CN104117230A - Filter, filtering method, acylate cellulose film and making method thereof - Google Patents

Filter, filtering method, acylate cellulose film and making method thereof Download PDF

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Publication number
CN104117230A
CN104117230A CN201410162597.XA CN201410162597A CN104117230A CN 104117230 A CN104117230 A CN 104117230A CN 201410162597 A CN201410162597 A CN 201410162597A CN 104117230 A CN104117230 A CN 104117230A
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CN
China
Prior art keywords
filter
dope
film
cellulose
foreign matter
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CN201410162597.XA
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Chinese (zh)
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CN104117230B (en
Inventor
长浜慎太郎
鹫谷公人
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富士胶片株式会社
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Priority to JP2013091228 priority
Priority to JP2014022222 priority
Priority to JP2014-022222 priority
Application filed by 富士胶片株式会社 filed Critical 富士胶片株式会社
Publication of CN104117230A publication Critical patent/CN104117230A/en
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Publication of CN104117230B publication Critical patent/CN104117230B/en

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Abstract

The invention aims to provide a filter, a filtering method, an acylate cellulose film and a making method thereof capable of highly efficiently removing unreacted cellulose, being insoluble foreign matter, from a dope; the acylate cellulose film has less bright spot foreign metters; a surface of a fiber body (65) forming the filter filtering the dope is provided with a cationic polymer layer (66) containing cationic polymers (67); therefore, a surface of the filter carries positive electricity; the unreacted cellulose being insoluble foreign matter with negative electricity in the dope can be fixed on the surface of the filter (62) with the positive electricity, and thus being removed from the dope.

Description

Filter, filter method, cellulose acylate film and manufacture method thereof

Technical field

The present invention relates to a kind of filter, filter method, cellulose acylate film and manufacture method thereof.

Background technology

In continuous universal in recent years liquid crystal indicator, the multiple bloomings such as the diaphragm of use Polarizer, phase retardation film, anti-reflective film.These bloomings are to use polymer film.Particularly the operability when manufacturing is excellent and demonstrate the aspect of good optical characteristics, is widely used cellulose acylate film.

Manufacture method known melting masking method or the solution film-forming method of cellulose acylate film.Melting masking method for by the acylated cellulose through melting with the membranaceous method that obtains cellulose acylate film of extruding.Solution film-forming method is following methods: solution (hereinafter referred to as the dope) curtain coating that acidylates cellulose dissolution gained in solvent is arrived on the supporters such as metal cylinder (drum) or band (band); make it dry, obtain thus cellulose acylate film.Compared to utilizing melting masking method to manufacture, to utilize in the situation that solution film-forming method manufactures, the possibility that acylated cellulose is subject to fire damage is little, therefore can stably manufacture that transparency is high, the film of flatness or optical characteristics excellence.

In dope, acylated cellulose used is by being synthesized by the cellulose acylated of the natural goods gained such as linter (1inter) or slurry (pulp).Therefore, in acylated cellulose, be not dissolved in solvent foreign matter (hereinafter referred to as not dissolving foreign matter) form and contain hemicellulose (hemicellulose) or without cellulose (hereinafter referred to as unreacted cellulose) of acidylate etc.Unreacted cellulose becomes foreign matter in film, if by this film for display unit, turn white and in sight with the form of bright spot in the position that has foreign matter in display frame.Below, the foreign matter that causes this bright spot is called to bright spot foreign matter.

In order stably to manufacture, transparency is high, the film of flatness or optical characteristics excellence, hemicellulose or unreacted cellulose etc. must not dissolved to foreign matter and removes from dope.Do not dissolve foreign matter and be mainly and remove by filtering.During filtration, use by the hydrophobic filter of the mades such as the metallic fibers such as the synthetic fibers such as polypropylene or stainless steel or by the hydrophilic filter of the mades such as cellulose fibre etc.For example, in patent documentation 1, disclose a kind of surface to filter and implemented hydrophobization processing so that do not dissolve the filter that does not produce hydrogen bond between foreign matter and filter.

[prior art document]

[patent documentation]

[patent documentation 1] Japanese Patent Laid-Open 2004-292570 communique

Yet the filter existence of patent documentation 1 is difficult to the problem that unreacted cellulose is removed efficiently.In addition, if unreacted cellulose is removed and with metallic filter, is replaced the filter of patent documentation 1, from starting to filter, filter presses (filter pressure) slowly to rise, if more than filter presses and reach certain value, must stop filtration and frequently changes metallic filter.Therefore the problem that, has Expenses Cost (cost).

Summary of the invention

Therefore, the object of the present invention is to provide a kind of using cellulose acylate film and the manufacture method thereof of the filter of removing efficiently as the unreacted cellulose that does not dissolve foreign matter, filter method, bright spot few foreign.

Filter of the present invention is consisted of the plurality of fibers that the cationic polymer layer that contains cationic polymer is being set on surface.

Compound shown in the preferred following formula of cationic polymer (1).In addition, deduct the quality 100 of the quality gained of cationic polymer layer with respect to the quality by the fiber of cationic polymer layer is being set on surface, the amount of compound is preferably in above, the scope below 15 mass parts of 1 mass parts.In addition, filter of the present invention is preferably for acidylating in the filter progress that the unreacted cellulose of cellulose dissolution in the solution of solvent gained remove.

[changing 1]

Wherein, m is 2 integers with fore-telling,

-A 1-,-A 2-,-A 3-be-CH 2-or-NH-.

Filter method of the present invention is used described arbitrary filter to filter acidylating cellulose dissolution solution of gained in solvent, and the unreacted cellulose in solution is removed.

The manufacture method of the cellulose acylate film of the present invention dope that curtain coating contains acylated cellulose and solvent on the supporter of continuous moving and form casting films; from supporter, strip casting films and make film; stripped film is simultaneously carried out to conveyance simultaneously utilizes drier to be dried; and in the manufacture method of described cellulose acylate film, dope is to use described filter method to carry out the dope filtering.

Cellulose acylate film of the present invention is being arranged between 2 Polarizers of cross Nicols (crossed nicols) configuration, and from a side irradiate light, while observing from opposite side, every 1cm 2in to be of a size of the bright spot foreign matter that 10 μ m are above, brightness is at least more than 80cd be below 4.

[effect of invention]

Filter of the present invention and filter method can will be removed efficiently as the unreacted cellulose that does not dissolve foreign matter.Therefore, can manufacture the cellulose acylate film of bright spot few foreign.In addition, filter presses to rise and is also inhibited, if therefore use filter of the present invention and filter method, without the frequent filter of changing.In addition, cellulose acylate film of the present invention and manufacture method thereof suppress the bright spot in display unit.

Accompanying drawing explanation

Fig. 1 is the key diagram of the summary of explanation dope manufacturing equipment.

Fig. 2 is for representing the summary section of an example of filter.

Fig. 3 is for representing the summary enlarged drawing of filter.

Fig. 4 is for representing the summary section of the cationic fiber of formation filter.

Fig. 5 is that the cationic of cationic fiber shows machine-processed key diagram.

Fig. 6 is the key diagram of the unreacted cellulose absorption mechanism of filter.

Fig. 7 is the key diagram of the 1st bright spot foreign matter and the 2nd bright spot foreign matter.

Fig. 8 is for representing the key diagram of the summary of membrane producing device.

The explanation of symbol:

10: dope manufacturing equipment

11: flux bath

12: additive tank

13: hopper

15: mixing channel

17,34: chuck

18,19,35: motor

20: the 1 mixers

22: the 2 mixers

26: heater

27: dope

29,80: register

30: the 1 filters

30a: body

30b: cap

30c: plate

30d: lid member

31,32,45: pipe arrangement

33: storage tank

36: mixer

40: flash distillation plant

41,83: retracting device

42: regenerating unit

44: the 2 filters

46: flowmeter

49: the 3 filters

50: membrane producing device

62: filter

63: cationic fiber

65: fiber bodies

66: cationic polymer layer

67: cationic polymer

70: unreacted cellulose

71: curtain coating chamber

73: feed block

75: casting films

76: casting mold

77: curtain coating cylinder

78: cooling medium feedway

79: pressure-reducing chamber

82: condensed device

85: angle stripper

86: transfer part

87: drying device

88: stenter

90: film

92: trimming device

94: disintegrating machine

95: batch chamber

96: roller

97: hothouse

99: absorbing recovery device

100: cooling chamber

103: force neutralizer

104: annular knurl is given roller

107: pressure roller

108: takers-in

P1, P2, P3: pump

V1, V2, V3: valve

U1: curve

The specific embodiment

About cellulose acylate film and the manufacture method thereof of filter of the present invention, filter method, bright spot few foreign, one side illustrates example and is simultaneously illustrated.In addition, the form shown in is here an example of the present invention, does not limit the present invention.

As shown in Figure 1, dope manufacturing equipment 10 has flux bath 11, additive tank 12, hopper (hopper) 13 and mixing channel 15.In flux bath 11, accumulating the solvent of the raw material that becomes dope, in additive tank 12, accumulating in advance by the additive solution of additive and solvent gained.In addition, hopper 13 is supplied with to acylated cellulose.These flux baths 11, additive tank 12 and hopper 13 are all connected with mixing channel 15, become suitably appropriate various dope raw materials are sent to the structure in mixing channel 15.From the supply of the raw material of flux bath 11 and additive tank 12 and to stop be that switching by valve V1, valve V2 is adjusted.

Various dope raw materials are transported to order in mixing channel 15, send into form etc. and be not particularly limited, for example, about sequence of batching products, can carry various dope raw materials simultaneously, also can be and will in the mixture of solvent and polymer mixed gained, add additivated form.In addition, additive not necessity is made solution, as long as suitably change according to the form of used additive.For example, in the situation that additive is liquid under normal temperature, as long as keep this liquid condition directly to add, in the situation that additive is solid, also can add with hopper etc.Additive is such as having delustering agent, ultra-violet absorber etc.

Chuck (jacket) 17 is installed on the mixing channel 15 of stainless steel.By heating and the heat insulation effect of chuck 17, the temperature of the dope in mixing channel 15 27 is remained roughly certain in the scope of-10 ℃~55 ℃.In addition, on mixing channel 15, the 1st mixer 20 and the 2nd mixer 22 that by motor 18, motor 19, drive are respectively installed.The 1st mixer 20 and the 2nd mixer 22 continuous rotations are uniformly mixed various dope raw materials, prepare thus dope 27.

In mixing channel 15, the dope 27 of preparation is to be admitted in heater 26 by pump P1.By utilizing heater 26 to become the mode of the roughly uniform temperature in the scope of 0 ℃~97 ℃, dope 27 to be heated, can improve the solubility in solvent such as acylated cellulose.The method that improves the solubility of dope 27 is not limited to this, also can use in addition the method for dope 27 being pressurizeed by pressing mechanism or by cooling body by the cooling method of dope 27 etc.

The dope 27 that has improved solubility is admitted in register 29, through being adjusted into roughly room temperature.Through register, being adjusted into the roughly dope 27 of room temperature is transported in the 1st filter 30 by pipe arrangement 31.In addition, dope 27, without contained solid constituent is all dissolved in solvent, also can be the form that solid constituent (solid content) disperses in solvent.Below, the concentration of dissolving in dope 27 or be dispersed in the solid constituent in solvent is called to solid component concentration.

The 1st filter 30 catches dopes 27 contained hemicellulose or unreacted cellulose, do not dissolve gel etc. does not dissolve foreign matter (filter progress).The valve V3 that is arranged on pipe arrangement 32 is switched to storage tank (stock tank) 33 or flash distillation (flash) device 40 by the link of the 1st filter 30.Thus, the dope 27 by the 1st filter 30 is transported in storage tank 33 or flash distillation plant 40 by switchable valve V3.About the details of the 1st filter 30, will describe below.

In the situation that the solid component concentration of filtered dope 27 meets desirable value, dope 27 is admitted to storage tank 33 through having adjusted in advance the valve V3 of aperture, is accumulated in this storage tank 33.Storage tank 33 and mixing channel 15 similarly, are installed with and have the chuck 34 of heating/heat insulation effect and by the mixer 36 that motor 35 rotates, through being adjusted into the both inside of the storage tank 33 of fixed temperature, stirring dope 27 always.Thus, can be for before curtain coating, suppress the cohesions such as solid constituent of dope 27 and the situation of generation foreign matter and this dope 27 is held in to uniform state.

In addition, also can, in preparation concentration after the dope 27 lower than target solids constituent concentration, be concentrated, be improved thus solid component concentration, be prepared the dope 27 of required solid component concentration.In this case, the dope 27 after the 1st filter 30 filters is transported in flash distillation plant 40 through having adjusted in advance the valve V3 of aperture.Flash distillation plant 40 makes the contained a part of solvent evaporation of dope 27, and dope 27 is concentrated.Be accompanied by concentrated and by retracting device 41, reclaimed after the condensing liquefaction of condensed device (not shown) at the solvent gas of flash distillation plant 40 interior generations.Utilize regenerating unit 42 solvent through the condensing liquefaction contained impurity such as moisture removed thereafter.The solvent of this impurity through removing can be used as dope raw material again.

Through concentrated dope 27, be, after being drawn out of flash distillation plant 40, to send in the 2nd filter 44 by pump P2.In the 2nd filter 44, possessing average pore size is the filter of the Porous below 100 μ m.The material of this filter is not particularly limited, such as using aptly the metallic filters such as stainless steel or organic filter such as cellulose-based.The aperture of this filter is to consider to be used for a certain amount of dope 27 is carried out suitably selecting after the filter efficiencies such as time (filtration time) of filtration treatment.The dope 27 filtering through the 2nd filter 44 is admitted to storage tank 33, for before curtain coating, is accumulating.

The dope 27 of accumulating in storage tank 33 is that one side is adjusted sendout by pump P3, and one side is transported in pipe arrangement 45.One side is confirmed flow by flowmeter 46, and one side is transported to dope 27 in the 3rd filter 49 that is arranged in trip more on the lower.The 3rd filter 49 can use the filter identical with the 2nd filter 44 aptly.The dope 27 that has been undertaken filtering by the 3rd filter 49 is transported in membrane producing device 50 and supplies curtain coating.

Use Fig. 2, the details of the 1st filter 30 is illustrated.The 1st filter 30 is the filter of multiple filter (multifilter) mode.The profile of the 1st filter 30 is formed by body 30a cylindraceous and to cover respectively a pair of roughly discoid cap 30b that the mode at the two ends of body 30a arranges.In the through hole that the substantial middle of the cap 30b of the upstream side on the flow direction of dope 27 is partly located to arrange, with respect to cap 30b, generally perpendicularly connecting pipe arrangement 31, in the through hole of partly locating to arrange in the substantial middle of the cap 30b in downstream, with respect to cap 30b, generally perpendicularly connecting pipe arrangement 32.

In the inner side of body 30a, with respect to cap 30b, discoid plate 30c is being set substantially in parallel, this discoid plate 30c possesses the through hole of a plurality of circular.Filter 62 is all being set in each through hole.Each filter 62 all forms hollow cylindrical, with respect to plate 30c and the state of substantially vertical setting is fixed on the upstream side of plate 30c.Thus, each filter 62 is fixed on the inner side of body 30a.The end in the downstream of each filter 62 be arranged in plate 30c corresponding through hole around.The lid member 30d of inaccessible hollow bulb is being set in the end of the upstream side of each filter 62.Dope 27 is directed to the 1st filter 30 from the pipe arrangement 31 of upstream side, by the through hole by filter 62, plate 30c successively, is filtered, and sends in the pipe arrangement 32 in downstream.

Like this, more than 62 structures of arranging side by side of filter that form hollow cylindrical can not changed to the size of the profile of filter 30, and increase the area (hereinafter referred to as filter area) that dope 27 contacts with filter 62, therefore preferably.In addition, in Fig. 2,3 place's through holes are being set in plate 30c, filter 62 are being set respectively on these through holes, but are the invention is not restricted to this, no matter at the 1st filter 30, interior that several places filter 62 is set is all harmless.In addition, the formation of the 1st filter 30 is not limited to this, as long as filter 62 in internal placement, can be any formation.

As shown in Figure 3, filter 62 is that many cationic fibers 63 are entwined brokenly and formed.As shown in Figure 4, each cationic fiber 63 is to be formed by fiber bodies 65 and 66, surperficial cationic polymer layer covering fiber bodies 65.As shown in Figure 5, cationic polymer layer 66 is consisted of cationic polymer 67.For cationic polymer 67, use alkane (polyamide epichlorohydrin) in the daiamid epoxy chlorine shown in following formula (1).Here, the mean molecule quantity of daiamid epoxy chloropropane is preferably in the scope more than 5000, below 80000.

[changing 2]

Wherein, m is 2 integers with fore-telling,

-A 1-,-A 2-,-A 3-be-CH 2-or-NH-.

In the daiamid epoxy chloropropane of formula (1), for example, can use aptly the compound shown in following formula (2)~formula (5).Here, the compound of formula (2) be in formula (1) m=2 and-A 1-,-A 2-,-A 3-be-CH 2-compound.The compound of formula (3) be in formula (1) m=4 and-A 1-,-A 2-,-A 3-be-CH 2-compound.The compound of formula (4) be in formula (1) m=2 and-A 1-,-A 2-be-CH 2-,-A 3-be-compound of NH-.The compound of formula (5) be in formula (1) m=2 and-A 1-,-A 2-,-A 3the compound of-be-NH-.

[changing 3]

[changing 4]

[changing 5]

[changing 6]

For fiber bodies 65, such as using aptly, using slurry or the linter fiber such as cellulose-based as organic natural polymer of raw material.In addition,, about the raw material that slurry and linter are mixed, it is allocated than being not particularly limited.

Filter 62 is apply cationic polymer 67 and obtain on the surface that forms the filter paper of each fiber bodies 65 gained.The method of manufacturing filter 62 by coating cationic polymer 67 for example can be used following methods: using the cellulose fibre of raw material that becomes filter paper as fiber bodies 65, the coating fluid that coating contains cationic polymer 67 in this fiber bodies 65, with coated fiber bodies 65 paper processed, make the coated paper of gained dry.In addition, replace the method, also can be for being made filter paper by fiber bodies 65, by this filter paper impregnation in the solution of cationic polymer 67 and other well-known any means such as be dried.By these methods, be formed on the filter 62 that possesses each cationic fiber 63 of cationic polymer layer 66 on the surface of each fiber bodies 65.

The average pore size of filter 62 is not particularly limited, for example, preferably below 100 μ m.More reduce the average pore size of filter 62, can catch the finer foreign matter that do not dissolve, therefore preferably, if but average pore size is too small, and elongated the and filter of filtration time presses liter, and filter efficiency easily reduces.On the other hand, excessive if average pore size surpasses 100 μ m, be sometimes difficult to catch the contained fine foreign matter that do not dissolve of dope 27.Therefore, the aperture of filter is to consider suitably to select after the filter efficiencies such as filtration time or filter pressure.

About forming the cationic fiber 63 of filter 62, catch efficiently the mechanism of not dissolving foreign matter, the inventor etc. are presumed as follows.

In dope 27, the nitrogen-atoms place positively charged of the formation quaternary ammonium compound that cationic polymer 67 has in molecule, thus cationization.Limiting condition when above the state shown in Chinese style (1)~formula (5) is each cationic polymer 67 cationization.Thus, as shown in Figure 5, the surface band positive electricity of cationic fiber 63.

By the surface band positive electricity of cationic fiber 63, as shown in Figure 6, the surface band positive electricity of filter 62.On the other hand, in dope 27, electronegative as the unreacted cellulose 70 that does not dissolve foreign matter.Therefore, unreacted cellulose 70 is adsorbed to the near surface of filter 62.

Like this, the positively charged electronegative unreacted cellulose 70 of filter 62 chemisorbed.In addition also other electronegative foreign matters of chemisorbed of filter 62.Therefore, filter 62 catches efficiently the electronegative foreign matter that comprises unreacted cellulose 70 and is removed from dope 27.Result is manufactured the aftermentioned cellulose acylate film (hereinafter referred to as film) 90 (with reference to Fig. 8) of bright spot few foreign.

Moreover, about bright spot foreign matter, have confirm the 1st bright spot foreign matter that is present in film and there is no actual damage, with film group is entered to time in the display unit such as liquid crystal indicator to confirm the 2nd bright spot foreign matter that is present in display unit and has actual damage.The 2nd bright spot foreign matter, because of also visible in display unit, is therefore called as observability foreign matter sometimes.In addition, the 2nd bright spot foreign matter has actual damage in display unit, is therefore also sometimes referred to as actual damage foreign matter.Certainly, it is desirable to be present in the bright spot few foreign in film, wherein, for liquid crystal indicator etc. in the situation that, special requirement the 2nd bright spot few foreign.

Here, bright spot foreign matter is to confirm in the following manner in this example.First, between 2 Polarizers through cross Nicols configuration, arrange through making the film 90 of sheet.From one-sided irradiation light, from opposition side, utilize light microscope (50 times) to observe.Then, the bright spot from bright spot in the scope of sensed luminance L more than 30cd, below 255cd, usings detected bright spot as the bright spot foreign matter in film.In addition, brightness L is that 256 grades of, integer 255cd below above with 0cd are through standardization.In addition, use this film production liquid crystal indicator, using the bright spot foreign matter that can confirm in this liquid crystal indicator as the 2nd bright spot foreign matter.On the other hand, using confirm in this liquid crystal indicator less than bright spot foreign matter as the 1st bright spot foreign matter.In addition, each the 1st bright spot foreign matter, the 2nd bright spot foreign matter are with the bright spot foreign matter of observing in film any be corresponding.

Chart shown in Fig. 7 (graph) obtains as below.First, the longitudinal axis of chart is got the size S (unit: μ m), the longitudinal axis is got to brightness L (unit: cd) of bright spot.Here, the size of bright spot refers to the diameter of bright spot.Then, for this chart, with the mark (by the shape of ◇ longitudinal tensile strain gained) of diamond type, describe the 1st bright spot foreign matter, with the mark of star-like (☆), describe the 2nd bright spot foreign matter.Learn thus, the 2nd bright spot foreign matter is to determine according to the benchmark that size S and brightness L are set.In the example shown in Fig. 7, the size S of the 2nd bright spot foreign matter is more than 10 μ m, and brightness is more than 80cd, is to be depicted in more set curve U 1 region closer to the top in chart.In addition the benchmark (curve U 1) of, determining the 2nd bright spot foreign matter changes according to display unit sometimes.

Filter 62 is removed bright spot foreign matter efficiently, wherein the 2nd bright spot foreign matter is removed efficiently.Therefore, be manufactured on the film 90 that in display unit, bright spot is inhibited.

When the quality settings of fiber bodies 65 is 100 mass parts, the amount of cationic polymer 67 is preferably in above, the scope below 15 mass parts of 1 mass parts.Here, the quality of fiber bodies 65 is that mass M 1 by cationic fiber 63 deducts the mass M 2 of cationic polymer layer 66 and calculates.In the situation that with respect to the fiber bodies 65 of 100 mass parts and the amount of cationic polymer 67 is more than 1 mass parts, compare with the situation that is less than 1 mass parts, foreign matter is not more dissolved in filter 62 absorption.On the other hand, even if with respect to the fiber bodies 65 of 100 mass parts and make cationic polymer 67 be greater than 15 mass parts, the amount of not dissolving foreign matter of chemisorbed is compared with the situation below 15 mass parts and is not also almost changed, and therefore can cause the cost of filter 62 to increase.

In addition,, from advantages such as corrosion resistance or excellent heat resistances, the pipe arrangement that forms the various devices of dope manufacturing equipment 10 and member and be by stainless steel is connected.In addition, the pump arranging in dope manufacturing equipment 10 or the number of valve or position is set is not particularly limited, be optionally and suitably change.

< acylated cellulose >

The acylated cellulose using in the present invention particularly preferably be utilize carboxylic acid by the ratio of cellulosic hydroxy esterification, be all conditions that the substitution value (hereinafter referred to as acyl substituted degree) of acyl group meets following formula (1)~formula (3).In addition, in (1)~(3), A and B are acyl substituted degree, and the acyl group of A is acetyl group, and the acyl group of B is that carbon number is 3~22 acyl group.

24≤A+B≤3.0…(1)

0≤A≤3.0…(2)

0≤B≤2.9…(3)

Glucose (glucose) unit that forms cellulose and carry out β-Isosorbide-5-Nitrae bond has free hydroxyl on 2,3 and 6.Acylated cellulose 20 is that this cellulosic part or all hydroxyl is through the polymer of hydrogen more than 2 acyl substituted through carbon number of esterification, hydroxyl.In addition, if a hydroxyl in glucose unit through 100% esterification, substitution value is 1, so in the situation of acylated cellulose, if 2,3 and 6 s' hydroxyl respectively through 100% esterification, substitution value becomes 3.

Here; the acyl substituted degree of 2 in glucose unit is set as to DS2, the acyl substituted degree of 3 are set as DS3, the acyl substituted degree of 6 is set as DS6; total acyl substituted degree of being obtained by " DS2+DS3+DS6 " preferably 2.00~3.00; more preferably 2.22~2.90, and then preferably 2.40~2.88.And then " DS6/ (DS2+DS3+DS6) " preferably more than 0.32, more preferably more than 0.322, and then preferably 0.324~0.340.

Acyl group can be only a kind of, also can be two or more.When acyl group is while being two or more, preferably wherein a kind of is acetyl group.Acetyl group is being set as to DSA to the summation of the substitution value of the hydrogen of 2,3 and 6 s' hydroxyl; when the summation of the substitution value by the acyl group gained beyond acetyl group on 2,3 and 6 is set as DSB; the value of " DSA+DSB " preferably 2.2~2.86, particularly preferably 2.40~2.80.DSB is preferably more than 1.50, particularly preferably more than 1.7.And preferably it more than 28% is the replacement of 6 hydroxyls to DSB, take more preferably more than 30% so that preferably more than 31%, particularly preferably more than 32% as being substituted by of 6 hydroxyls is suitable.In addition, the value of " DSA+DSB " of 6 of acylated cellulose 20 is preferably more than 0.75, more preferably more than 0.80, particularly preferably more than 0.85.By using acylated cellulose as above, can obtain polymer solution used when making solution film-forming and preferred dissolubility.

Carbon number is that more than 2 acyl groups can be aliphatic group and also can be aryl, is not particularly limited.Such as having cellulosic alkyl-carbonyl ester, alkenyl carbonyl ester or aromatic series carbonyl ester, aromatic series alkyl-carbonyl ester etc., these groups can have respectively the group being further substituted.Can enumerate: propiono, bytyry, valeryl, caproyl, caprylyl, capryl, dodecanoyl, tridecanoyl base, myristoyl base, hexadecanoyl group, octadecanoyl, isobutyryl, tertiary bytyry, cyclohexane carbonyl, oleoyl (oleoyl), benzoyl, naphthyl carbonyl, cinnamyl etc.In these groups, more preferably propiono, bytyry, dodecanoyl, octadecanoyl, tertiary bytyry, oleoyl, benzoyl, naphthyl carbonyl, cinnamyl etc., particularly preferably propiono, bytyry.

The solvent that becomes the raw material of dope 27 can be used as the solvent of the dope in the situation of utilizing solution film-forming to manufacture cellulose acylate film and well-known solvent.Such as being carrene, various alcohol, various ketone etc.In addition, also solvent can be set as to the mixture that comprises multi-solvents composition.

About the manufacture method of polymer film of the present invention, one side illustrates example one side and is illustrated.In addition, this example is only an example of the present invention, does not limit the present invention.

< membrane producing device >

As shown in Figure 8, by the prepared dope 27 of dope manufacturing equipment 10, by pipe arrangement, be admitted in the feed block (feed block) 73 in the curtain coating chamber 71 in membrane producing device 50.In the inside of feed block 73, the runner of the corresponding dope 27 of the layer structure of the casting films 75 forming with wish is being set, decide thus the configuration of dope 27.

Then, dope 27 is transported in casting mold 76.In casting mold 76, formed the flow export of dope 27, with this flow export be positioned at curtain coating cylinder 77 roughly directly over mode casting mold 76 is set.From viewpoints such as durability, heat resistances, material is preferably used the stainless steel of precipitation hardening type.Also can use aptly the material having in the pressure corrosion test in electrolyte aqueous solution with SUS316 system corrosion resistance about equally.

The curtain coating cylinder 77 playing a role as supporter has function that can continuous moving.In the inside of curtain coating cylinder 77, formed the runner of cooling medium.Cooling medium feedway 78 make cooling medium and curtain coating cylinder 77 between circulation, thus the runner of curtain coating cylinder 77 is supplied with to cooling medium continuously.Whereby, the surface temperature of curtain coating cylinder 77 is set as in the scope more than-40 ℃, below 30 ℃ roughly certain.From the flow export of casting mold 76, both dopes 27 of fixed temperature are flowed out to through the curtain coating cylinder 77 of rotation.Here, adjust the internal temperature of feed block 73 or casting mold 76 etc., the temperature of dope 27 is set as roughly certain in the scope of-10 ℃~55 ℃.The temperature of the dope 27 of this example is to be set as-5 ℃.Whereby, curtain coating through high efficiency and effectively cooling, forms gelatinous casting films 75 in the short time to the lip-deep dope 27 of curtain coating cylinder 77.

In this example, use curtain coating cylinder 77 as supporter, but the form of supporter is not particularly limited.For example, supporter also can be hang in the pair of rolls that comprises a driven roller, the casting belt of loopy moving.In addition, from thering is the aspects such as corrosion resistance or high strength, the preferred stainless steel of supporter.And then, in order to form the casting films 75 of flatness excellence, preferably as far as possible its surface is ground.

By being arranged on the pressure-reducing chamber 79 of curtain coating cylinder 77 sides of casting mold 76, by the back side of the dope 27 of institute's curtain coating, be in the pressure of upstream side of curtain coating cylinder 77 scope more than (atmospheric pressure-2000Pa), below (atmospheric pressure-10Pa), be set as roughly certain.Therefore thus, dope 27 is attracted to the curtain coating cylinder 77 in decompression state, is suppressed at and between casting films 75 and curtain coating cylinder 77, is involved in air (air).The internal temperature of curtain coating chamber 71 is to be adjusted in the scope of-10 ℃~57 ℃ roughly certain by register 80.Solvent gas from evaporation in dope 27 or casting films 75 is reclaimed by retracting device 83 after condensed device (condenser (condenser)) 82 condensing liquefaction.Then, solvent gas is sent in the regenerating unit (not shown) being connected with retracting device 83 and removes impurity, makes regenerated solvent.This regenerated solvent can be prepared the solvent of use again as dope.

By carrying out the cooling of casting films 75 in the enterprising step of curtain coating cylinder 77, gelation is further carried out.Carry out gelation until to have the casting films 75 of self-supporting be that one side is supported by angle stripper 85, one side is endowed tension force and is stripped from curtain coating cylinder 77 in conveyance direction.Casting films 75 after just having stripped preferably its residual solvent amount in the scope of 10 quality %~200 quality %.Casting films 75 is sent in the transfer part 86 that is configuring a plurality of delivery rolls (pass roller).In transfer part 86, casting films 75 by each delivery roll, supported and in addition conveyance during in, by a kind of drying device 87 as drier, blow attached temperature required dry wind, promote the dry of casting films 75.

Casting films 75 is delivered in stenter 88.In stenter 88, near its entrance at the both side ends of the casting films 75 a plurality of pins (pin) that puncture.For stenter 88, utilize in advance as the alternative register (not shown) of drier and adjust internal temperature, thus temperature is set as roughly certain in the scope more than 120 ℃, below 180 ℃.Therefore, both side ends through fixing casting films 75 in stenter 88 by conveyance during in, promote the dry of casting films 75.Along with the entrance from stenter 88 is towards outlet, the width being arranged between the track (rail) in stenter 88 constantly expands.Therefore, casting films 75 slowly expands during by conveyance along with track on width.Thus, the molecule orientation of the width of casting films 75 is controlled, and promotes dry and become film 90.In addition, also can not utilize the expansion of track extend and utilize shrinker that width is extended.Near the outlet of stenter 88, remove utilize pin to carry out film 90 fixing.In addition, in this example, illustrate there is pin pin (pin) formula stenter as fixed mechanism, but be not particularly limited, for example also can use fixture (clip) formula stenter as fixed mechanism, described fixture type stenter possesses the fixture of the both side ends of a plurality of gripping casting films 75.

By trimming device 92, the both side ends excision of the film 90 of the puncture scar of selling will have been produced in stenter 88.The both side ends of the film 90 through cutting off is fed in disintegrating machine (crusher) 94, is ground into fragment (chip).In addition, this excision operation also can be omitted, and in order to obtain the film 90 that defect is few, also preferably in curtain coating chamber 71, to arbitrary place of batching chamber 95, carries out.

Film 90 is sent in the hothouse 97 that is configuring a plurality of rollers 96, by each roller 96, is supported and conveyance in addition.During this period, utilize becomes roughly certain mode with the face temperature of film 90 as the alternative tempering machine (not shown) of drier and adjusts in the scope of 60 ℃~145 ℃.Whereby, can in the situation that not being subject to fire damage, promote the dry of film 90.In addition, in hothouse 97, from film 90, the solvent gas of volatilization is, after being reclaimed by absorbing recovery device 99, to remove solvent composition, again in hothouse 97, with the form of dry wind, supplies with.

The degree of drying of casting films 75 or film 90 can be usingd its residual solvent amount and held as standard.Residual solvent amount is to be set as following value: the object that wish is measured to residual solvent amount is as sample, by the quality settings of this sample be x, while making quality settings after sample bone dry be y, by { (x-y)/y} * 100 (unit: the value of the dry basis of %) calculating.

Film 90 is sent in cooling chamber 100, in the mode that becomes room temperature roughly through cooling.Cooling means is not particularly limited, for example, can be film 90 is placed in the cooling chamber 100 through being set as room temperature roughly and makes its naturally cooling method, also can be the method that pressure fan is supplied with cold wind is installed in cooling chamber 100.

Then, utilize and force neutralizer 103 to adjust the with voltage of film 90.The with voltage of film 90 is not particularly limited, preferably-more than 3kV, in+scope below 3kV, be set as roughly certain.Thereafter, utilizing annular knurl (knurling) to give roller 104 is processed and is given annular knurl to the both side ends of film 90 by embossing.Finally, film 90 is sent to and batches in chamber 95, and one side is given pressing force by pressure roller (press roller) 107 and adjusted flatness one side and batched by takers-in 108.

By above operation, manufacture the film 90 by the caused bright spot few foreign of unreacted cellulose 70.Film 90 is due to bright spot few foreign, the 2nd bright spot few foreign particularly, therefore can be aptly for liquid crystal indicator etc.According to the method, the length that can manufacture continuously especially aptly conveyance direction is at least 100m above and the film 90 of the length of width in the scope of 1400mm~1800mm.But the present invention is also greater than the film 90 of 1800mm to the length of width certainly, the length of width is less than the film 90 performance effects of 1400mm.The thickness of the film 90 completing is not particularly limited, preferably in the scope of 20 μ m~500 μ m.More preferably, in the scope of 30 μ m~300 μ m, particularly preferably be in the scope of 35 μ m~200 μ m, but in the situation that the thin film 90 in the scope of thickness in 15 μ m~100 μ m also can obtain effect of the present invention.

In addition,, in this example, the 1st filter 30 is used to the filter of multiple filter mode, but be not limited to this, as long as for using the form of filter 62 or cationic fiber 63, can be any form.In addition, in this example, filter 62 is to use on the surface of filter paper that forms each fiber bodies 65 gained to apply the filter of cationic polymer 67 gained, but is not limited to this.Also can use and on the surface of each fiber bodies 65, apply the filter that forms filter shape gained after cationic polymer 67.No matter be which kind of filter, all can utilize the effect of above-mentioned cationic polymer layer 66 that the unreacted cellulose 70 that causes the 1st bright spot foreign matter or the 2nd bright spot foreign matter is suitably removed from dope.

Below, illustrate to confirm the example of the experiment of effect of the present invention, the present invention is illustrated.But example shown here is only an example of the present invention, does not limit the present invention.

Experiment 1~experiment 8

In the present invention, by being arranged in formation on the surface of each fiber bodies 65 of the filter 62 in the 1st filter 30, cationic polymer layer 66 is set, and the unreacted cellulose 70 as electronegative insoluble matter is removed efficiently from dope 27.As below, evaluate effect of the present invention.

Use following raw material, utilize the dope manufacturing equipment 10 shown in Fig. 1 to prepare dope 27.

[dope raw material]

The viscosity that described cellulose triacetate is that substitution value is 2.84, viscosity average polymerization degree is 306, moisture content is 6 quality % in 0.2 quality %, dichloromethane solution is that 315mPas, average grain diameter are the powder that 1.5mm, standard deviation are 0.5mm, plasticiser A is triphenyl phosphate, plasticiser B is phosphoric acid Biphenyl Ester, and particulate is that average grain diameter is that 15nm, Mohs' hardness (Mohs ' hardness) are about 7 silica.In addition, while preparing dope, to become the mode of 1.8 quality % with respect to total solid composition, add delay controlling agent (N-N-bis--toluyl groups-N-p-methoxyphenyl-1,3,5-triazines-2,4,6-triamine).

[manufacture of dope]

Open respectively valve V1, valve V2, from flux bath 11 and additive tank 12, appropriate solvent and additive solution are sent into mixing channel 15, from hopper 13, appropriate acylated cellulose is sent into mixing channel 15 simultaneously.In mixing channel 15, the 2nd mixer 22 rotations that made to possess the 1st mixer 20 of the anchor shape wing (anchor blade) and dissolved type (dissolver type) by motor 18, motor 19, mix various dope raw materials, prepare dope 27.Now, the internal temperature of mixing channel 15 be in the scope of-10 ℃~55 ℃, be set as roughly certain.The temperature of mixing channel 15 is by making it circulate to adjust, keep after the heat transfer medium of adjusting is delivered in chuck 17 temperature.Utilize pump P1 that dope 27 is extracted out from mixing channel 15, deliver in heater 26, improved after the solubility of solid constituent in solvent, utilized register 29 to be set as roughly room temperature, obtained the dope 27 (dope before filtering) utilizing before the 1st filter 30 filters.

Dope before this filtration is delivered in the 1st filter 30 that possesses filter 62, utilized the 1st filter 30 to filter, obtain the dope 27 (the 1st filters rear dope) utilizing after the 1st filter 30 filters.Control valve V3 and after filtering the 1st dope send into flash distillation plant 40, make solvent evaporation and concentrate, obtain concentrated after dope.Then, after dope 27 extracts from flash distillation plant 40 after utilizing pump P2 to concentrate, utilize the 2nd filter 44 further to filter, obtain thus the dope 27 (the 2nd filters dope afterwards) utilizing after the 2nd filter 44 filters.The 2nd filter after dope in during before curtain coating, in storage tank 33, one side stirs one side and accumulates.After dope is sent in pipe arrangement 45 after the 2nd appropriate filtration of accumulating in storage tank 33, by the 3rd filter 49, filtered, be sent in membrane producing device 50.

In each experiment, about filter 62 used in the 1st filter 30, use respectively the filter that applies gained at the compound shown in the hurdle of " compound " of the upper coating of the filter (manufacture of Japan filter paper limited company) of the model shown in " the non-coating filter " of table 1 table 1.Here, model is that the filter of " 63LB ", " 63LS ", " 63 " is to utilize and usings linter and slurry as organic filter of the cellulose fibre made of raw material, and average pore size is respectively approximately 21 μ m, approximately 20 μ m, approximately 12 μ m.

About be coated with compound, the compound of cloth of coating-type (2) in experiment 1 and experiment 4, the compound of cloth of coating-type (3) in experiment 2, the compound of cloth of coating-type (4) in experiment 3, the compound of cloth of coating-type (5) in experiment 5.In experiment 6, experiment 7 and experiment 8, painting compound not.With respect to the quality by cationic fiber 63, deduct the quality 100 of the quality gained of cationic polymer layer 66, the coating weight of the compound of formula (2)~formula (5) is to be made as 10 mass parts.In " m " on the hurdle of " compound " of table 1 and the hurdle of " n ", with numeral, " value of m " in formula (1) and " number that is present in the NH base in the repetitive of compound " is shown respectively.In addition, about the not experiment of painting compound on non-coating filter (experiment 6, experiment 7, experiment 8), in " m " of compound and the hurdle of " n ", show work "-", "-".In addition, in all experiments, in the 2nd filter 44 and the 3rd filter 49, using the average pore size by stainless steel fibre made is the metallic filter of 10 μ m.In addition, in the 1st filter~3rd filter 30,44,49, all filter area is set as to 30m 2.

[changing 7]

[changing 8]

[changing 9]

[changing 10]

[film manufacture]

Use the membrane producing device 50 shown in Fig. 8, by utilizing described method to manufacture film 90 by the dope 27 of dope manufacturing equipment 10 mades.First, from dope manufacturing equipment 10, through 73 pairs of casting molds of feed block 76, carry after appropriate dope 27, on the curtain coating cylinder 77 of continuous rotation, from the curtain coating mouth of casting mold 76, flow out dope 27 and form casting films 75.During curtain coating, utilize curtain coating cylinder 77 sides of the dope 27 of the 79 pairs of institute's curtain coatings in pressure-reducing chamber to reduce pressure, the mode that simultaneously becomes 60 μ m with the thickness of dried film 90 is adjusted the discharge of dope 27.

About curtain coating cylinder 77, use can utilize drive unit (not shown) to control the stainless steel cylinder of rotating speed, by heat transfer medium feedway (not shown), supply with cooling medium, thus surface temperature is adjusted into-10 ℃, the rotary speed during by masking is set as 100r/min. (unit: the r/min. unit of referring to: rotating speed/minute).In addition, about casting mold 76, using the form that has the flow export that comprises the slit that width is 1.8m and be used for adjusting the chuck (not shown) of internal temperature, is 30 ℃ by the Temperature Setting of the dope 27 of institute's curtain coating.About feed block 73 or become the pipe arrangement etc. of the runner of dope 27, use the form with temperature adjustment function, its internal temperature is all held in to 30 ℃.

One side is supported by angle stripper 85, and one side strips and carries out cooling gel until have the casting films 75 of self-supporting from curtain coating cylinder 77.Then, casting films 75 is delivered in transfer part 86, in one side, by a plurality of delivery rolls, supported one side carry out conveyance during, by drying device 87, supply with through being adjusted into the dry wind of 40 ℃ and promote the dry of casting films 75.Then, casting films 75 is moved in the stenter 88 with a plurality of pins, after utilizing a plurality of pins that the both side ends of casting films 75 is fixing, casting films 75 one sides are extended to one side on width and carry out conveyance, during this period, by drying device (not shown), supply with the dry wind of 100 ℃ and within 20 minutes, be dried and make film 90.

Use is arranged in 30 seconds with the interior trimming device 92 that possesses NT type cutting machine apart from the outlet of stenter 88, and the position by the both side ends from film 90 towards inner side 50mm cuts off.The both side ends of the film 90 through cutting off is to be delivered in disintegrating machine 94 by chopping pressure fan (cutter blower) (not shown), is ground into average 80mm 2the fragment of left and right.

Predrying chamber (not shown) is set between trimming device 92 and hothouse 97 and supplies with the dry wind of 100 ℃, after thus film 90 being preheated, move in hothouse 97.In hothouse 97, the mode that becomes 140 ℃ in the face temperature with film 90 utilizes temperature adjustment device (not shown) to adjust in the hothouse 97 of internal temperature, and one side hangs over one side conveyance film 90 on a plurality of rollers 96, and making during this period, film 90 is dry.Be to be set as 10 minutes the drying time of the film 90 in hothouse 97.Here, the face temperature of film 90 be use be arranged on film 90 conveyance path directly over and the thermometer (not shown) of near surface measure.In hothouse 97, use the absorbing recovery device 99 of the desorbing agent there is the adsorbent that comprises active carbon and comprise dry nitrogen, after the solvent gas of volatilization in film 90 is reclaimed, with amount of moisture, become the moisture that mode below 0.3 quality % is removed solvent gas.

Damping chamber (not shown) is set between hothouse 97 and cooling chamber 100, to film 90 supplying temperatures, be after 50 ℃, dew point are the air of 20 ℃, the air that directly to blow attached 90 ℃, humidity be 70% carries out damping, and curling (curl) that in film 90, produce corrected.Then, film 90 is delivered in cooling chamber 100, by film 90 slowly cooling until 30 ℃ following after, use and force that neutralizer 103 is above by the with voltage being set as-3kv of film 90, in+scope below 3kV.Then, the both side ends of using annular knurl to give 104 pairs of films 90 of roller is given annular knurl, by the concavo-convex rectification producing on surface.In addition, the width of film 90 being given to annular knurl is set as to 10mm, with concavo-convex height, compared with the mode of the high average 12 μ m of the average thickness of film 90, adjusts the pressing force that annular knurl is given roller 104, film 90 is carried out to embossing processing.

Film 90 is delivered to and batched in chamber 95, and one side utilizes 107 pairs of films 90 of pressure roller to give the pressing force of 50N/m, and one side is utilized the takers-in 108 of 169mm carries out curling.While batching, the tension force that the coiling of film 90 is started is set as 300N/m, and the tension force finishing of reeling is set as 200N/m.By above operation, obtain the film 90 of web-like.The thickness of the film 90 completing is 60 μ m.In addition, in ownership membrane process, by the average rate of drying of casting films 75 or film 90 be set as 20 quality %/minute.

In each experiment, as following, obtain the filter efficiency of filter used in the 1st filter 30.(the Japanese Industrial Standards of Dui Shi Japanese Industrial Standards, JIS) 8 kinds of powders (comprise clay mineral, the soil of the fertile layer in the Northeast (1oamy layer of the Kanto district)) disperse water that is dispersed in water gained is filtered with constant flow rate, according to the population before and after filtering, calculates filter efficiency.The concentration of the JIS8 kind powder in disperse water is to be set as 5ppm.Flow while filtering with constant flow rate is to be set as 6.6mi/min.cm 2.In addition so-called " mi/min.cm, 2", mean every 1cm in 1 minute 2in flow through the flux unit of the volume (m1) of disperse water.Filter efficiency be by (population before filtration)-(population after filtration)) ÷ (population before filtration) * 100 (unit: %) calculate.By in the hurdle of " the JIS powder filter efficiency " that the results are shown in table 1 of this filter efficiency.

Owing to cannot directly measuring the cellulosic amount of unreacted contained in raw material, be therefore difficult to directly calculate to the cellulosic filter efficiency of unreacted.Therefore, first as described above, as filter specification, evaluate the filter efficiency to the disperse water of JIS8 kind powder here.In addition, as aftermentioned, film 90 to dope 27 mades when using filter 62 of the present invention carries out the evaluation of bright spot foreign matter number and the 2nd bright spot foreign matter number, confirms thus the effect of the present invention of " can will cause bright spot foreign matter, particularly the 2nd bright spot foreign matter and remove efficiently as the unreacted cellulose that does not dissolve foreign matter ".

In each experiment, as below, obtain the number of the bright spot foreign matter in film 90.First, between 2 Polarizers through cross Nicols configuration, arrange through making the film 90 of sheet.From a side, irradiate light, from opposite side, utilize microscope to observe.Then, detect the bright spot in the scope of brightness L more than 30cd, below 255cd in bright spot, using detected bright spot as the bright spot foreign matter in film 90, obtain every 1cm 2the number of bright spot foreign matter.Microscopical condition is now 50 times of multiplying powers and transmitted light source.Then, this number is applied to following benchmark, with tetra-grades of A~D, evaluates.Evaluation result is shown in each " bright spot foreign matter " hurdle of table 1.

A: be less than 10

B:10 is above, be less than 20

C:20 is above, be less than 50

More than D:50

In addition, with this film 90, make the liquid crystal indicator with above-mentioned homotype, using the bright spot that confirms in this liquid crystal indicator as the 2nd bright spot foreign matter in film 90, obtain every 1cm 2the number of the 2nd bright spot foreign matter.This number is applied to following benchmark, with tetra-grades of A~D, evaluates.Evaluation result is shown in each " the 2nd bright spot foreign matter " hurdle of table 1.

Below A:3

B: more than 3 and be below 4

C: more than 4, and be below 5

D: more than 5

In addition, to utilizing visible the 2nd bright spot foreign matter of said method size up S and brightness L under the condition determination of above-mentioned bright spot foreign matter, it is more than 10 μ m that result is size S, and brightness is more than 80cd, confirms bright spot foreign matter and is present in the region closer to the top of more set curve U 1 in chart.

In addition, in each experiment, as below, evaluate the rising degree (pressing liter hereinafter referred to as filter) of the internal pressure (filter is pressed) of the 1st filter 30.Adjust the design temperature of heater 26 to become 90 ℃, (filter pressure) value is pressed in the maximum filter of measuring in the 1st filter 30.Use this maximum filter pressure value, by following benchmark, filter is pressed to rise and evaluate.Evaluation result is shown in each " filter presses liter " hurdle of table 1.

A: maximum filter pressure value is less than 0.3MPa

B: maximum filter pressure value be 0.3MPa above, be less than 0.5MPa

C: maximum filter pressure value is more than 0.5MPa

Table 1

According to above results verification, arrive, the filter 62 that cationic polymer layer 66 is being set on the surface of each fiber bodies 65 is compared with not there is not the filter of cationic polymer layer 66, better to the filter efficiency of the disperse water of JIS8 kind powder.

In addition confirm, if the dope 27 that the filter 62 of cationic polymer layer 66 filters be set on the surface of each fiber bodies 65 manufacturing with utilizing, compare with using the situation of the filter that does not have cationic polymer layer 66, can the bright spot foreign matter in film 90 be suppressed still less, especially can the 2nd bright spot foreign matter be suppressed still less.Can confirm thus, the filter 62 that cationic polymer layer 66 is being set on the surface of each fiber bodies 65 catches and removes the unreacted cellulose 70 as electronegative insoluble matter efficiently in dope 27.

Also can confirm in addition, even if by the filter 62 that cationic polymer layer 66 is being set on the surface in each fiber bodies 65 for the 1st filter 30, also with the situation of using the filter there is not cationic polymer layer 66 similarly, the filter in the 1st filter 30 is pressed and can excessively do not risen.

Claims (8)

1. a filter, is characterized in that: it is consisted of the plurality of fibers that the cationic polymer layer that contains cationic polymer is being set on surface.
2. filter according to claim 1, is characterized in that: described cationic polymer is the compound shown in following formula (1),
[changing 11]
Wherein, m is more than 2 integer,
-A 1-,-A 2-,-A 3-be-CH 2-or-NH-
3. filter according to claim 2, it is characterized in that: with respect to the quality by the fiber of cationic polymer layer is being set on surface, deduct the quality 100 of the quality gained of cationic polymer layer, the amount of described compound is in the scope more than 1 mass parts, below 15 mass parts.
4. filter according to claim 1, is characterized in that: in its filter progress that is used to the unreacted cellulose acidylating in the solution of cellulose dissolution gained in solvent to remove.
5. filter according to claim 3, is characterized in that: in its filter progress that is used to the unreacted cellulose acidylating in the solution of cellulose dissolution gained in solvent to remove.
6. a filter method, is characterized in that: use and filter acidylating cellulose dissolution solution of gained in solvent according to the filter described in any one in claim 1 to 5, the unreacted cellulose in described solution is removed.
7. the manufacture method of a cellulose acylate film; it is characterized in that: the dope that curtain coating contains acylated cellulose and solvent on the supporter of continuous moving and form casting films; from described supporter, strip described casting films and make film; stripped described film is simultaneously carried out to conveyance and simultaneously utilize drier to be dried, and
Described dope is to use filter method according to claim 6 to carry out the dope filtering.
8. a cellulose acylate film, is characterized in that: it is being arranged between 2 Polarizers of cross Nicols configuration, and from a side irradiate light, while observing from opposite side, every 1cm 2in be of a size of that 10 μ m are above, brightness for bright spot foreign matter more than 80cd be at least below 4.
CN201410162597.XA 2013-04-24 2014-04-22 Filter, filtering method, acylate cellulose film and making method thereof CN104117230B (en)

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