0	150	2.2	Ca(OH) ₂	2.2	150	0.10	2
Embodiment 132	2.0	0.8		0.8	2.8	450	145	Methylene dichloride	9.5	The precipitator method	50	6	150	2.2	Ca(OH) ₂	2.2	150	0.18	5	Embodiment 131	1.6	1.2		1.2	2.8	450	140	Methylene dichloride	9.5	The precipitator method	50	2	0	150	2.2	Ca(OH) ₂	2.2	150	0.10	2
Embodiment 132	2.0	0.8		0.8	2.8	450	145	Methylene dichloride	9.5	The precipitator method	50	6	150	2.2	Ca(OH) ₂	2.2	150	0.18	5	Embodiment 133	0.6	2.0		2.0	2.6	450	132	Methylene dichloride	9.5	The precipitator method	50	2	0	150	2.2	Ca(OH) ₂	2.2	150	0.07	2
Embodiment 134	0.4	2.0		2.0	2.4	450	135	Methylene dichloride	9.5	The precipitator method	50	4	150	2.2	Ca(OH) ₂	2.2	150	0.18	4	Embodiment 133	0.6	2.0		2.0	2.6	450	132	Methylene dichloride	9.5	The precipitator method	50	2	0	150	2.2	Ca(OH) ₂	2.2	150	0.07	2
Embodiment 134	0.4	2.0		2.0	2.4	450	135	Methylene dichloride	9.5	The precipitator method	50	4	150	2.2	Ca(OH) ₂	2.2	150	0.18	4	Embodiment 135	1.5		1.2	1.2	2.7	450	135	Methylene dichloride	9.5	The precipitator method	50	4	0	150	2.2	Ca(OH) ₂	2.2	150	0.09	1
Embodiment 136	1.0		1.7	1.7	2.7	450	130	Methylene dichloride	9.5	The precipitator method	50	2	150	2.2	Ca(OH) ₂	2.2	150	0.10	1	Embodiment 135	1.5		1.2	1.2	2.7	450	135	Methylene dichloride	9.5	The precipitator method	50	4	0	150	2.2	Ca(OH) ₂	2.2	150	0.09	1
Embodiment 136	1.0		1.7	1.7	2.7	450	130	Methylene dichloride	9.5	The precipitator method	50	2	150	2.2	Ca(OH) ₂	2.2	150	0.10	1	Embodiment 137	0.4		2.5	2.5	2.9	450	125	Methylene dichloride	9.5	The precipitator method	50	4	0	150	2.2	Ca(OH) ₂	2.2	150	0.11	1

^*M: basic metal molal quantity and alkaline-earth metal molal quantity sum

S: sulfate groups molal quantity

(4) stretch:

By obtaining the tensile cellulose acylate film with the embodiment A same way as.Similar to embodiment A, the film of the present invention of these embodiment has good performance.

(5) test the high temperature ageing variable color of tensile not or tensile cellulose acylate film:

By testing with the embodiment A same way as and estimating film (weather stain), the results are shown in table 3.

(6) structure polarizer:

By and the embodiment A same way as, make the film saponification by dipping, the preparation polarization film, they are laminated and be combined in the liquid crystal indicator, test.The results are shown in table 3 (flavescence among the LCD).The film of the present invention of these embodiment all has the good optical performance.

(7) optical compensating film:

By and the embodiment A same way as, with the present invention not tensile or tensile cellulose acylate film be used to form optical compensating film, they have the good optical performance.

(8) low refractive index film:

Press and the embodiment A same way as, cellulose acylate film of the present invention is used to form low refractive index film, they have the good optical performance.

(9) structure liquid crystal indicator:

Press and the embodiment A same way as, the structure liquid crystal indicator, the liquid crystal indicator that comprises cellulose acylate film of the present invention has the good optical performance.

The cellulose acylate pellet (10/90 of the cellulose acylate pellet of mix embodiment 101 and embodiment 1; 30/70; 70/30; 10/90); the mixture that obtains is used to form film; and, be used to form polarizer, optical compensating film, low refractive index film and liquid crystal indicator by stretching with embodiment 101 same way as.These also have good result.

Industrial applicibility

Can flavescence when cellulose acylate film of the present invention also uses in being combined into liquid crystal indicator for a long time. Therefore, the cellulose acylate film utmost point of the present invention is applicable to polarizer, optical compensating film and anti-reflection film. In addition, according to cellulose acylate pellet of the present invention and manufacture method thereof, can make in a simplified manner cellulose acylate film. Therefore, the present invention has very high industrial applicibility.

Claims

1. cellulose acylate pellet, its crystallization fusion heat is 10J/g at the most.

2. cellulose acylate pellet as claimed in claim 1, wherein the quantity of needle-like impurity is 50/mg at the most.

3. cellulose acylate pellet as claimed in claim 1 or 2, its sulphate groups mass contg are that 0ppm is extremely less than 200ppm.

4. as each described cellulose acylate pellet of claim 1-3, wherein the ratio of (basic metal molal quantity and group II metal molal quantity sum)/(sulfate groups molal quantity) is 0.3-3.0.

5. cellulose acylate pellet as claimed in claim 4, wherein said group II metal is a calcium.

6. as each described cellulose acylate pellet of claim 1-5, it satisfies following formula (S-1)-(S-3):

(S-1)2.6≤X+Y≤3.0，

(S-2)0≤X≤1.8，

(S-3)1.0≤Y≤3；

7. as each described cellulose acylate pellet of claim 1-6, it is a pellet.

8. make the method for cellulose acylate pellet, it is included in twin screw and kneads in the forcing machine with the screw speed of 50-300rpm and the cellulose acylate resin of kneading under the resin-pressure of kneading of 2-9MPa.

9. the method for manufacturing cellulose acylate pellet as claimed in claim 8, it is included in 160 ℃-220 ℃ described cellulose acylate resins and with its granulation kneaded and extrude.

10. make the method for cellulose acylate pellet as claimed in claim 8 or 9, wherein knead the interior pressure of forcing machine for being lower than 1 normal atmosphere described resin granulation by controlling described twin screw.

11., wherein knead in the forcing machine described resin granulation rare gas element being introduced described twin screw as the method for each described manufacturing cellulose acylate pellet of claim 8-10.

12. make the method as each described cellulose acylate pellet of claim 9-11, it comprises the pellet that grinding forms through granulation.

13., described cellulose acylate and the carbonate that is selected from least a metal in sodium, potassium, magnesium and the calcium, supercarbonate, oxyhydroxide or oxide compound reaction are neutralized to knead as the method for each described manufacturing cellulose acylate pellet of claim 8-12.

14. make the method for cellulose acylate pellet, it comprise by SP value for dissolving cellulos acylate in the solvent of 7-10 to prepare cellulose acylate solution, solidify described cellulose acylate then.

15. the method for manufacturing cellulose acylate pellet as claimed in claim 14, wherein said SP value is that the SP value is the ketone solvent of 7-10 for the ester solvent of 7-10, halogenated hydrocarbon solvent or the SP value that the SP value is 7-10 for the solvent of 7-10.

16., wherein realize described curing to remove described solvent by the described cellulose acylate solution of drying as the method for claim 14 or 15 described manufacturing cellulose acylate pellets.

17., wherein realize described curing so that described cellulose acylate is precipitated by described cellulose acylate solution is introduced in the poor solvent as the method for claim 14 or 15 described manufacturing cellulose acylate pellets.

18. make the method for cellulose acylate film, it comprises each described cellulose acylate pellet fusion curtain coating of claim 1-7 is become film.

19. the method for manufacturing cellulose acylate film as claimed in claim 18 is wherein by using touch roll to form described film under the line pressure of 3kg/cm-100kg/cm.

20. the method for manufacturing cellulose acylate film as claimed in claim 18 is wherein by using touch roll to form described film under the contact pressure of 0.3MPa-3MPa.

21. as the method for each described manufacturing cellulose acylate film of claim 18-20, it also is included at least one direction with the cellulose acylate film stretching 1%-300% that forms.

22. a cellulose acylate film, it is made according to each described manufacture method of claim 18-21.

23. a cellulose acylate film, it is formed by each described cellulose acylate pellet of claim 1-7, and its residual solvent content is 0.01 quality % at the most.

24. a polarizer, it comprises polarization film and at least one claim 22 or 23 described cellulose acylate films that close layer by layer thereon.

25. an optical compensating film, it comprises claim 22 or the 23 described cellulose acylate films base material as it.

26. an anti-reflection film, it comprises claim 22 or the 23 described cellulose acylate films base material as it.

27. a liquid crystal indicator, it comprises at least a in the described polarizer of claim 24, the described optical compensating film of claim 25 and the described anti-reflection film of claim 26.