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CN101027175B - Cellulose acylate film, its manufacturing method, drawn cellulose acylate film and its manufacturing method - Google Patents

Cellulose acylate film, its manufacturing method, drawn cellulose acylate film and its manufacturing method Download PDF

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Publication number
CN101027175B
CN101027175B CN2005800319340A CN200580031934A CN101027175B CN 101027175 B CN101027175 B CN 101027175B CN 2005800319340 A CN2005800319340 A CN 2005800319340A CN 200580031934 A CN200580031934 A CN 200580031934A CN 101027175 B CN101027175 B CN 101027175B
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China
Prior art keywords
film
cellulose acylate
acylate film
oriented
equal
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Expired - Fee Related
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CN2005800319340A
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Chinese (zh)
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CN101027175A (en
Inventor
大岁正明
桥本齐和
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Fujifilm Corp
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/916—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means using vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
    • B29C48/917—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means by applying pressurised gas to the surface of the flat article
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
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    • B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
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    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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    • G02B5/00—Optical elements other than lenses
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    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

An unstretched cellulose acylate film hardly breakable upon stretching can be produced by melt film forming and as a result, a highly oriented stretched cellulose acylate film can be obtained. Using an extruder with a screw compression ratio of 2.5 to 4.5 and an L/D of 20 to 50, a cellulose acylate resin is extruded into a sheet at an extrusion temperature of 190 DEG C to 240 DEG C from a die to a cooling drum, and solidified by cooling to prepare an unstretched cellulose acylate film 16, which is then stretched to produce a stretched cellulose acylate film.

Description

Cellulose acylate film and its preparation method, oriented cellulose acylate film and its preparation method
Technical field
The present invention relates to a kind of cellulose acylate film and preparation method thereof; oriented cellulose acylate film and preparation method thereof; particularly relate to a kind ofly by being melt into the not technology of oriented cellulose acylate film of film preparation, described not oriented cellulose acylate film is used to prepare the oriented cellulose acylate film with the quality that is suitable for LCD.
Background technology
Conventionally, oriented cellulose acylate film to be postponing (Re) and the delay on thickness direction (Rth) in the generation face, and put into practice by use this film as the phase shift films that is used for LCD to enlarge the visual angle.
The example of the method for oriented cellulose acylate film comprises: in the stretch method of (longitudinal stretching) of vertical (length) direction, and the method for on horizontal (width) direction, stretch (cross directional stretch) and carry out longitudinal stretching simultaneously and cross directional stretch method (while is biaxial stretch-formed).Wherein, longitudinal stretching is because its device compactness is used so far in many cases.Usually, in longitudinal stretching, at least two pairs of nip rolls, film is heated to glass transition temperature (Tg) or higher temperature, and under the transfer rate with the nip rolls of outlet side is set at situation faster than the transfer rate of the nip rolls of entrance side, stretches in the vertical.
Patent document 1 has been described the longitudinal stretching method of cellulose esters.In patent document 1, by with the side of film curtain coating is carried out longitudinal stretching in the opposite direction, can improve the angle scrambling of the axle that lags behind.Patent document 2 has been described a kind of drawing process, wherein settles in drawing zone with more than or equal to 0.3 and be equal to or less than the nip rolls of 2 length/width than the little span location of (L/W).According to patent document 2, can improve the orientation (Rth) on thickness direction.The value that length/width described herein obtains divided by the width (W) of the cellulose acylate film that will stretch than the distance (L) that is meant between the nip rolls that is used to stretch.
[patent document 1] Japanese Unexamined Patent Publication No 2002-311240
[patent document 2] Japanese Unexamined Patent Publication No 2003-315551
Yet; when the oriented cellulose acylate film that will adopt patent document 1 and 2 described method preparations is used as the phase shift films of LCD; may produce small demonstration scrambling, and as the phase shift films of LCD, the quality of this film is unsatisfactory.
The shortcoming of the conventional cellulose acylate film by being melt into film preparation is; they trend towards fracture when stretching when stretch rate increases; and when they are used as phase shift films; stretch rate can not be brought up to the level that is enough to realize postponing in the required face (Re) and the delay on thickness direction (Rth), therefore can not obtain height-oriented oriented cellulose acylate film.
The present invention considers this situation and carries out; aim to provide a kind of cellulose acylate film; by this cellulose acylate film; by by be melt into the not oriented cellulose acylate film that film preparation is ruptured hardly when stretching; can obtain height-oriented oriented cellulose acylate film; the method for preparing this cellulose acylate film, oriented cellulose acylate film and preparation method thereof.
Summary of the invention
In order to achieve the above object; the method for preparing cellulose acylate film of first aspect present invention is a kind of by being melt into the method for film preparation cellulose acylate film; this method may further comprise the steps: using the screw compression ratio is 2.5 to 4.5; L/D is 20 to 50 extruder; the through port mould is on coolant carrier; in 190 ℃ to 240 ℃ extrusion temperatures with the resin extruded one-tenth sheet material of acylated cellulose, and by this sheet material of cooling curing.
When by being melt into embrane method when preparing cellulose acylate film, the cellulose acylate film of preparation trends towards yellowing, and way therefore commonly used is to reduce the extrusion temperature of extruder.Yet; the present inventor has advanced intensive research to extrusion condition; the problem that ruptures when improving the above-mentioned stretching that will solve; and find that too low extrusion temperature causes microlite to be retained in the cellulose acylate film; this crystal hinders and stretches, thereby when stretching the cellulose acylate film of preparation the film fracture takes place easily.In addition, also find for microlite is stayed after preparation in the cellulose acylate film, with the screw compression of extruder than and L/D to be arranged on suitable level also be important.Finish the present invention based on these discoveries.
According to first aspect; because using the screw compression ratio is 2.5 to 4.5; L/D is 20 to 50 extruder; the through port mould is on coolant carrier; in 190 ℃ to 240 ℃ extrusion temperatures (outlet of extruder temperature) with the resin extruded one-tenth sheet material of acylated cellulose and by cooling curing, so can prepare a kind of cellulose acylate film that is difficult to yellowing and is not easy to cause fracture when stretching.As using in this manual, abbreviate the not oriented cellulose acylate film that is meant of " cellulose acylate film " as, and the cellulose acylate film after stretching is called " oriented cellulose acylate film ".In addition, screw compression is than the ratio of the volume of measuring unit in volume that is meant feed unit and the extruder, and L/D is the ratio of barrel diameter (D) and barrel length (L).
In order to achieve the above object, the elongation at break during ℃ uniaxial tension is equal to or greater than 50% to the cellulose acylate film of second aspect present invention in glass transition temperature Tg+10.
Second aspect defines the elongation at break of the cellulose acylate film of the phase shift films that is suitable for functional membrane such as LCD, and when at glass transition temperature Tg+10 this film of ℃ uniaxial tension, elongation at break must be equal to or greater than 50%.
In this, elongation at break is equal to or greater than 50% and is meant based on the original size before stretching, and successfully stretches more than 50% before film ruptures, and in other words, when the value defined before stretching is 1, is meant to be equal to or greater than 1.5 times.
Can prepare elongation at break by the method for first aspect and be equal to or greater than 50% cellulose acylate film.As for the method for measuring elongation at break, use is equipped with the cupping machine of heater, for example, by Toyo Seiki Co., Ltd. " the Heated Tensilon " of Zhi Zaoing, and membrane sample being heated in sample Tg+10 ℃ the stove preheating after 1 minute, is to measure elongation at break (differences before and after stretching) under 100mm/ minute the condition for 100mm and draw speed in chuck (chuck) distance.
The cellulose acylate film of third aspect present invention is the film according to second aspect; the mist degree of this film is equal to or less than 2.0%; yellowness index (YI value) be equal to or less than 10 and endothermic peak be equal to or less than 4.0J/g, this peak appears in the zone that is equal to or higher than glass transition temperature Tg in DSC (differential scanning calorimetry).
The third aspect is except that limiting above-mentioned elongation at break; also define the acylated cellulose film properties of the phase shift films that is suitable in functional membrane such as the LCD; and this film must satisfy: mist degree is equal to or less than 2.0%; yellowness index (YI value) be equal to or less than 10 and endothermic peak be equal to or less than 4.0J/g, this peak appears in the zone that is equal to or higher than glass transition temperature Tg in DSC (differential scanning calorimetry).
The cellulose acylate film that can have such optical property by the method preparation of first aspect.
The cellulose acylate film of fourth aspect present invention is that wherein the acidylate group satisfies following substitution value according to second or the film of the third aspect:
2.5≤A+B＜3.0, and
1.25≤B＜3.0
Wherein A represents degree of substitution with acetyl group, and B represents total substitution value of propiono, bytyry, valeryl and caproyl.
The cellulose acylate film that satisfies this substitution value has following characteristic; as low melting point; stretch easily and excellent moisture resistance, and they can obtain the oriented cellulose acylate film of the phase shift films that is used for functional membrane such as LCD of excellence when combining with above-mentioned performance.
The cellulose acylate film of fifth aspect present invention be according to second or fourth aspect in the film of either side, the molecular weight of this film is 20,000 to 100,000.When molecular weight is higher than at 100,000 o'clock, melt viscosity increase and thus extrusion temperature raise, it is easier of thermal degradation causes yellowing to make.When molecular weight less than 20,000 o'clock, mechanical strength when forming film descends.
For achieving the above object, the method for preparing oriented cellulose acylate film of sixth aspect present invention comprises: 1 to 2.5 times step will stretch according to the not oriented cellulose acylate film of first aspect preparation at least one direction in the vertical and horizontal of film.
The 6th aspect is the method for preparing oriented cellulose acylate film, and this method comprises the step of stretching by the cellulose acylate film of the method preparation of first aspect.The cellulose acylate film of the application of the invention, 1 to 2.5 times of possibility that becomes stretches.Therefore, can obtain the oriented cellulose acylate film of the excellent phase shift films that is used for functional membrane such as LCD.
For achieving the above object, the oriented cellulose acylate film of seventh aspect present invention is to obtain by stretching 1 to 2.5 times at least one direction in the vertical and horizontal of film according to the not oriented cellulose acylate film of either side in second to the 5th aspect.
As for the oriented cellulose acylate film of the 7th aspect, the cellulose acylate film that has the performance of either side in second to the 5th aspect by stretching is with 1 to 2.5 times of stretching possibility that becomes.Therefore, can obtain the oriented cellulose acylate film of the excellent phase shift films that is used for functional membrane such as LCD.
The cellulose acylate film of eighth aspect present invention is the film according to the 7th aspect, and the thickness of this film is 30 to 300 μ m, postpone in the face (Re) be 0 to 500nm and the delay on thickness direction (Rth) be 30 to 500nm.
Cellulose acylate film as for eight aspect; by stretching 1 to 2.5 times at least one direction in the vertical and horizontal of film; obtained to be suitable for the oriented cellulose acylate film of the phase shift films in functional membrane such as the LCD; its thickness is 30 to 300 μ m, postpone in the face (Re) be 0 to 500nm and the delay on thickness direction (Rth) be 30 to 500nm.
The cellulose acylate film of ninth aspect present invention is the film according to eight aspect, and wherein the fluctuation of the fluctuation of Re and Rth all is equal to or less than 5% on width and length direction.
As for the cellulose acylate film of the 9th aspect, by the cellulose acylate film that stretching has the performance of either side in second to the 5th aspect, the fluctuation of the Re on width and length direction and the fluctuation of Rth can drop to and be equal to or less than 5%.
A tenth aspect of the present invention is a kind of polarizer, and this polarizer comprises the not oriented cellulose acylate film of stacked one deck at least according to either side in first to the 5th aspect.The tenth is a kind of compensate film that is used for LCD panel on the one hand, and this compensate film comprises the not oriented cellulose acylate film according to either side in first to the 5th aspect as its substrate.The 12 aspect is a kind of anti-reflective film, and this anti-reflective film comprises the not oriented cellulose acylate film according to either side in first to the 5th aspect as its substrate.
A thirteenth aspect of the present invention is a kind of polarizer, and this polarizer comprises the oriented cellulose acylate film of stacked one deck at least according to either side in the 7th to the 9th aspect.The 14 aspect is the compensate film that is used for LCD panel, and this compensate film comprises the oriented cellulose acylate film according to either side in the 7th to the 9th aspect as its substrate.The 15 aspect is a kind of anti-reflective film, and this anti-reflective film comprises the oriented cellulose acylate film according to either side in the 7th to the 9th aspect as its substrate.
According to the present invention, the not oriented cellulose acylate film by preparation is ruptured when stretching hardly can obtain height-oriented oriented cellulose acylate film.
As a result, can obtain to have the oriented cellulose acylate film of excellent optical property, therefore can obtain functional membrane such as phase shift films, this film shows the orientation of height when being attached to and be used for LCD.
The accompanying drawing summary
Fig. 1 for example understand to use the structure that is used to prepare the device of film of the present invention;
Fig. 2 is the schematic diagram of explanation extruder structure;
Fig. 3 A to 3E is a table of describing the embodiment of the invention; With
Fig. 4 is a table of describing the polarizer of the embodiment of the invention.
Denotational description
10... one-tenth membrane portions
11... extruder
12... mouthful mould
14... drum cooler
16... cellulose acylate film (not stretching)
20... longitudinal stretching part
22, the 24... nip rolls
26... machine barrel
28... screw shaft
30... cross directional stretch part
31... screw thread
32... single screw rod
34... inlet
36... discharge port
40... reel-up
A... the feed unit of extruder
B... the compression unit of extruder
C... the measuring unit of extruder
Implement best mode of the present invention
The preferred embodiment of cellulose acylate film of the present invention and its preparation method, oriented cellulose acylate film and its preparation method is described referring now to accompanying drawing.
Fig. 1 schematically illustrates an example of the apparatus structure that is used to prepare oriented cellulose acylate film.
As shown in Figure 1, this device mainly by the one-tenth membrane portions 10 that is used for preparing the cellulose acylate film before stretching, be used for longitudinal stretching and become longitudinal stretching part 20, the cross directional stretch part 30 that is used for cross directional stretch and the reel-up 40 of the not oriented cellulose acylate film of membrane portions 10 preparations to constitute.
In becoming membrane portions 10, will be in extruder 11 the acylated cellulose resin through port mould 12 of fusion extrude with sheet-form and curtain coating on the drum cooler 14 of rotation, preparation is cooling and the cellulose acylate film 16 that solidifies fast.Cellulose acylate film 16 is peeled off from drum cooler 14, and transferring to longitudinal stretching part 20 is that cross directional stretch part 30 stretches then, and batches rolling in reel-up 40.Thus, prepare oriented cellulose acylate film.
Fig. 2 shows single screw extrusion machine 11.As shown in Figure 2, single screw rod 32 that will have screw thread 31 on screw shaft 28 places machine barrel 26.The acylated cellulose resin is fed in the machine barrel 26 by inlet 34 by not shown feed hopper.Machine barrel 26 is by constituting with lower unit, and these unit begin to be followed successively by from inlet 34 sides: be used for continuous feed from the feed unit of the acylated cellulose resin of inlet 34 supply (zone of representing by A), be used to mediate and compress the compression unit (zone of representing by B) of acylated cellulose resin and be used to measure the measuring unit (zone of representing by C) of the acylated cellulose resin of mediating and compressing.To in extruder 11, be continuously fed in mouthful mould by discharge port 36 by the acylated cellulose resin of fusion.
The screw compression ratio of extruder 11 is set to 2.5 to 4.5, and L/D is set to 20 to 50.Herein, screw compression is than the ratio of the volume of volume that is meant feed unit and measuring unit, promptly, (volume of feed unit A unit length) ÷ (volume of measuring unit C unit length), it is to use external diameter, the groove diameter a1 among the feed unit A and the groove diameter a2 among the measuring unit C of screw shaft 28 in the outside diameter d 1, measuring unit C of screw shaft 28 among the feed unit A to calculate.L/D is the ratio of barrel diameter (D) and barrel length (L).Extrusion temperature is set to 190 ℃ to 240 ℃.When the temperature in the extruder 11 is higher than 240 ℃, can between extruder 11 and mouthful mould 12, settle the cooling device (not shown).
The acylated cellulose resin that uses extruder 11 fusions of above-mentioned structure is continuously fed into mouthful mould 12 and extrudes on drum cooler 14, to be cooled and to solidify with sheet-form.Thus, prepare the not oriented cellulose acylate film that also will in longitudinal stretching part 20 and cross directional stretch part 30, stretch.Also can use salband to replace drum cooler 14.
The method of cellulose acylate film produced according to the present invention; since use screw compression than be 2.5 to 4.5 and L/D be 20 to 50 extruder; the through port mould is on coolant carrier; in 190 ℃ to 240 ℃ extrusion temperatures with the resin extruded one-tenth sheet material of acylated cellulose; and cooling and curing can prepare a kind of yellowing and more difficult cellulose acylate film that causes fracture when stretching of being difficult to.Cellulose acylate film prepared according to the methods of the invention not only can be used as the raw material of preparation oriented cellulose acylate film, and itself is exactly the cellulose acylate film product.
Among the present invention; extruder 11 can be single screw extrusion machine or double screw extruder; but when screw compression than much smaller than 2.5 the time; mediate may be insufficient and some parts do not dissolve yet; and because it is little to shear the heat that produces; crystal melting is insufficient, causes some small crystal to be stayed in the cellulose acylate film of preparation.In addition, sneak into bubble easily.Therefore, when stretching this cellulose acylate film, remaining crystal hinders and stretches, and makes and orientation can not be brought up to sufficiently high degree.On the other hand, when screw compression than much larger than 4.5 the time, resin has received too high shear stress, thus easily by thermal degradation, the therefore easy yellowing of cellulose acylate film of preparation.And such shearing force of crossing causes molecular breakdown, molecular weight is reduced, thereby the mechanical strength of film reduces.Therefore, for the fracture when stretching of the cellulose acylate film that suppresses yellowing and prevent to prepare, the scope of screw compression ratio is preferably 2.5 to 4.5, and more preferably 2.8 to 4.2, preferred especially 3.0 to 4.0.
In addition, when L/D much smaller than 20 the time, fusion and mediate may be insufficient, and as the situation of low compression ratio, the residual small crystal of possibility in the cellulose acylate film of preparation.On the other hand, when L/D much larger than 50 the time, the holdup time of acylated cellulose resin in extruder 11 is long, and resin is degraded easily.The long holdup time so also causes molecular breakdown, and molecular weight is reduced, thereby the mechanical strength of film reduces.Therefore, for the cellulose acylate film yellowing that suppresses to prepare with prevent fracture when stretching, L/D is 20 to 50, in preferred 22 to 45, preferred especially 24 to 40 the scope.
When extrusion temperature during far below 190 ℃, the fusing of crystal may be tended to remain in the cellulose acylate film of preparation by insufficient and small crystal.When stretching cellulose acylate film such, remaining crystal hinders and stretches, and makes and orientation can not be brought up to sufficiently high degree.When extrusion temperature during far above 240 ℃, degraded of acylated cellulose resin and yellowness (YI value) increase.Therefore, for the cellulose acylate film yellowing that suppresses to prepare with prevent fracture when stretching, the scope of extrusion temperature is 190 ℃ to 240 ℃, preferred 195 ℃ to 235 ℃, and preferred especially 200 ℃ to 230 ℃.
The cellulose acylate film of the present invention that uses extruder 11 that extrusion condition wherein is set as mentioned above to form has excellent tensile properties: when in glass transition temperature Tg+10 during ℃ uniaxial tension; elongation at break is equal to or greater than 50% (for more than 1.5 times of value before stretching); and have following characteristic value: mist degree is equal to or less than 2.0%; yellowness index (YI value) is equal to or less than 10; and endothermic peak is equal to or less than 4.0J/g, and this peak appears in the zone that is equal to or higher than glass transition temperature Tg in DSC (differential scanning calorimetry).
As using in this specification, whether low excessively mist degree be extrusion temperature index, in other words, is the index of amount of crystal that remains in the cellulose acylate film value of preparation.When mist degree greater than 2.0% the time, relatively large small crystal remains in the cellulose acylate film of preparation, thereby cellulose acylate film may fracture when stretching easily.Whether too high yellowness index (YI value) be extrusion temperature index.When yellowness index (YI value) when being equal to or less than 10, yellow degree is not a problem.As mist degree, in DSC (differential scanning calorimetry), appear at endothermic peak in the zone that is equal to or higher than glass transition temperature Tg and be the whether low excessively index of extrusion temperature.When endothermic peak during greater than 4.0J/g, relatively large small crystal remains in the cellulose acylate film of preparation, thereby cellulose acylate film may fracture when stretching easily.
The cellulose acylate film that will have such tensile property and characteristic value then stretches in longitudinal stretching part 20 and cross directional stretch part 30.
Below, the stretching step for preparing oriented cellulose acylate film by the cellulose acylate film that is stretching in into preparation in the membrane portions 10 is described.
The purpose of oriented cellulose acylate film 16 is the molecularly oriented that acidylate in the cellulose membrane 16, to postpone (Re) and the delay on thickness direction (Rth) in the generation face.Postponing Re and Rth herein, calculates by following formula.
Re(nm)＝|n(MD)-n(TD)|×T(nm)
Rth(nm)＝|{(n(MD)+n(TD))/2}-n(TH)|×T(nm)
In the formula, n (MD), n (TD) and n (TH) are respectively the refractive indexes on length direction, width and the thickness direction, and T is to be the thickness of unit with nm.
As shown in Figure 1, at first in longitudinal stretching part 20 with cellulose acylate film 16 longitudinal stretching in the longitudinal direction.In the longitudinal stretching part 20, behind preheating cellulose acylate film 16, the cellulose acylate film 16 of heat is settled around two nip rolls 22,24.The speed of the nip rolls 24 transmission cellulose acylate films 16 of outlet side is faster than the nip rolls 22 of entrance side, thus, cellulose acylate film 16 is stretched in the vertical.
Preheat temperature in the longitudinal stretching part 20 is preferably Tg-40 ℃ to Tg+60 ℃, and more preferably Tg-20 ℃ to Tg+40 ℃, further preferred Tg to Tg+30 ℃.Draft temperature in the longitudinal stretching part 20 is preferably Tg to Tg+60 ℃, and more preferably Tg+2 ℃ to Tg+40 ℃, further preferred Tg+5 ℃ to Tg+30 ℃.Stretch rate vertically is preferably 1.01 to 3 times, and more preferably 1.05 to 2.5 times, further preferred 1.1 to 2 times.
Transfer to oriented cellulose acylate film on the longitudinal direction 16 in the cross directional stretch part 30 and cross directional stretch on width.In the cross directional stretch part 30, preferably use stenter, wherein with fixing two ends and this film that stretches in the horizontal on cellulose acylate film 16 widths of clip.This cross directional stretch produces bigger delay Rth.
The preferred stenter that uses carries out cross directional stretch.Draft temperature is preferably Tg to Tg+60 ℃, and more preferably Tg+2 ℃ to Tg+40 ℃, further preferred Tg+4 ℃ to Tg+30 ℃.Stretch rate is preferably 1.01 to 3 times, and more preferably 1.05 to 2.5 times, further preferred 1.1 to 2 times.Behind cross directional stretch, can on direction of vertical and horizontal or both direction, relax.This makes the angular distribution of the hysteresis axle on the width narrow down.
As such stretching result, Re is preferably 0 to 500nm, and more preferably 10 to 400nm, and further preferred 15 to 300nm.Rth is 30 to 500nm, and more preferably 50 to 400nm, and further preferred 70 to 350nm.
Wherein, preferably satisfy those of Re≤Rth, more preferably satisfy those of (Re * 2)≤Rth.In order to realize so high Rth and low Re, preferably will go up stretched film at vertical (length direction) as mentioned above and upward stretch at horizontal (width).In other words, although the difference of the orientation on the vertical and horizontal is corresponding to postponing (Re) in the face, by except that longitudinal stretching, also in perpendicular laterally stretching, can make the difference of the orientation on the vertical and horizontal become littler, orientation (Re) becomes littler in the face thereby can make.On the other hand, because by having improved area ratio,, and can improve Rth so the orientation on thickness direction improves along with reducing of thickness except that vertical also stretching in the horizontal.
The localised waving of Re and the localised waving of Rth all preferably are equal to or less than 5% on width and length direction, more preferably be equal to or less than 4%, further preferably are equal to or less than 3%.
As mentioned above; according to this embodiment; by using cellulose acylate film to prepare oriented cellulose acylate film by the inventive method preparation; cause the film fracture when stretching hardly; high stretch rate can be realized, and the localised waving of the Re on width and the length direction and the localised waving of Rth can be reduced.Therefore, can prepare oriented cellulose acylate film with excellent optical property.
Based on described program, describe the formation of the present invention not method and the method for handling cellulose acylate film of oriented cellulose acylate film of being applicable in detail now.
(acylated cellulose resin)
The acylated cellulose that uses among the present invention preferably has following characteristic.
Cellulose acylate film, wherein the acidylate group satisfies following substitution value:
2.5≤A+B≤3.0 Hes
1.25≤B≤3.0 (A: the substitution value of acetyl group, B: total substitution value of propiono, bytyry, valeryl and caproyl).
Preferred substitution value at least 1/2 of B during for propiono is
2.6≤A+B≤2.95
2.0≤B＜2.95
And during for propiono be in the less than 1/2 of B
2.6≤A+B≤2.95
1.3≤B≤2.5。
Also preferred substitution value at least 1/2 of B during for propiono is
2.7≤A+B≤2.95
2.4≤B≤2.9
And during for propiono be in the less than 1/2 of B
2.7≤A+B≤2.95
1.3≤B≤2.0。
The invention is characterized in and set the substitution value of the acetyl group in the acyl group low, set total substitution value of propionic acid ester group, bytyry, valeryl and caproyl high simultaneously.Thus, can make stretching back Re and Rth become littler over time.This is because by increasing the amount of the group longer than acetyl group, the flexible raising and the tensile property of film can be higher, and the orientation of acylated cellulose molecule is not easy to be subjected to stretch and disturbs, thereby the Re that shows and Rth descend over time.Yet, make acyl group than above-mentioned those longer remarkable declines that cause glass transition temperature (Tg) and elastic modelling quantity, therefore not preferred.For this reason, preferably be longer than propiono, bytyry, valeryl and the caproyl of acetyl group, more preferably propiono and bytyry, further preferred bytyry.
At Migita etc., Mokuzai Kagaku has described the basic principle that is used for synthetic this acylated cellulose in 180 to 190 pages (by Kyoritsu Shuppan Co., Ltd. publishes, 1968).Typical synthetic method is to use the liquid phase acetylation of carboxylic acid anhydrides/acetate/sulfuric acid catalyst.Particularly; after using an amount of acetate that cellulosic material such as velveteen or wood pulp are carried out preliminary treatment; material is poured in advance in the mixture of carboxylic acids of cooling and makes its esterification, synthetic thus complete acylated cellulose (the acyl substituted degree sum at 2,3 and 6 is about 3.00).Above-mentioned mixture of carboxylic acids comprises acetate as solvent usually, as the carboxylic acid anhydrides of esterifying agent with as the sulfuric acid of catalyst.Usually use carboxylic acid anhydrides with the amount of stoichiometry surplus, described amount be higher than with system in the acid anhydride that exists and the cellulosic total amount of water reaction.After acylation reaction is finished; with nertralizer (for example; the carbonate of calcium, magnesium, iron, aluminium or zinc, acetate or oxide) the aqueous solution add wherein so that in system residual excess carboxylic acid acid anhydride hydrolysis and in and in system the part of residual esterification catalyst.Then; with the complete acylated cellulose that obtains a small amount of acetylation (acetizing) catalysts (it typically is residual sulfuric acid) keep 50 to 90 ℃ down, thereby make its saponification and slaking to be converted into the acyl substituted degree with needs and the acylated cellulose of the degree of polymerization.When obtaining the acylated cellulose that needs; remain in catalyst in the system by neutralizing fully with nertralizer as mentioned above; or do not having under the situation of this neutralization; the acylated cellobiose cellulose solution is poured into (perhaps water or dilute sulfuric acid is poured in the acylated cellobiose cellulose solution) in water or the dilute sulfuric acid to separate acylated cellulose, then washing and stabilization processes are to obtain acylated cellulose.
The degree of polymerization of the preferred in the present invention acylated cellulose that uses in viscometric degree of polymerization, is 200 to 700, is preferably 250 to 550, more preferably 250 to 400, be preferably 250 to 350 especially.Viscosity average polymerization degree can be measured by the inherent viscosity method of (Kazuo Uda, Hideo Saito, Journal of theSociety of Fiber Science and Technology, Japan, 18 volumes, the 1st phase, 105-120,1962) such as Uda.In Japanese Unexamined Patent Publication No 9-95538, described this method in detail.
Viscometric degree of polymerization can also be regulated by removing lower-molecular-weight component.When removing these lower-molecular-weight components, mean molecule quantity (degree of polymerization) increases, but viscosity becomes effectively and is lower than the viscosity of common acylated cellulose.By with suitable organic solvent washing acylated cellulose, can remove lower-molecular-weight component.Molecular weight can also be regulated by polymerization.For example, when preparation comprises the acylated cellulose of a small amount of lower-molecular-weight component, be preferably based on the cellulose of 100 mass parts, the amount of the sulfuric acid catalyst in the acetylization reaction is adjusted to 0.5 to 25 mass parts.Be set to this scope by amount, can synthesize and have preferred molecular weight distribution the acylated cellulose of (molecular weight distribution uniformly) sulfuric acid catalyst.
Acylated cellulose for using in the present invention uses such acylated cellulose, and its weight average molecular weight Mw/ number-average molecular weight Mn ratio is preferably 1.5 to 5.5, and more preferably 2.0 to 5.0, preferred especially 2.5 to 5.0, most preferably 3.0 to 5.0.
Can use these acylated celluloses separately or with two or more form of mixtures.Can also use the mixture that wherein correspondingly mixes the high molecular component except that acylated cellulose.As the high molecular component that will mix, preferably have those of high-compatibility, and when forming film, transparency preferably is not less than 80%, more preferably is not less than 90%, further preferably is not less than 92% with cellulose esters.
In the present invention, by plasticizer is joined in the acylated cellulose, can reduce the crystalline melt temperature (Tm) of acylated cellulose.Molecular weight to the plasticizer that uses among the present invention is not particularly limited, and plasticizer can be low-molecular-weight or HMW.The example of this plasticizer comprises phosphorous acid esters, alkyl phthalyl base Glycolic acid Arrcostab, carboxylate and polyol fatty acid ester.Plasticizer can be solid or oily mater.That is, fusing point and the boiling point to plasticizer is not particularly limited.When carrying out the fusion film forming, especially preferably use non-volatile plasticisers.
The instantiation of phosphate comprises triphenyl phosphate, tributyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, trioctyl phosphate, tri naphthyl phosphate, tricresyl phosphate (dimethylbenzene) ester, the adjacent biphenyl ester of tricresyl phosphate, tricresyl phosphate phenyl ester, ODPP, phosphoric acid biphenyl diphenyl ester and phosphatase 11,4-phenylene-four phenyl ester.In addition, can use phosphate plasticizer described in the claim of announcing in the country of international patent application no 6-501040 3 to 7.
The example of alkyl phthalic acyl group Glycolic acid Arrcostab comprises methyl phthalyl Glycolic acid methyl esters; ethyl phthalylethyl glycolate; propyl group phthalyl Glycolic acid propyl ester; BPBG; octyl group phthalyl Glycolic acid monooctyl ester; methyl phthalyl ethyl glycolate; ethyl phthalyl Glycolic acid methyl esters; ethyl phthalyl Glycolic acid propyl ester; methyl phthalyl Glycolic acid butyl ester; ethyl phthalyl Glycolic acid butyl ester; butyl phthalyl Glycolic acid methyl esters; butyl phthalyl Glycolic acid ethyl ester; propyl group phthalyl Glycolic acid butyl ester; butyl phthalyl Glycolic acid propyl ester; methyl phthalyl Glycolic acid monooctyl ester; ethyl phthalyl Glycolic acid monooctyl ester; octyl group phthalyl Glycolic acid methyl esters and octyl group phthalyl Glycolic acid ethyl ester.
The example of carboxylate comprises phthalic acid ester, as repefral, diethyl phthalate, dibutyl phthalate, dioctyl phthalate and di (2-ethylhexyl) phthalate; Citrate is as citric acid acetyl three methyl esters, acetyl triethyl citrate and acetyl tributyl citrate; Adipate ester is as dimethyl adipate, dibutyl adipate, diisobutyl adipate, adipic acid two (the 2-ethyl is own) ester, diisodecyl adipate (DIDA) and adipic acid two (butyldiglycol) ester; The aromatic polycarboxylic acid ester is as tetraoctyl 1,2,4,5-benzenetetra-carboxylate and trioctyl trimellitate (TOTM); Aliphatic multi-carboxylate is as dibutyl adipate, dioctyl adipate, dibutyl sebacate, di-n-octyl sebacate, ethylazelaate, dibutyl azelate and dioctyl azelate; Polyol fatty acid ester is as glyceryl triacetate, tetraacethyl two glyceride, acetylation glyceride, monoglyceride and diglyceride.In addition, can be used alone or in combination butyl oleate, MAR, dibutyl sebacate or triacetin.
The other example of this plasticizer comprises: high molecular weight plasticizer, as the aliphatic polyester that constitutes by dihydroxylic alcohols and binary acid, as polyethylene glycol adipate, poly adipate succinic acid ester, polydiethylene glycol succinate and polybutylene succinate; The aliphatic polyester that constitutes by hydroxycarboxylic acid such as PLA and polyglycolic acid; The aliphatic polyester that is made of lactone is as polycaprolactone, poly-propiolactone and poly-valerolactone; And polyvinyl, as polyvinylpyrrolidone.These plasticizer can use separately or with monomerics.
Polyol plasticiser has the excellent compatibility with cellulose fatty acid ester; and have significant thermoplasticity and give effect; the example comprises glyceride compounds such as glyceride and two glyceride; PAG such as polyethylene glycol and polypropylene glycol, and wherein acyl group is attached to compound on the hydroxyl of PAG.
The instantiation of glyceride includes but not limited to: the glycerin diacetate stearate, the glycerin diacetate palmitate, the glycerin diacetate myristinate, the glycerin diacetate laurate, the glycerin diacetate decylate, the glycerin diacetate pelargonate, the glycerin diacetate caprylate, the glycerin diacetate heptanoate, the glycerin diacetate capronate, the glycerin diacetate valerate, the glycerin diacetate oleate, the glyceryl acetate dicaprate, the glyceryl acetate dipelargonate, the glyceryl acetate dicaprylate, glyceryl acetate two heptanoates, glyceryl acetate two capronates, glyceryl acetate two valerates, the glyceryl acetate dibutyrate, glycerine dipropionate decylate, glycerine dipropionate laurate, glycerine dipropionate myristinate, glycerine dipropionate palmitate, glycerine dipropionate stearate, glycerine dipropionate oleate, glycerin tributyrate, phocenin, the glycerine monopalmitate, glyceryl monostearate, glycerol distearate, glycerine propionic ester laurate and glyceryl oleate propionic ester.These can be used alone or in combination.
Wherein, preferably glycerine diacetate esters caprylate, glycerin diacetate pelargonate, glycerin diacetate decylate, glycerin diacetate laurate, glycerin diacetate myristinate, glycerin diacetate palmitate, glycerin diacetate stearate, glycerin diacetate oleate.
The instantiation of two glyceride includes but not limited to: the nitration mixture ester of two glycerine, as two glycerine tetracetates, two glycerine, four propionic esters, two glycerine, four butyrates, two glycerine, four valerates, two glycerine, four capronates, two glycerine tetraheptanoates, two glycerine, four caprylates, two glycerine, four pelargonates, two glycerine, four decylates, two glycerine cinnamic acid in April esters, two glycerine, four myristinates, two glycerine, four palmitates, two glycerol triacetate propionic esters, two glycerol triacetate butyrates, two glycerol triacetate valerates, two glycerol triacetate capronates, two glycerol triacetate heptanoates, two glycerol triacetate caprylates, two glycerol triacetate pelargonates, two glycerol triacetate decylates, two glycerol triacetate laurates, two glycerol triacetate myristinates, two glycerol triacetate palmitates, two glycerol triacetate stearates, two glycerol triacetate oleates, two glycerin diacetate dipropionates, two glycerin diacetate dibutyrates, two glycerin diacetates, two valerates, two glycerin diacetates, two capronates, two glycerin diacetates, two heptanoates, two glycerin diacetate dicaprylates, two glycerin diacetate dipelargonates, two glycerin diacetate dicaprates, two glycerin diacetate dilaurates, two glycerin diacetates, two myristinates, two glycerin diacetate dipalmitates, two glycerin diacetate distearates, two glycerin diacetate dioleates, two monoacetin tripropionates, two monoacetins, three butyrates, two monoacetins, three valerates, two monoacetins, three capronates, two monoacetins, three heptanoates, two monoacetins, three caprylates, two monoacetins, three pelargonates, two monoacetins, three decylates, two monoacetin trilaurins, two monoacetins, three myristinates, two monoacetin tripalmitates, two monoacetin tristearates, two monoacetin trioleates, Rikemal L 71D, two stearines, two glycerol caprylates, two glycerine myristate esters and two glyceryl oleates.These can be used alone or in combination.
Wherein, preferred two glycerine tetracetates, two glycerine, four propionic esters, two glycerine, four butyrates, two glycerine, four caprylates and two glycerine cinnamic acid in April esters.
The instantiation of PAG comprises, but is not limited to have the polyethylene glycol and the polypropylene glycol of 200 to 1000 mean molecule quantity, and these can be used alone or in combination.
The instantiation that wherein acyl group is attached to the compound on the hydroxyl of PAG includes, but are not limited to the polyoxyethylene acetic acid esters; the polyoxyethylene propionic ester; Polyoxyethylene butyrate; the polyoxyethylene valerate; the polyoxyethylene capronate; the polyoxyethylene heptanoate; the polyoxyethylene caprylate; the polyoxyethylene pelargonate; the polyoxyethylene decylate; polyoxyethylene laurate; the polyoxyethylene myristinate; the polyoxyethylene palmitate; Myrj 45; polyoxyethylene oleate; the polyoxyethylene linoleate; the polyoxypropylene acetic acid esters; the polyoxypropylene propionic ester; the polyoxypropylene butyrate; the polyoxypropylene valerate; the polyoxypropylene capronate; the polyoxypropylene heptanoate; the polyoxypropylene caprylate; the polyoxypropylene pelargonate; the polyoxypropylene decylate; the polyoxypropylene laurate; the polyoxypropylene myristinate; the polyoxypropylene palmitate; the polyoxypropylene stearate; polyoxypropylene oleate and polyoxypropylene linoleate.These can be used alone or in combination.
The addition of plasticizer is 0 to 20 weight %, and more preferably 2 to 18 weight % most preferably are 4 to 15 weight %.When the content of plasticizer was higher than 20 weight %, although improved the thermal fluidity of acylated cellulose, plasticizer may be exuded on the surface of the film that forms by fusion, and shows that stable on heating glass transition temperature Tg may reduce.
In addition, in case of necessity, can be in the limit of not damaging the performance that needs, will be used for preventing that thermal degradation or painted stabilizing agent from joining in the acylated cellulose that the present invention uses.
As stabilizing agent, can use phosphite (phosphite) compound, bi-ester of phosphite, phosphate, thiophosphate, weak organic acid or epoxide separately, perhaps two or more mixing with them adds.As the instantiation of phosphites stabilizers, can preferably use the compound of in Japanese Unexamined Patent Publication No 2004-182979 [0023] to [0039] section, describing.As the instantiation of bi-ester of phosphite, can use the compound of in Japanese Unexamined Patent Publication No 51-70316,10-306175,57-78431,54-157159 and 55-13765, describing.
Stabilizing agent is 0.005 to 0.5 weight % based on the addition of acylated cellulose among the present invention, more preferably 0.01 to 0.4 weight %, more preferably 0.05 to 0.3 weight %.When described amount during, in being melt into membrane process, prevent to degrade and painted effect deficiency, thereby this scope is not preferred less than 0.005 weight %.When described amount greater than 0.5% the time, stabilizing agent may be exuded on the surface of the cellulose acylate film that forms by fusion, thus this scope is not preferred.
In addition, can preferably add anti-degradation agent and antioxidant.When adding phenolic compounds, sulfide compound or phosphorus compound as anti-degradation agent or antioxidant, the anti-degraded and the antiopxidant effect that can obtain working in coordination with.Other example as other stabilizing agent can preferably use " Kokai Giho of JapanInstitute of Invention ﹠amp; Innovation " (Kogi No.2001-1745, publish March 15 calendar year 2001, Japanese Institute of Invention; Innovation) material of describing in detail in the 17-22 page or leaf.
The acylated cellulose of Shi Yonging can comprise ultraviolet protective agent in the present invention, and can add one or more ultra-violet absorbers.As the ultra-violet absorber that is used for liquid crystal, preferred those ultra-violet absorbers: from the viewpoint of the degraded that prevents liquid crystal, it has the ultraviolet excellent ability that absorbing wavelength is equal to or less than 380nm, and from the viewpoint of the display performance of liquid crystal, its hardly absorbing wavelength be equal to or greater than the visible light of 400nm.The example comprises hydroxyl benzophenone cpd, benzotriazole cpd, salicylate compound, benzophenone cpd, alpha-cyanoacrylate ester compounds and nickel complex salt compound.Particularly preferred ultra-violet absorber comprises benzotriazole cpd and benzophenone cpd.Wherein, preferred benzotriazole cpd is because cellulose esters acylated cellulose unnecessary painted few for example.
Preferred ultra-violet absorber comprises 2,6-di-t-butyl-paracresol, [3-(3 for pentaerythrite base-four, 5-di-t-butyl-4-hydroxyphenyl) propionic ester], triethylene glycol-two [3-(the 3-tert-butyl group-5-methyl-4-hydroxyphenyl) propionic ester], 1, [3-(3 for 6-hexylene glycol-two, 5-two-tert-butyl group-4-hydroxyphenyl) propionic ester], 2,4-two (positive hot sulfenyl)-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1,3, the 5-triazine, 2,2-sulfo--diethylidene two [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-acrinyl) benzene and three-(3,5-di-t-butyl-4-acrinyl)-isocyanuric acid ester.
In addition, preferred 2,6-di-t-butyl-paracresol, pentaerythrite base-four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], triethylene glycol-two [3-(the 3-tert-butyl group-5-methyl-4-hydroxyphenyl) propionic ester].In addition, can use hydrazine matal deactivator such as N together, N '-two [3-(3,5-di-t-butyl-4-hydroxyphenyl) propiono] hydrazine, or phosphorus is handled stabilizing agent as three (2, the 4-di-tert-butyl-phenyl) phosphite ester.Based on cellulose esters, acylated cellulose for example, the addition of these compounds is preferably 1ppm to 3.0 quality %, more preferably 10ppm to 2 quality %.
As these ultra-violet absorbers, can use following commercially available product.
The example of benzotriazole UV absorbers comprise TINUBIN P (Ciba SpecialtyChemicals K.K.), TINUBIN 234 (Ciba Specialty Chemicals K.K.), TINUBIN320 (Ciba Specialty Chemicals K.K.), TINUBIN 326 (Ciba SpecialtyChemicals K.K.), TINUBIN 327 (Ciba Specialty Chemicals K.K.), TINUBIN328 (Ciba Specialty Chemicals K.K.) and Sumisorb 340 (Sumitomo ChemicalCo., Ltd.).The example of benzophenone UV-absorber comprise Seesorb 100 (SHIPRO KASEIKAISHA LTD.), Seesorb 101 (SHIPRO KASEI KAISHA LTD.), Seesorb 101S (SHIPRO KASEI KAISHA LTD.), Seesorb 102 (SHIPRO KASEI KAISHALTD.), Seesorb 103 (SHIPRO KASEI KAISHA LTD.), ADK STAB LA51 (ASAHI DENKA CO., LTD.), Chemisorp 111 (CHEMIPRO KASEI KAISHALTD.) and UVINUL D-49 (BASF).The example of oxanilide (oxalic acid anilide) ultra-violet absorber comprises TINUBIN 312 (Ciba Specialty Chemicals K.K.) and TINUBIN 315 (Ciba Specialty Chemicals K.K.).In addition, as the salicylic acid ultra-violet absorber, Seesorb201 (SHIPRO KASEI KAISHA LTD.) and Seesorb 202 (SHIPRO KASEIKAISHA LTD.) are commercially available, and the example of cyanoacrylate ultra-violet absorber comprises Seesorb 501 (SHIPRO KASEI KAISHA LTD.) and UVINUL N-539 (BASF).
Among the present invention, oriented cellulose acylate film and oriented cellulose acylate film preferably do not have following Re and Rth.
That is, not oriented cellulose acylate film of the present invention preferably satisfies following various Re and Rth:
0≤Re≤20
0≤Rth≤80，
More preferably
0≤Re≤15
0≤Rth≤70，
Further preferred
0≤Re≤10
0≤Rth≤60。
Oriented cellulose acylate film of the present invention preferably satisfies following various Re and Rth:
0≤Re≤500
30≤Rth≤500，
More preferably
10≤Re≤400
50≤Rth≤400，
Further preferred
15≤Re≤300
70≤Rth≤350。
(fusion film forming)
(1) drying
Although can use the acylated cellulose resin, more preferably use the pelletizing resin to reduce the varied in thickness of the film that forms with powder type.
Be adjusted in moisture and be equal to or less than 1%, more preferably be equal to or less than 0.5% the acylated cellulose resin.Further preferably be equal to or less than after 0.1%, this resin be incorporated in the loading hopper of extruder.At this moment, feed hopper temperature is set in Tg-50 ℃ to Tg+30 ℃, more preferably Tg-40 ℃ to Tg+10 ℃, further preferred Tg-30 ℃ to Tg.This prevents that the moisture in the loading hopper from adsorbing again, and can easily reach the efficient of above-mentioned drying.In addition, dehydration air or inert gas (for example, nitrogen) can be incorporated in the loading hopper.
(2) mediate and extrude
Mediate with at 190 ℃ to 240 ℃, more preferably 195 ℃ to 235 ℃, further preferred 200 ℃ to 230 ℃ molten resins.In this stage, melt temperature can be constant, perhaps will control being divided under the situation of some parts.The kneading time is preferably 2 to 60 minutes, and more preferably 3 to 40 minutes, more preferably 4 to 30 minutes.In addition, can flow in inertia in the extruder under (nitrogen etc.), perhaps under the situation that use is equipped with the extruder of air vent to vacuumize, mediate.
(3) curtain coating
Make fusion acylated cellulose resin by gear pump to eliminate pulsation from extruder 11, filter with metal cloth filter, and be expressed on the drum cooler 14 with sheet-form by the T-shape mouth mould 12 of linking the filter back.Can use the form extrusion resin of branch manifold mouth mould or feed head (feed block) mouthful mould with single or multiple lift.At this moment, by adjusting the antelabium interval of mouthful mould, can be controlled at the thickness offset on the width.
Then, with resin extruded to drum cooler 14.In this stage, use electrostatic coating method, air knife method, air compartment method, vacuum nozzle method or touch roll method, can be increased in drum cooler 14 and melt extrude adhesiveness between the sheet material.Can carry out this adhesiveness raising processing to the sheet material that melt extrudes of all or part (for example, only at two ends).
The temperature of drum cooler 14 is preferably 60 ℃ to 160 ℃, and more preferably 70 ℃ to 150 ℃, further preferred 80 ℃ to 140 ℃.Then this sheet material is peeled off and batched by nip rolls 22,24 and stenter from drum cooler 14.Batch speed and be preferably 10 to 100m/ minutes, more preferably 15 to 80m/ minutes, further preferred 20 to 70m/ minutes.
The width of the film that forms is 1 to 5m, and more preferably 1.2 to 4m, further preferred 1.3m to 3m.The thickness of thus obtained not oriented cellulose acylate film is preferably 30 μ m to 400 μ m, more preferably 40 μ m to 300 μ m, further preferred 50 μ m to 200 μ m.
Preferred prune the two ends of thus obtained cellulose acylate film 16 and on winding unit 40, once batch.With prune the sheet crushing that the back produces carry out granulation, depolymerization as required or again polymerization with once more as of the same race or different types of acylated cellulose membrane material.In addition, consider to prevent scar, preferably before batching, laminated film is coated at least one surface.
The glass transition temperature of thus obtained cellulose acylate film (Tg) is preferably 70 ℃～180 ℃, and more preferably 80 ℃～160 ℃, further preferred 90 ℃～150 ℃.
(processing of cellulose acylate film)
The cellulose acylate film that will form by said method is according to said method single shaft or biaxial stretch-formed, the preparation oriented cellulose acylate film.This film can use separately, perhaps uses with the polarizer combination, perhaps can form liquid crystal layer thereon, has the layer (antiradar reflectivity layer) or the hard conating of controllable refractive index.Can realize these structures according to following method.
(1) surface treatment
By cellulose acylate film is carried out surface treatment, can improve the adhesiveness between this film and each functional layer (for example, priming coat and back sheet).Can use for example glow discharge processing, ultraviolet irradiation, sided corona treatment, flame treatment and acid or alkali treatment.It can be 10 that glow discharge is in the case handled -3To the following cold plasma that produces of the low pressure of 20Torr, perhaps also preferred plasma treatment under atmospheric pressure.Plasma exciatiaon gas refers to can excite the gas into plasma under condition as mentioned above, and the example comprises argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, CFC such as tetrafluoromethane and their mixture.At " Kokai Giho of Japan Institute ofInvention ﹠amp; Innovation " (Kogi No.2001-1745, publish March 15 calendar year 2001, JapanInstitute of Invention; Innovation) in the 30-32 page or leaf these details have been described.Just causing in the plasma treatment under atmospheric pressure of concern at present, under 10 to 1000Kev condition, using 20 to 500Kgy irradiation energy, and more preferably under 30 to 500Kev condition, using 20 to 300Kgy irradiation energy.
In these were handled, special preferred bases saponification was handled.
In the alkali soap processing, can or it can be coated with saponification liquor (rubbing method) (infusion process) in this film immersion saponification liquor.Can finish infusion process as follows: making film was 10 to 14 the NaOH or the groove of the KOH aqueous solution by holding pH in 0.1 to 10 minute, and the described aqueous solution is heated to 20 ℃ to 80 ℃, is neutralization subsequently, washing and dry.
For rubbing method, can use dip-coating, curtain coating, extrusion coated, blade coating and the coating of E type.As the solvent that is used for alkali soap processing coating fluid, the following solvent of preferred selection, described solvent has and is suitable for saponification liquor is coated to excellent wetability on the transparent carrier, and can keep the surface of good state, and does not produce irregular on the surface of transparent carrier.Particularly, preferred alcohols solvent, and preferred especially isopropyl alcohol.In addition, can use aqueous surfactant solution as solvent.As the alkali that is used for the alkali soap coating fluid, preferably dissolve in those alkali in the above-mentioned solvent, and more preferably KOH and NaOH.The pH of saponification coating fluid preferably is not less than 10, more preferably is not less than 12.For the reaction condition of alkali soapization, reaction can be carried out in room temperature, lasts preferred 1 second to 5 minutes, and more preferably 5 seconds to 5 minutes, preferred especially 20 seconds to 3 minutes.After the alkali soap reaction, can water, or wash the surface that scribbles saponification liquor then with water with acid.Handle with the coating of the alignment films of describing after a while and can carry out continuously by the saponification of coating, reduce number of steps thus.In for example Japanese Unexamined Patent Publication No 2002-82226 and WO 02/46809, these method for saponification have been specifically described.
Can also form priming coat with the adhesion work ergosphere.Can after above-mentioned surface treatment or under, form these layers by coating without any the surface-treated situation.At " Kokai Giho of JapanInstitute of Invention ﹠amp; Innovation " (Kogi No.2001-1745, publish March 15 calendar year 2001, Japan Institute of Invention; Innovation) details of priming coat has been described in 32 pages.
These surface treatment step and primary coat step can be included in the final stage of film forming procedure, can independently carry out, and perhaps can carry out in the process that applies the following function layer.
(coating of functional layer)
Cellulose acylate film of the present invention can be used with the functional layer of describing in following document: " Kokai Giho of Japan Institute of Invention ﹠amp; Innovation " (Kogi No.2001-1745, publish March 15 calendar year 2001, Japan Institute of Invention; Innovation) 32-45 page or leaf.Especially preferably apply polarization layer (polarizer), layer of compensation (compensating plate) or anti-reflecting layer (anti-reflective film).
(A) coating of polarization layer (preparation of polarizer)
The thickness of the diaphragm of polarizing coating (layer) is preferably 25 to 350 μ m, more preferably 30 to 200 μ m, further preferred 40 to 120 μ m.When with cellulose acylate film of the present invention during, can use in unstretching film or the stretched film any as the diaphragm of polarizing coating.Oriented cellulose acylate film of the present invention can be used as the diaphragm of polarizing coating, and is preferably used as retardation compensation film.
The polarizer that obtains can have structure as described below:
Polaroid A: oriented cellulose acylate film/polarizing coating/FUJITAC not
Polarizer B: the oriented cellulose acylate film of oriented cellulose acylate film/polarizing coating/not
Polarizer C: oriented cellulose acylate film/polarizing coating/FUJITAC
Polarizer D: the oriented cellulose acylate film of oriented cellulose acylate film/polarizing coating/not
Polarizer E: oriented cellulose acylate film/polarizing coating/oriented cellulose acylate film
(A-1) material of Shi Yonging
Current, commercially available polarization layer prepares usually by the following method: strained polymer is immersed in the iodine or dichroic dye solution in the groove, thereby iodine or dichroic dye are penetrated in the adhesive.As polarizing coating, can also use typically the application type polarizing coating that can obtain from Optiva Inc..In polarizing coating, iodine or dichroic dye are orientated to show polarization characteristic in adhesive.As dichroic dye, can use azo dyes, stilbene dye, pyrazolone dye, triphenhlmethane dye, quinoline dye, oxazine dye, thiazine dye or anthraquinone dye.And preferred water dissolubility dichroic dye.This dichroic dye preferably comprises hydrophilic substituent (for example sulfo group, amino or hydroxyl).The example is included in " Kokai Giho of Japan Institute of Invention ﹠amp; Innovation " the compound of describing in (KogiNo.2001-1745, March 15 calendar year 2001 publish) 58 pages.
As the adhesive that is used for polarizing coating, can use self can be crosslinked polymer, crosslinked polymer or their combination in the presence of crosslinking agent.The example of adhesive is included in methacrylate copolymer, styrol copolymer, polyolefin, polyvinyl alcohol, modified polyvinylalcohol, poly-(N hydroxymethyl acrylamide), polyester, polyimides, vinyl acetate copolymer, carboxymethyl cellulose and the Merlon of describing in [0022] section of specification of Japanese Unexamined Patent Publication No 8-338913.Can use silane coupler as this polymer.Wherein, the preferred water soluble polymer (for example, poly-(N hydroxymethyl acrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol and modified polyvinylalcohol), more preferably gelatin, polyvinyl alcohol and modified polyvinylalcohol, and most preferably polyvinyl alcohol and modified polyvinylalcohol.Especially preferably use the polyvinyl alcohol or the modified polyvinylalcohol of two kinds of different polymerization degrees.This polyvinyl alcohol preferably have be preferably 70 to 100%, 80 to 100% saponification degree more preferably.The degree of polymerization of polyvinyl alcohol is preferably 100 to 5,000.The example of modified polyvinylalcohol has been described in Japanese Unexamined Patent Publication No 8-338913,9-152509 and 9-316127.Two or more polyvinyl alcohol or modified polyvinylalcohol can be used together.
The lower limit of the thickness of adhesive is preferably 10 μ m.For the upper limit of described thickness, from the viewpoint that the light of LCD leaks, described adhesive is preferably thin as far as possible.The described adhesive preferably thickness (about 30 μ m) than present commercially available polarizer is thinner, more preferably is equal to or less than 25 μ m, further preferably is equal to or less than 20 μ m.
The adhesive that can be used in polarizing coating is crosslinked.Polymer or monomer with crosslinkable functionality can be mixed with adhesive, perhaps crosslinkable functionality directly can be added on the binder polymer.Can change making adhesive crosslinked by light, heat or pH, can form adhesive then with cross-linked structure.In the number of issuing 23297 crosslinking agent has been described again at United States Patent (USP).In addition, can use boron compound (for example, boric acid and borax) as crosslinking agent.The binding agent based amount of amount that joins the crosslinking agent in the adhesive is preferably 0.1 to 20 quality %.In this scope, the orientation of polarizer and the humidity resistance of polarizing coating are improved.
After cross-linking reaction was finished, the amount of unreacted crosslinking agent preferably was not higher than 1.0 quality %, more preferably no higher than 0.5 quality %.This makes can improve weatherability.
(A-2) stretching of polarization layer
Preferably polarizing coating is stretched (pulling method) or friction (rubbing manipulation), then with iodine or dichroic dye dyeing.
In pulling method, the stretch rate of this film is preferably 2.5 to 30.0 times, more preferably 3.0 to 10.0 times.Can stretch by the dry method tension under air or wherein with the water-immersed wet method stretching of film.Stretch rate in dry method tension is preferably 2.5 to 5.0 times, and the stretch rate in wet method stretches is preferably 3.0 to 10.0 times.Can be with machine direction parallel drawing (parallel drawing) or (the tiltedly stretching) film that stretches obliquely.Stretching can be carried out once or several times.By stretching several times, even when stretching with high stretch rate, this film equably also can stretch.
A) parallel drawing
Before stretching, make PVA film swelling.Its swellbility (based on before swelling and after the ratio of film weight) be 1.2 to 2.0 times.Then, film is shifted continuously by deflector roll etc., and at the groove that holds aqueous medium or hold in the staining trough of dichroic material of dissolving and stretch, the groove temperature is preferably 15 ℃ to 50 ℃, more preferably 17 ℃ to 40 ℃.By the fixing film and setting under the situation of rate travel greater than the rate travel of the nip rolls of front of nip rolls of back of two pairs of nip rolls, can stretch.From the viewpoint of above-mentioned effect and advantage, stretch rate, promptly after stretching/length ratio (following identical) of starting stage, be preferably 1.2 to 3.5 times, more preferably 1.5 to 3.0 times.Then, with described film 50 ℃ to 90 ℃ dryings to obtain polarizing coating.
B) tiltedly stretch
For this stretching, can use the use in Japanese Unexamined Patent Publication No 2002-86554, the described drawing process of outstanding stenter in an inclined direction.Because under air, carry out this stretching, this film must be carried out hydration in advance so that stretch.Moisture is preferably 5% to 100%, and more preferably 10% to 100%.
Temperature when stretching is preferably 40 ℃ to 90 ℃, more preferably 50 ℃ to 80 ℃.Humidity is preferably 50%rh to 100%rh, more preferably 70%rh to 100%rh, further preferred 80%rh to 100%rh.Translational speed in the vertical preferably was not less than 1m/ minute, more preferably was not less than 3m/ minute.After stretching is finished, preferably at 50 ℃ to 100 ℃, more preferably carry out drying at 60 ℃ to 90 ℃, last preferred 0.5 to 10 minute, more preferably 1 to 5 minute.
The angle of the absorption axes of the polarizing coating that obtains thus is preferably 10 to 80 degree, and more preferably 30 to 60 degree further preferably are essentially 45 degree (40 to 50 degree).
(A-3) adhere to
Adhere to the preparation polarizer with the saponification cellulose acylate film with by the polarization layer that stretching prepares.For the direction that adheres to, preferably their are adhered to and make the direction of curtain coating axle of cellulose acylate film and the tensile axis direction of polarizer form miter angle.
The adhesive that is used to adhere to is not particularly limited, and the example comprises PVA resin (comprising the PVA with acetoacetyl, sulfonic acid, carboxyl or oxyalkylene group modification), and comprise the aqueous solution of boron compound.Wherein, preferred especially PVA resin.Adhesive phase has after drying and is preferably 0.01 to 10 μ m, is preferably the thickness of 0.05 to 5 μ m especially.
The polarizer that obtains thus preferably has higher light transmittance and the degree of polarization of Geng Gao.To wavelength is the light of 550nm, and the light transmittance of described polarizer is being preferably 30 to 50%, more preferably 35 to 50%, most preferably be in 40 to 50% the scope.For wavelength is the light of 550nm, and its degree of polarization is being preferably 90 to 100%, more preferably 95 to 100%, and most preferably in 99 to 100% the scope.
The polarizer that obtains thus and λ/4 are slice stacked to produce circularly polarized light.In this case, they are stackedly made that the angle between the absorption axes of the phase retardation axle of λ/4 slice and polarizer is 45 degree.λ/4 of using in this manual slice are not particularly limited, but preferably have those of the more little wavelength dependency of the short more delay of wavelength.In addition, the preferred use: tilt the in the vertical polarizing coatings of 20 to 70 degree and the optical anisotropic layer of making by liquid-crystal compounds of absorption axes wherein by the following λ that constitutes/4.
(B) coating of layer of compensation (preparation of compensating plate)
Layer of compensation is the liquid-crystal compounds of compensation in liquid crystal cells when LCD shows black, and prepare by forming alignment films and apply optical anisotropic layer thereon on cellulose acylate film.
(B-1) alignment films
On above-mentioned surface-treated cellulose acylate film, form alignment films.Described alignment films has the function of the differently-oriented directivity that limits liquid crystal molecule.Yet, in case liquid-crystal compounds is oriented and subsequently alignment state be fixed, this alignment films is a primary element of the present invention no longer just, because described function is accomplished.In other words, can also be transferred to polarizer by the optical anisotropic layer with fixed orientation attitude that only will on alignment films, form and prepare polarizer of the present invention.
Can form alignment films in the following way: for example, the friction treatment of organic compound (preferred polymers), the oblique evaporation of inorganic compound, have micro-recesses layer formation or according to gather (the LB film) of the organic compound (for example ω-tricosanic acid, two (octadecyl) ammonio methacrylate and methyl stearate) of Langmuir-Blodgett method.In addition, by applying electric field, applying magnetic field or the alignment films by realizing the orientation function with light irradiation is known.
Preferably form alignment films by polymer being carried out friction treatment.In principle, the polymer that is used for alignment films has the molecular structure that can make liquid crystal molecular orientation.
In the present invention, except that the function that makes liquid crystal molecular orientation, can also (for example, two keys) side chain be attached in the main chain, perhaps can will the crosslinkable functionality of liquid crystal molecular orientation is incorporated in the side chain with containing crosslinkable functionality.
The polymer that is used for alignment films can be the polymer that self can be crosslinked, crosslinked polymer in the presence of crosslinking agent, or their combination.The example of these polymer is included in methacrylate copolymer, styrol copolymer, polyolefin, polyvinyl alcohol, modified polyvinylalcohol, poly-(N hydroxymethyl acrylamide), polyester, polyimides, vinyl acetate copolymer, carboxymethyl cellulose and the Merlon of describing in Japanese Unexamined Patent Publication No 8-338913's [0022] section.Can use silane coupler as this polymer.Wherein, the preferred water soluble polymer (for example, poly-(N hydroxymethyl acrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol and modified polyvinylalcohol), more preferably gelatin, polyvinyl alcohol and modified polyvinylalcohol, and most preferably polyvinyl alcohol and modified polyvinylalcohol.Especially preferably use the polyvinyl alcohol or the modified polyvinylalcohol of two kinds of different polymerization degrees.This polyvinyl alcohol preferably have be preferably 70 to 100%, 80 to 100% saponification degree more preferably.The degree of polymerization of polyvinyl alcohol is preferably 100 to 5,000.
Side chain with the function that makes liquid crystal molecular orientation contains hydrophobic group usually as functional group.Based on the kind of liquid crystal molecule and the alignment state that needs, determine the concrete kind of these functional groups.Can introduce the modification group of modified polyvinylalcohol by copolymerization, chain transfer or block polymerization.The modification examples of groups comprises alkyl, thioether group, polymerizable groups (unsaturated polymerizable group, epoxy radicals, aziridinyl) and the alkoxysilyl (trialkoxysilyl, dialkoxy silicyl, monoalkoxy silicyl) that hydrophilic group (carboxyl, sulfonic group, phosphonate group (phosphonic group), amino, ammonium, acylamino-, mercapto), the alkyl that contains 10 to 100 carbon atoms, fluorine replace.At Japanese Unexamined Patent Publication No 2000-155216,0022 to 0145 section and Japanese Unexamined Patent Publication No 2002-62426 have described the instantiation of these modified polyvinylalcohols in 0018 to 0022 section.
Be attached in the main chain of alignment films polymer by the side chain that allows to have crosslinkable functionality, the crosslinkable functionality that perhaps will have the function that makes liquid crystal molecular orientation is incorporated in the side chain, can make alignment films polymer and the polyfunctional monomer combined polymerization that comprises in optical anisotropic layer.As a result, not only polyfunctional monomer self, and alignment films polymer self, and in addition polyfunctional monomer and alignment films polymer by covalent bond combination securely.Therefore, by crosslinkable functionality being incorporated in the alignment films polymer, can significantly improve the intensity of compensating plate.
The same with polyfunctional monomer, the crosslinkable functionality of alignment films polymer preferably comprises polymerizable groups.At Japanese Unexamined Patent Publication No 2000-155216, its instantiation has been described in 0080 to 0100 section.Can use crosslinking agent, and, make the alignment films crosslinked polymer not only by above-mentioned crosslinkable functionality.
The example of this crosslinking agent comprises aldehyde, N-methylol compound ， dioxane derivatives, the compound that works when activated carboxylic, active vinyl-compound, active halogen compound ， isoxazole and dialdehyde starch.Can be used in combination two or more crosslinking agent.Its instantiation is included in Japanese Unexamined Patent Publication No 2002-62426, the compound of describing in 0023 to 0024 section.Preferred high activity aldehyde, particularly glutaraldehyde.
The addition of crosslinking agent is preferably 0.1 to 20 quality % based on the amount of polymer, more preferably 0.5 to 15 quality %.The amount of remaining unreacted crosslinking agent preferably is not more than 1.0 quality % in alignment films, more preferably no more than 0.5 quality %.By in this scope, regulating this amount, even alignment films long-time use or indwelling for a long time under high temperature and high humility atmosphere in LCD also can obtain enough durability under the situation that does not produce net.
Can form alignment films basically by the following method: will comprise the solution of above-mentioned polymer, and promptly be used to form the material of alignment films and the solution of crosslinking agent and be coated on the transparent substrates, and, and carry out friction treatment by heat drying (crosslinked).As mentioned above, can carry out cross-linking reaction described solution being coated to any stage later on the transparent substrates.When using water-soluble polymer such as polyvinyl alcohol when being used to form the material of alignment films, coating fluid is preferably the organic solvent (for example, methyl alcohol) with froth breaking effect and the mixture of water.Water is preferably 0: 100 to 99: 1 to the mass ratio of methyl alcohol, more preferably 0: 100 to 91: 9.This prevents that foam from producing and can significantly reduce defective in alignment films, therefore reduces the lip-deep defective at optical anisotropic layer.
As the method for coating alignment films, preferred spin coating, dip-coating, curtain coating, extrusion coated, rod is coated with and roller coat, and wherein, preferred especially rod is coated with.Film thickness is preferably 0.1 to 10 μ m after drying.Can carry out drying by heating 20 ℃ to 110 ℃ temperature.Crosslinked fully in order to realize, baking temperature is preferably 60 ℃ to 100 ℃, is preferably 80 ℃ to 100 ℃ especially.Be generally 1 minute to 36 hours drying time, be preferably 1 to 30 minute.In addition, the crosslinking agent for using can be adjusted to optimum value with pH, and when using glutaraldehyde as crosslinking agent, pH is preferably 4.5 to 5.5, and preferred especially 5.0.
Alignment films is placed on above-mentioned transparent carrier or the priming coat.By making above-mentioned polymeric layer crosslinked, then friction treatment is carried out on the surface of described layer, can obtain alignment films.
For friction treatment, can use the method that is widely used in the liquid crystal aligning that makes LCD.More specifically, can make with the following method: the surface of wherein using paper, gauze, felted terxture, rubber, nylon or polyester fiber friction orientation film on fixed-direction is to obtain orientation.Usually, this is to carry out on the friction film surface for several times by the cloth of evenly transplanting with the fiber of equal length and diameter on it.
When on commercial scale, implementing this production, contact by the transmission film that spin friction roller and polarization layer have been adhered on it, carry out friction treatment.The circularity of friction roller, cylindricity and deviation (eccentricity) all preferably are equal to or less than 30 μ m.The cornerite of the relative friction roller of film (wrap angle) is preferably 0.1 to 90 °.Yet,, can also realize stable friction more than 360 ° by film is reeled around roller as described in the Japanese Unexamined Patent Publication No 8-160430.The translational speed of film is 1 to 100m/min.For angle of friction, select suitable angle of friction in from 0 to 60 ° the scope.When using described film in LCD, angle of friction is preferably 40 to 50 °, is preferably 45 ° especially.
The alignment films that obtains thus has the film thickness that is preferably 0.1 to 10 μ m.
Then, the liquid crystal molecule in the optical anisotropic layer is orientated on alignment films.Subsequently, the polyfunctional monomer that allows to comprise in alignment films polymer and the optical anisotropic layer reacts, and perhaps uses crosslinking agent to make the alignment films crosslinked polymer as required.
The liquid crystal molecule that is used for 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 HMW liquid crystal or combinations of low molecular weight liquid crystals, and can comprise that wherein to make combinations of low molecular weight liquid crystals crosslinked, thereby do not have liquid crystal liquid crystal property those.
(B-2) rod shaped liquid crystal molecule
As rod shaped liquid crystal molecule, preferred azomethine class, azoxy compound, the cyanobiphenyl class used, cyano-phenyl ester class, benzoates, cyclohexane-carboxylic acid phenylester class, cyano-phenyl cyclohexanes, the phenyl pyrimidine class that cyano group replaces, phenyl pyrimidine class, Ben Ji dioxane, tolans (tolan) compound and alkenyl cyclohexyl benzonitrile class that alkoxyl replaces.
Rod shaped liquid crystal molecule can be a metal complex.Can also use the liquid crystal polymer that in repetitive, comprises rod shaped liquid crystal molecule as rod shaped liquid crystal molecule.In other words, rod shaped liquid crystal molecule can be attached in (liquid crystal) polymer.
At Survey of Chemistry by the editor of Japanization association (1994), quarterly, 22 volumes, " Chemistry of Liquid Crystal ", 4th, 7 and 11 chapters, promote " the Liquid Crystal Device Handbook " that 142 committees of association edit with Japanese science, described rod shaped liquid crystal molecule in the 3rd chapter.
The birefringence of rod shaped liquid crystal molecule is preferably in 0.001 to 0.7 scope.For the fixed orientation attitude, rod shaped liquid crystal molecule can comprise polymerizable groups.Described polymerizable groups is preferably the unsaturated group of free redical polymerization or the group of cationically polymerizable.Its instantiation is included in Japanese Unexamined Patent Publication No 2002-62427, polymerizable groups and the polymerisable liquid crystal compound described in 0064 to 0086 section.
(B-3) discotic liquid-crystalline molecules
The example of plate-like (dish shape) liquid crystal molecule is included in C.Destrade etc., Mol.Cryst.71 volume, the benzene derivative of describing in the research report of 111 pages (1981); At C.Destrade etc., Mol.Cryst.122 volume, the research report and the Phyicslett. of 141 pages (1985), A, 78 volumes, three polyindenes (truxene) derivative of describing in 82 pages (1990); At B.Kohne etc., Angew.Chem.Soc.96 volume, the cyclohexane derivant of describing in the research report of 70 pages (1984); With at J.M.Lehn etc., J.Chem.Commun., the research report of 1794 pages (1985) and J.Zhang etc., J.Am.Chem.Soc.116 volume, the aza-crown (azacrown) or the big ring of phenylacetylene of description in the research report of 2655 pages (1994).
As discotic liquid-crystalline molecules, comprise that also the benzoyloxy of wherein straight chained alkyl, alkoxyl, replacement constitutes the liquid-crystal compounds of side chain, these groups exist as the substituting group that the parent nucleus that is positioned at the branch subcenter directly makes progress.Preferably wherein molecule or molecular cluster have rotational symmetry, thereby can produce the compound of certain orientation.For the optical anisotropic layer that forms by discotic liquid-crystalline molecules, the compound that finally comprises in optical anisotropic layer is not to be necessary for discotic liquid-crystalline molecules, and can comprise for example following compound, wherein make the low-molecular-weight discotic liquid-crystalline molecules polymerization that comprises the group that heat or light are reacted or crosslinked, thereby molecular weight increases and the liquid crystal liquid crystal property forfeiture.The preferred embodiment of discotic liquid-crystalline molecules has been described in Japanese Unexamined Patent Publication No 8-50206.The polymerization of discotic liquid-crystalline molecules has been described in Japanese Unexamined Patent Publication No 8-27284 specification (describes).
For by the fixing discotic liquid-crystalline molecules of polymerization, must be attached on the disc-shaped core of discotic liquid-crystalline molecules as substituent polymerizable groups.Preferred wherein by the compound of linking group in conjunction with disc-shaped core and polymerizable groups, and adopt this structure, even in polymerisation, also can keep alignment state.This examples for compounds is included in Japanese Unexamined Patent Publication No 2000-155216, the compound of describing in 0151 to 0168 section.
In hybrid orientation, the angle between the plane of the main shaft (dish plane) of discotic liquid-crystalline molecules and polarizing coating along with depth direction at optical anisotropic layer on distance from the polarizing coating plane increase and increase or reduce.Described angle preferably reduces when described distance increases.In addition, may changing of angle comprises the interrupted variation that increases continuously, reduces continuously, intermittently increases, intermittently reduces, comprises the variation that increases continuously and reduce continuously and comprise increase and reduce.In interrupted the variation, there is wherein indeclinable zone on thickness direction, inclination angle.For this angle,, can there be the wherein indeclinable zone of angle as long as angle increases on the whole or reduces.In addition, described angle preferably is continually varying on the whole.
Usually the material by selecting discotic liquid-crystalline molecules or the material of oriented layer perhaps by selecting rubbing method, can be controlled at the mean direction of main shaft of the discotic liquid-crystalline molecules of polarizing coating side.Usually by the material of the additive selecting discotic liquid-crystalline molecules or use with discotic liquid-crystalline molecules, can be controlled at the direction of the main shaft (dish plane) of the discotic liquid-crystalline molecules of face side (air side).The example of the additive that uses with discotic liquid-crystalline molecules comprises plasticizer, surfactant, polymerisable monomer and polymer.In addition, by selecting the kind of discotic liquid-crystalline molecules and additive as mentioned above, can be controlled at the intensity of variation on the differently-oriented directivity of main shaft.
(B-4) component of other in optical anisotropic layer
Plasticizer, surfactant or polymerisable monomer can be used orientation characteristic of uniformity, film strength and the liquid crystal molecule of filming etc. with raising with above-mentioned liquid crystal molecule.Preferred these components can compatiblely with described liquid crystal molecule make them can change the inclination angle of liquid crystal molecule or not hinder orientation.
The example of polymerisable monomer can be the compound of free redical polymerization or cationically polymerizable, and be preferably can with the polyfunctional monomer of the free redical polymerization of the above-mentioned liquid-crystal compounds combined polymerization that comprises polymerizable groups.The example is included in Japanese Unexamined Patent Publication No 2002-296423, those that describe in 0018 to 0020 section.The addition of described compound based on the amount of discotic liquid-crystalline molecules usually in the scope of 1 to 50 quality %, in the scope of preferred 5 to 30 quality %.
Described surfactant can be conventional known compound, but preferred especially fluorochemical.Its instantiation is included in Japanese Unexamined Patent Publication No 2001-330725, the compound of describing in 0028 to 0056 section.
Preferably the polymer that uses with discotic liquid-crystalline molecules can play a effect in the inclination angle that changes discotic liquid-crystalline molecules.
The example of this polymer is a cellulose esters.At Japanese Unexamined Patent Publication No 2000-155216, the preferred embodiment of cellulose esters has been described in 0178 section.For fear of the orientation that hinders liquid crystal molecule, the addition of polymer based on the amount of liquid crystal molecule preferably in the scope of 0.1 to 10 quality %, more preferably in the scope of 0.1 to 8 quality %.
Transition temperature from dish shape nematic liquid crystal to solid phase is preferably 70 to 300 ℃, more preferably 70 to 170 ℃.
(B-5) formation of optical anisotropic layer
Be coated on the alignment films by the coating fluid that will comprise liquid crystal molecule and following polymerization initiator in case of necessity or optional components, can form optical anisotropic layer.
As the solvent that is used to prepare described coating fluid, preferably with an organic solvent.The example of this organic solvent comprises that acid amides (for example, N, dinethylformamide), sulfoxide (for example, methyl-sulfoxide), heterocyclic compound (for example, pyridine), hydrocarbon (for example benzene, hexane), alkyl halide (for example chloroform, carrene, tetrachloroethanes), ester (for example methyl acetate, butyl acetate), ketone (for example acetone, methyl ethyl ketone) and ether (for example oxolane, 1,2-dimethoxy-ethane).Wherein, preferred alkyl halogen and ketone.Two or more organic solvent can be used together.
Can apply described coating fluid by known method (for example coiling rod coating, extrusion coated, direct intaglio printing coating, reverse gravure coating and mouthful pattern coating).
Optical anisotropic layer has and is preferably 0.1 to 20 μ m, and 0.5 to 15 μ m more preferably most preferably is the thickness of 1 to 10 μ m.
(B-6) the liquid crystal molecular orientation attitude is fixing
Can be at the liquid crystal molecule that keeps fixed orientation under the situation of alignment state.Preferably fix by polymerisation.This polymerisation comprises heat polymerization that uses thermal polymerization and the photopolymerization reaction that uses Photoepolymerizationinitiater initiater, and the preferred light polymerisation.
The example of Photoepolymerizationinitiater initiater comprises that the alpha-carbonyl compound is (at U.S. Patent number 2,367,661 and 2,367, described in 670), acyloin ether is (at U.S. Patent number 2,448,828 describe), the aromatics acyloin compound that α-hydrocarbon replaces (at U.S. Patent number 2,722,512 describe), the multinuclear naphtoquinone compounds is (at U.S. Patent number 3,046, describe in 127 and 2,951,758), the combination of triarylimidazoles dimer and p-aminophenyl ketone is (at U.S. Patent number 3,549, describe in 367), acridine or compound phenazine (in Japanese Unexamined Patent Publication No 60-105667 and U.S. Patent number 4,239,850) Yi is described Ji the oxadiazole compound (at U.S. Patent number 4, describe in 212,970).
The use amount of Photoepolymerizationinitiater initiater based on the solid constituent in the coating fluid be preferably 0.01 to 20 quality %, more preferably in the scope of 0.5 to 5 quality %.
For using so that the light irradiation of polymerizable liquid crystal molecule preferably uses ultraviolet light.
Irradiation energy is being preferably 20mJ/cm 2To 50J/cm 2, more preferably 20 to 5,000mJ/cm 2, also preferred 100 to 800mJ/cm 2Scope in.In order to promote photopolymerization reaction, can under heating, carry out light irradiation.
Can on optical anisotropic layer, form protective layer.
Can also be preferably with this compensate film and polarization layer combination.Particularly, the coating fluid that is used for optical anisotropic layer as mentioned above is coated on the surface of polarizing coating to form optical anisotropic layer.Therefore, do not using between polarizing coating and the optical anisotropic layer under the situation of any polymer film, can prepare the little thin polarizer of stress (strain * cross-sectional area * elastic modelling quantity) that the change in size of polarizing coating wherein causes.When being attached to polarizer of the present invention in the large scale liquid crystal display, can showing image, and not cause problem as the light leakage with high display quality.
For the inclination angle between polarization layer and layer of compensation, preferably stretching makes described inclination angle and the angle coupling between the axis of homology of two polarizers on the both sides that adhere to the liquid crystal cells that constitutes LCD and liquid crystal cells vertical or horizontal.Described inclination angle is generally 45 °, but has developed wherein inclination angle not always 45 ° transmission, reflection and semi-transmission LCD recently, therefore it is desirable to and can arbitrarily adjust draw direction according to the design of LCD.
(B-7) LCD
To the liquid crystal mode that wherein uses this compensate film be described.
(TN mode LCD)
This pattern is widely used in the colored TFT LCD most, and in many publications its description is arranged.For the alignment state in the liquid crystal cells in the TN pattern that shows black, with the core arranged vertical of rod shaped liquid crystal molecule in the unit, and this molecule is horizontal near unit substrate.
(ocb mode liquid crystal display)
In this pattern, liquid crystal cells is in the curved orientation pattern, wherein the rod shaped liquid crystal molecule in the upper and lower basically on the contrary (symmetrically) orientation.At U.S. Patent number 4,583, the LCD that uses this curved orientation mode liquid crystal unit is disclosed in 825 and 5,410,422.Because the rod shaped liquid crystal molecule in the upper and lower is a symmetric orientation, so curved orientation mode liquid crystal unit has from optical compensation function.Therefore, this pattern is also referred to as OCB (optical compensation curved) liquid crystal mode.
For the alignment state of the ocb mode liquid crystal unit that shows black, as in the TN pattern, with the core arranged vertical of rod shaped liquid crystal molecule in the unit, and this molecule is horizontal near unit substrate.
(VA mode LCD)
This pattern is characterised in that rod shaped liquid crystal molecule is substantially vertically arranged when not applying voltage.VA mode liquid crystal unit comprises: the VA mode liquid crystal unit of (1) narrow sense, wherein rod shaped liquid crystal molecule is substantially vertically arranged when not applying voltage, and their substantial horizontal are arranged (describing) in Japanese Unexamined Patent Publication No 2-176625 when applying voltage; (2) be in the liquid crystal cells of pattern (MVA pattern), in this pattern, the VA pattern changed into the multidomain pattern to enlarge visual angle (at SID97, Digest oftech.Papers (pre-prints) describes in 28 (1997), 845); (3) be in the liquid crystal cells of pattern (n-ASM pattern), wherein rod shaped liquid crystal molecule is substantially vertically arranged when not applying voltage, and when applying voltage they in multidomain aligned twisted (at Preprints of Symposium on JapaneseLiquid Crystal Society, (1998), describe among the 58-59); (4) be in the liquid crystal cells (announce) of SURVAIVAL pattern in LCD International 98.
(IPS mode LCD)
This pattern is characterised in that the rod shaped liquid crystal molecule substantial horizontal is arranged in the plane when not applying voltage, and by changing the liquid crystal arrangement direction by applying or do not apply voltage, carries out switch.Particularly, can use 2004-12731,2004-215620,2002-221726, those that describe among 2002-55341 and the 2003-195333 at Japanese Unexamined Patent Publication No 2004-365941.
(other LCD)
For ECB and STN pattern, can realize optical compensation based on method same as described above.
(C) coating of anti-reflecting layer (anti-reflective film)
Usually prepare anti-reflective film by the following method: on transparent substrates, form also serve as the low-index layer of stain-proofing layer and at least one deck wherein refractive index be higher than layer (that is, the high refractive index layer or the medium refractive index layer) of the refractive index of described low-index layer.
Forming wherein, the method for the multilayer film of the inorganic compound of stacked different refractivity (metal oxide etc.) transparent membrane comprises chemical vapor deposition (CVD) method, physical vapor deposition (PVD) method and following method: with metallic compound such as metal alkoxide by sol-gal process to form the film of colloidal metallic oxide particle, subsequently by post processing (ultraviolet irradiation of in Japanese Unexamined Patent Publication No 9-157855, describing, or the plasma treatment of in Japanese Unexamined Patent Publication No 2002-327310, describing) to form film.
On the other hand, as large-duty anti-reflective film, the various anti-reflective films that form by the stacked film that is scattered in the inorganic particle in the matrix have been proposed.
Can also use the anti-reflective film that contains anti-reflecting layer, described anti-reflective film is by forming the fine irregular anti-dazzle property that is endowed in the superiors of the anti-reflective film for preparing according to above-mentioned coating process.
Although any in the said method can be used for cellulose acylate film of the present invention, preferred especially rubbing method (coating type).
(C-1) the layer structure of coating type anti-reflective film
Design has the anti-reflective film as lower floor's structure, wherein forms medium refractive index layer, high refractive index layer and low-index layer (outermost layer) in the following order on substrate at least, so that this film has the refractive index that satisfies following relation:
The refractive index of the refractive index＞low-index layer of the refractive index＞transparent substrates of the refractive index＞medium refractive index layer of high refractive index layer.
Can between transparent substrates and medium refractive index layer, form hard conating.Described anti-reflective film can be made of medium refractive index hard conating, high refractive index layer and low-index layer.
The example of this layer structure has been described in Japanese Unexamined Patent Publication No 8-122504,8-110401,10-300902,2002-243906 and 2000-111706.In addition, these layers can have other function, and the example of these layers comprises low-index layer with soil resistance and the high refractive index layer with antistatic property (for example, Japanese Unexamined Patent Publication No 10-206603,2002-243906).
Anti-reflective film has and preferably is not more than 5%, the mist degree more preferably no more than 3%.Measured according to the pencil hardness test of JIS K5400 as passing through, film strength preferably is equal to or higher than H, more preferably is equal to or higher than 2H, and most preferably is equal to or higher than 3H.
(C-2) high refractive index layer and medium refractive index layer
The high refractive index layer of anti-reflective film is to comprise average particle size particle size at least to be equal to or less than the high index of refraction inorganic compound ultra-fine grain of 100nm and the curable film of matrix binder.
The inorganic compound ultra-fine grain of high index of refraction can be the inorganic compound with the refractive index that is not less than 1.65, preferably is not less than 1.9.The example of inorganic compound comprises the oxide of Ti, Zn, Sb, Sn, Zr, Ce, Ta, La or In and the composite oxides that comprise these metallic atoms.
Can form this ultra-fine grain by the following method: for example, (for example use surface conditioning agent, silane coupler, Japanese Unexamined Patent Publication No 11-295503,11-153703 and 2000-9908, perhaps anionic compound or organic metal coupling agent, Japanese Unexamined Patent Publication No 2001-310432) handles particle surface, (for example form nucleocapsid structure that high refractive index particle wherein constitutes nuclear, Japanese Unexamined Patent Publication No 2001-166104), the dispersant that perhaps uses appointment together (for example, Japanese Unexamined Patent Publication No 11-153703, U.S. Patent number 6,210,858B1 and Japanese Unexamined Patent Publication No 2002-2776069).
The material that constitutes matrix can be conventionally known thermoplastic resin or curable resin films.
Described material is preferably at least a composition that is selected from the following composition: comprise the composition of polyfunctional compound, described polyfunctional compound contains the group of at least two free redical polymerizations and/or the group of cationically polymerizable; The composition that comprises the organo-metallic compound of hydrolyzable groups and comprise its partial condensate.The example is included in the compound of describing among Japanese Unexamined Patent Publication No 2000-47004,2001-315242,2001-31871 and the 2001-296401.
The also preferred curable film that uses the colloidal metal oxide preparation that obtains from the hydrolytic condensate and the metal alkoxide compositions of metal alkoxide.For example, this film has been described among the Japanese Unexamined Patent Publication No 2001-293818.
Described high refractive index layer has and is generally 1.70 to 2.20 refractive index and is preferably 5nm to 10 μ m, the more preferably thickness of 10nm to 1 μ m.
The refractive index of adjusting medium refractive index layer makes it between the refractive index of the refractive index of low-index layer and high refractive index layer.Medium refractive index layer has and is preferably 1.50 to 1.70 refractive index.
(C-3) low-index layer
Low-index layer is layered on the high refractive index layer.Low-index layer has 1.20 to 1.55, is preferably 1.30 to 1.50 refractive index.
Be preferably formed this layer as outermost layer with resistance to marring and soil resistance.As the means that are used to significantly improve resistance to marring, giving the surface is effectively with slip, and can use conventionally known passing through to introduce the method for siloxanes or fluorine formation thin layer.
The refractive index of fluorochemical is preferably 1.35 to 1.50, and more preferably 1.36 to 1.47.Preferably comprise the fluorine atom of 35 to 80 quality % and the compound of crosslinkable or polymerizable functional group.
This examples for compounds is included in Japanese Unexamined Patent Publication No 9-222503,0018 to 0026 section; Japanese Unexamined Patent Publication No 11-38202,0019 to 0030 section; Japanese Unexamined Patent Publication No 2001-40284,0027 to 0028 section; With describe among the Japanese Unexamined Patent Publication No 2000-284102 those.
As silicone compounds, preferably in polymer chain, have polysiloxane structure, and comprise curable functional group or polymerizable functional group, thereby in film, form the silicone compounds of cross-linked structure.The example comprises active siloxanes (for example, Silaplane (can obtain from CHISSO CORPORATION) and comprise the polysiloxanes (Japanese Unexamined Patent Publication No 11-258403) of silanol group at two ends.
Preferably when coating comprises the outermost coating composition of being used to form of polymerization initiator and sensitizer or thereafter, by light irradiation or by heating, carry out this crosslinked or polymerisation that comprises the fluoropolymer and/or the siloxane polymer of crosslinkable or polymerizable groups.
In addition, also preferred sols gel solidification film wherein in the presence of catalyst, makes organo-metallic compound such as silane coupler solidify with the silane coupler that comprises specific fluorine-containing alkyl by condensation reaction.The example comprises silane compound or its partial hydrolysis condensation product (compound of describing) that comprises Polyfluoroalkyl in Japanese Unexamined Patent Publication No 58-142958,58-147483,58-147484,9-157582,11-106704; With the silyl compound (compound of describing among Japanese Unexamined Patent Publication No 2000-117902,2001-48590 and the 2002-53804) that comprises as poly-(perfluoroalkyl ethers) base of long chain fluorine-containing group.
Except that said components, low-index layer can also comprise additive, (for example, has the low-refraction inorganic compound of 1 to 150nm average primary particle size, as filler as silica (silica) and fluorine-containing particle (magnesium fluoride, calcirm-fluoride, barium fluoride); At Japanese Unexamined Patent Publication No 11-3820; [0020] organic fine particles of describing to [0038] section; Silane coupler; Lubricant and surfactant.
When low-index layer is placed in outermost, can passes through vapor phase method (vacuum vapor deposition, sputter, ion plating or plasma CVD) and form low-index layer.Preferably form low-index layer, because can cheaply produce by coating.Low-index layer has and is preferably 30 to 200nm, and more preferably 50 to 150nm, and most preferably is 60 to 120nm film thickness.
(C-4) hard conating
On the surface of transparent carrier, form hard conating to give anti-reflective film with physical strength.Especially, preferably between transparent carrier and high refractive index layer, form hard conating.
Preferably by photocurable or thermal curable compound are carried out cross-linking reaction or polymerisation formation hard conating.
Curable functional group is preferably the functional group of photopolymerization, and the organo-metallic compound that comprises hydrolyzable functional group is preferably the organoalkoxysilane based compound.
The instantiation of these compounds with in the situation of high refractive index layer, enumerate those are identical.The instantiation that constitutes the composition of hard conating is included in those that describe among Japanese Unexamined Patent Publication No 2002-144913,2000-9908 and the WO 0/46617.
High refractive index layer can also serve as hard conating.This layer is to use the technology of describing in the part of high refractive index layer, form in the hard conating by disperseing molecule subtly and they being incorporated into.By the particle that adding has the average particle size particle size of 0.2 to 10 μ m, hard conating can also serve as the antiglare layer (describing after a while) with anti-dazzle function.
Can suitably design the thickness of hard conating according to application target.Hard conating has and is preferably 0.2 to 10 μ m, the more preferably film thickness of 0.5 to 7 μ m.Measured according to the pencil hardness test of JIS K5400 as passing through, the intensity of hard conating preferably is equal to or higher than H, more preferably is equal to or higher than 2H, and most preferably is equal to or higher than 3H.In addition, after the Taibo test according to JIS K5400, the wearing and tearing of sample are the smaller the better.
(C-5) forward scattering layer
Settle the forward scattering layer when being attached to film in the LCD, increasing the visual angle, and make the visual angle upwards, downwards, and be tilted to the right left.By disperse the particulate of different refractivity in hard conating, the forward scattering layer can also have the function of hard conating.
The example of this layer comprises those (the Japanese Unexamined Patent Publication No 11-38208) with particular forward scattering coefficient, wherein the relative index of refraction of transparent resin and particulate in particular range those (Japanese Unexamined Patent Publication No 2000-199809) and have those (Japanese Unexamined Patent Publication No 2002-107512) that are not less than 40% regulation haze value.
(C-6) other layer
Except that above-mentioned layer, anti-reflecting layer can also have at the end (primer) layer, antistatic layer, priming coat or protective layer.
(C-7) coating process
According to dip-coating, airblade coating, curtain coating, roller coat, the coating of coiling rod, intaglio coating, the coating of miniature intaglio and extrusion coated (at U.S. Patent number 2,681,294 in describe), can form the layer of anti-reflective film by coating.
(C-8) anti-dazzle function
Anti-reflective film can have anti-dazzle function with the light of scattering from the outside.Can obtain anti-dazzle function by on the surface of anti-reflective film, forming scrambling.When anti-reflective film had anti-dazzle function, the haze value of anti-reflective film was preferably 3 to 30%, more preferably 5 to 20% and most preferably be 7 to 20%.
As the method that on the surface of anti-reflective film, forms scrambling, can use any method that can keep this irregular surface profile satisfactorily.For example, wherein particulate is used for low-index layer on the film surface, to form the method (for example, Japanese Unexamined Patent Publication No 2000-271878) of scrambling; Larger particles (particle size: 0.05 to 2 μ m) add in the layer (high refractive index layer, medium refractive index layer or hard conating) that will below low-index layer, form with a small amount of (0.1 to 50 quality %), the film that has irregular surface with formation, under the situation that keeps surface configuration, form the method (for example, Japanese Unexamined Patent Publication No 2000-281410,2000-95893,2001-100004 and 2001-281407) of low-index layer then thereon; And comprise coating the superiors' (stain-proofing layer), then with the method (for example, the embossing method among Japanese Unexamined Patent Publication No 63-278839,11-183710 and 2000-275401s described) of scrambling physical transfer to its surface.
Below the measuring method of using among the present invention will be described.
The method of measure R e and Rth
With sample film the humidity regulation of 5 ℃ temperature and 60%rh at least 3 hours.Use automatic birefringence analyzer (KOBRA-21ADH/PR, make by Oji Science Instruments), at 25 ℃ and 60%rh, the wavelength of 550nm is measured length of delay on the direction on vertical sample film surface and the direction with respect to membrane plane normal slope ± 40 °.By postponing (Re) in the value calculating face on the vertical direction, and by with tilt delay (Rth) on the measured value calculated thickness direction on ± 40 ° the direction of vertical direction.
Re on Re, Rth, length direction and the width and the fluctuation of Rth
(1) MD sampling
On the length direction of film, go out 100 1 square centimeter sheet with the cut-space of 0.5m.
(2) TD sampling
Go out 50 1 square centimeter sheet with uniform cut-space by the whole width of film.
(3) measurement of Re and Rth
With sample film the humidity regulation of 5 ℃ temperature and 60%rh at least 3 hours.Use automatic birefringence analyzer (KOBRA-21ADH/PR, make by Oji Science Instruments), at 25 ℃ and 60%rh, the wavelength of 550nm is measured length of delay on the direction on vertical sample film surface and the direction with respect to membrane plane normal slope ± 40 °.By postponing (Re) in the value calculating face on the vertical direction, and by with tilt delay (Rth) on the measured value calculated thickness direction on ± 40 ° the direction of vertical direction.
The mean value of all sample points is defined as Re and Rth respectively.
(4) fluctuation of Re and Rth
The difference of 100 points in the vertical and the maximum of 50 points transversely and minimum of a value is represented divided by separately mean value and with percentage, is defined as the fluctuation of Re and the fluctuation of Rth.
Elongation at break when stretching with Tensilon
Using by Toyo Seiki Co., Ltd. the Tensilon of the heating of Zhi Zaoing, with sample preheating after 1 minute in the Tg+10 that is heated to each sample ℃ stove, be that the stretching sample is measured elongation at break until fracture under 100mm/ minute the condition in the chuck distance for 100mm and draw speed.
The substitution value of acylated cellulose
According to the method for in Carbohydr.Res.273 (1995) 83-91 (Tezuka etc.), describing, use the acyl substituted degree in the 13C-NMR measurement acylated cellulose.
DSC
The DSC-50 that use is made by Shimadzu Corporation measures the calorie J/g at the endothermic peak place that occurs immediately with calculating, and simultaneously, measures Tg behind Tg at 10 ℃/minute programming rate.
Mist degree
Use is by Nippon Denshoku Industries Co., and the TurbidimeterNDH-1001DP that Ltd. makes measures mist degree.
Yellowness index (YI value)
According to JIS K7105 6.3, use Z-II OPTICAL SENSOR to measure yellow degree (YI: yellowness index).
The yellow degree of pellet is measured by method for reflection, and under the situation of film, measures three simulations (stimulus) value by transmission method, adopts these values, calculates the YI value according to following formula.
YI＝{(1.28X-1.06Z)/Y}×100
The YI value of each film that will calculate by following formula converts it into the value of every 1mm divided by the thickness of film, and the value that relatively obtains.
Molecular weight
Membrane sample is dissolved in the carrene and by the gpc measurement molecular weight.
[embodiment]
[acylated cellulose resin]
The acylated cellulose with different acyl and different degree of substitution of preparation shown in the table 1 of Fig. 3 A to 3E.Particularly, add sulfuric acid (is 7.8 weight portions based on 100 weight portion celluloses), and add carboxylic acid, carry out acylation reaction at 40 ℃ as the acyl substituted based raw material as catalyst.Based on the kind and the amount of carboxylic acid, the kind and the substitution value of control acyl group.After acidylate, will obtain thing 40 ℃ of slakings.Determine the degree of polymerization of the acylated cellulose obtain thus by the following method, and be shown in the table of Fig. 3 A to 3E.
(measuring the method for the degree of polymerization)
With the acylated cellulose of the accurate weighing bone dry of amount of about 0.2g, and it is dissolved in carrene: in the 100ml mixed solvent of ethanol=9: 1 (mass ratio).Use the Ostwald viscosimeter, at the Drain time of 25 ℃ of measurement mixtures by second, and according to the following formula calculating degree of polymerization.
ηrel＝T/T0
[η]＝(1nηrel)/C
DP＝[η]/Km
T: measure the Drain time of sample by second
T0: independent solvent is by the Drain time of second
C: concentration (g/l)
Km：6×10 -4
Measure the Tg of these resins by the following method and be shown in the table of Fig. 3 A to 3E.For wherein adding those of plasticizer, demonstration be to add the value of measuring behind the plasticizer.
(measurement of Tg)
The 20mg sample is put into the DSC dish.Sample is flowed down at nitrogen, be heated to 250 ℃ (for the first time strokes) from 30 ℃, be cooled to 30 ℃ with-10 ℃/minute then with 10 ℃/minute.Then, sample is heated to 250 ℃ (strokes for the second time) once more from 30 ℃.In second time stroke, the temperature that baseline begins to depart from low temperature side is defined as glass transition temperature (Tg), and it is presented in the table of Fig. 3 A to 3E.In addition, the silicon dioxide microparticle (AEROSIL R972V) with 0.05 quality % joins in all samples.
[fusion film forming]
It is that 3mm and length are the cylindrical pellets of 5mm that above-mentioned acylated cellulose is formed diameter.At this moment, mix from those (the table of Fig. 3 A to 3E, showing) middle selection plasticizer of description after a while and with itself and pellet.To obtain thing 110 ℃ of dryings in vacuum desiccator, and be equal to or less than after 0.1%, be introduced in the loading hopper that is adjusted to Tg-10 ℃ in the control moisture.In the table of Fig. 3 A to 3E, TPP: triphenyl phosphate, BDP: phosphoric acid biphenyl diphenyl ester, DOA: adipic acid two (the 2-ethyl is own) ester, PTP:1,4-phenylene-tetraphenylphosphonium acid esters.
Regulate melt temperature and make that melt viscosity is 1000Pa.s, and use the single screw extrusion machine 11 fusion pellets that are set in 210 ℃.If the T-mouth mould 12 by being adjusted to melt temperature is extruded fused materials and is being adjusted on Tg-5 ℃ the drum cooler 14 with sheet-form, and by cooling curing, forms cellulose acylate film.In this stage, each sample is used electrostatic coating method (from the 10kV wire of the placement of the melt landing point 10cm on drum cooler 14).The sheet material that solidifies is peeled off and batched.Before will batching, prune two ends (respectively be overall width 3%), and thicken processing (annular knurl) with the width that reaches 10mm and the height of 50 μ m.With all width is that 1.5m, length are that the sample of 3000m batched with 30m/ minute.
[stretching]
, stretch under temperature of in the table of Fig. 3 A to 3E, describing and the length-width ratio then by the above-mentioned cellulose acylate film that is melt into film preparation with the preheat roll preheating.Draft temperature in table with " relatively Tg " expression, promptly with+or-the temperature representation, how much more high or low expression is than the Tg of the resin of each embodiment and comparative example.Longitudinal stretching and cross directional stretch " draft temperature " described uniform temp in as table carries out.
In the embodiment 1-1 to 1-24 shown in the table of Fig. 3 A to 3E and comparative example 1-1 and 1-2, the quality of the oriented cellulose acylate film for preparing is estimated to use each cellulose acylate film for preparing under the membrance casting condition described in the table.Elongation at break when the quality evaluation project comprises Re and fluctuation, Rth and fluctuation thereof, mist degree, YI value, film thickness and stretching.
" quality evaluation of oriented cellulose acylate film "
Value in the table of Fig. 3 A to 3E has shown the acceptable mass value of membrance casting condition, stretching condition and oriented cellulose acylate film, and they are specific as follows.
● the screw compression ratio of extruder: 2.5 to 4.5
● the L/D:20 to 50 of extruder
● extrusion temperature: 190 to 240 ℃
● the preheat temperature in the longitudinal stretching: Tg-40 ℃ to Tg+60 ℃
● the stretch rate in the longitudinal stretching: 1.01 to 3.0
● the stretch rate in the cross directional stretch: 1.0 to 2.5
● DSC endothermic peak: be equal to or less than 4.0J/g
● Re:0 to 500nm
● Re coefficient of variation: be equal to or less than 5%
● Rth:30 to 500nm
● Rth coefficient of variation: be equal to or less than 5%
● haze value: be equal to or less than 2%
● YI value: be equal to or less than 10
● film thickness: 30 to 300 μ m
● the elongation at break during stretching: be equal to or greater than 50% (before stretching 1.5 of value)
With reference to the table of figure 3A to 3E, in embodiment 1-1 to 1-3, the extrusion temperature during preparation cellulose acylate film (stretch) is set at 190 ℃ (lower limits), 220 ℃ and 240 ℃ (upper limit), and these values are in the scope that the present invention defines.On the other hand, in comparative example 1-1 and 1-2, extrusion temperature is set at 185 ℃ (being lower than lower limit of the present invention) and 245 ℃ (being higher than the upper limit of the present invention), outside these are worth in the scope of the present invention's definition.
When prepare under the extrusion temperature condition of using at the foregoing description and comparative example oriented cellulose acylate film does not prepare oriented cellulose acylate film the time; elongation at break during stretching among the embodiment 1-1 to 1-3 be 70% (before stretching 1.7 times of value) to 180% (before stretching 2.8 times of value), show the draftability of excellence.The following fact has also proved the improvement of draftability: be equal to or less than 4J/g and mist degree as the DSC endothermic peak and be equal to or less than 1.5% as indicated in (DSC endothermic peak and mist degree all are the indexes of the amount of small crystal residual in the cellulose acylate film), not residual basically small crystal in the cellulose acylate film that forms.Therefore, to show Re be that 40 to 50 (coefficient of variation 2 to 4%) and Rth are the good result of 240 to 260 (coefficient of variation 2 to 4%) to oriented cellulose acylate film.In addition, because extrusion temperature is equal to or less than 240 ℃, obtain the YI value and be 3 to 6 good result, this shows yellowing does not take place basically.
On the other hand; in comparative example 1-1, the elongation at break the during stretching of film is 47% (value before stretching 1.47 times), this value less than and lattice point 50% (value before stretching 1.5 times); and film fracture in stretching step therefore can not the preparation oriented cellulose acylate film.This is consistent with the following fact: the index of the amount of residual small crystal is big in the cellulose acylate film, that is, the DSC endothermic peak is 5.4J/g, and greater than 4J/g, and haze value is 2.3%, greater than 2%.In addition; in comparative example 1-2; because melt extruding temperature is 245 ℃; be higher than 240 ℃; the good result of (value before stretching 2.2 times) that elongation at break when having obtained to stretch is 220%; but this film has 11 high YI value, and this value has surpassed and lattice point 10, thereby the serious yellowing of cellulose acylate film.
Embodiment 1-4 to 1-8 changes under the situation of longitudinal stretching preheat temperature in Tg-40 ℃ to Tg+60 ℃ scope, carries out at 230 ℃ constant extrusion temperatures.Elongation at break when the oriented cellulose acylate film that obtains by the prepared cellulose acylate film that stretches has the Re, Re coefficient of variation, Rth, Rth coefficient of variation, mist degree, YI value, film thickness of optimal level and stretching.
Embodiment 1-9 to 1-13 changes under the situation of screw compression ratio in 2.5 to 4.5 scopes that the present invention limits, and carries out at 230 ℃ constant extrusion temperatures.Elongation at break when the oriented cellulose acylate film that obtains by the prepared cellulose acylate film that stretches has the Re, Re coefficient of variation, Rth, Rth coefficient of variation, mist degree, YI value, film thickness of acceptable quality level and stretching.
Embodiment 1-14 to 1-18 changes in 190 ℃ to the 240 ℃ scopes that the present invention limits under the situation of extrusion temperature, and constant screw compression ratio 3.5 and 50 constant L/D (this value is its upper limit that the present invention limits) carry out.Elongation at break when the oriented cellulose acylate film that obtains by the prepared cellulose acylate film that stretches has the Re, Re coefficient of variation, Rth, Rth coefficient of variation, mist degree, YI value, film thickness of acceptable quality level and stretching.
Embodiment 1-19 to 1-24 is that the glass transition temperature that acidylates celluosic resin changes in 120 ℃ to 170 ℃ scope and carries out under the situation by substitution value that changes acylated cellulose and molecular weight.Elongation at break when the oriented cellulose acylate film that obtains by the prepared cellulose acylate film that stretches has the Re, Re coefficient of variation, Rth, Rth coefficient of variation, mist degree, YI value, film thickness of acceptable quality level and stretching.
The table of Fig. 3 A to 3E has only shown the wherein situation of the scope of screw compression ratio satisfied 2.5 to 4.5.When screw compression than greater than 4.5 the time, molecular breakdown, thereby molecular weight reduces, thus cause the mechanical strength of prepared cellulose acylate film significantly to descend.Therefore do not carry out stretching step subsequently.When screw compression than less than 2.5 the time, fusion is insufficient and produce the particle of not fusion, perhaps sneaks into bubble.Therefore do not carry out stretching step subsequently yet.
The table of Fig. 3 A to 3E has only shown the wherein situation of the scope of L/D satisfied 20 to 50.When L/D less than 20 the time, produce the particle of not fusion, thereby do not carry out stretching step subsequently.When L/D greater than 50 the time, molecular breakdown, thereby molecular weight reduces, thus cause the mechanical strength of prepared cellulose acylate film significantly to descend.Therefore do not carry out stretching step subsequently.
[preparation of polarizer]
(1) preparation of polarizer
Under the membrance casting condition of the embodiment 1 of the table 1 shown in Fig. 3 A to 3E, prepare unstretching film, and, prepare following polarizer as the material (substitution value, the degree of polymerization, plasticizer) of change film as described in the table 2 among Fig. 4.
(1-1) saponification of cellulose acylate film
By infusion process saponification described below oriented cellulose acylate film not.The acylated cellulose that do not stretch that carries out saponification by following coating process also obtains substantially the same result.
(i) saponification by being coated with
The water of 20 mass parts is joined in the isopropyl alcohol of 80 mass parts, and dissolve KOH therein until 2.5N.The mixture that obtains is adjusted to 60 ℃ to be used as saponification liquor.With saponification liquor with 10g/m 2Amount be coated on 60 ℃ the cellulose acylate film, to carry out 1 minute saponification.Subsequently, use sprayer with 50 ℃ of hot water with 10L/m 2Minute spray 1 minute with the washing film.
(ii) saponification by flooding
The NaOH aqueous solution that uses 2.5N is as saponification liquor.Saponification liquor is adjusted to 60 ℃, cellulose acylate film was flooded 2 minutes therein.Then, cellulose acylate film was flooded 30 seconds in the 0.1N aqueous sulfuric acid, and make it by water-bath.
(1-2) preparation of polarization layer
According to the embodiment 1 of Japanese Unexamined Patent Publication No 2001-141926, with two pairs of nip rolls of distinguishing peripheral speed, stretched film in the longitudinal direction, preparation thickness is the polarization layer of 20 μ m.
(1-3) adhere to
Use 3% the PVA aqueous solution (PVA-117H; available from Kuraray Co.; Ltd.), the FUJITAC (the triacetic acid film does not stretch) of not stretching and the oriented cellulose acylate film and the saponification of thus obtained polarization layer, above-mentioned saponification is combined in the draw direction of polarizing coating and the film forming flow direction (length direction) of cellulose acylate film is gone up stacked with following as adhesive.
Polaroid A: oriented cellulose acylate film/polarization layer/FUJITAC not
Polarizer B: the oriented cellulose acylate film of oriented cellulose acylate film/polarization layer/not
(1-4) change color of polarizer
On 1 to 10 yardstick, estimate the change color degree (number is big more, and change color is big more) of thus obtained polarizer.All polarizers prepared in accordance with the present invention all show good result.
(1-5) the curling evaluation of humidity
The humidity of the polarizer that obtains as mentioned above by the said method evaluation is curled.After forming polarizer, also show excellent performance (low humidity curls) even use polarizer of the present invention.
Preparation is the polarizer of stacked each layer wherein, so that the length direction of polarization axle and cellulose acylate film is crossing with right angle or miter angle, and carries out identical evaluation.As above-mentioned parallel stacked situation, all obtain similar result under two kinds of situations.
(2) preparation of compensate film and LCD
To remove attached to the polarizer of observer's side of 22 inches LCDs that use VA type liquid crystal (by Sharp Corporation preparation); and when using above-mentioned delay polaroid A or B to replace; separate polarizer; and use adhesive that polarizer is sticked to observer's side, make cellulose acylate film be positioned at liquid crystal cell side.The location polarizer makes that the axis of homology of polarizer of the axis of homology of polarizer of observer's side and backlight side is vertical mutually, thereby finishes LCD.
Very little humidity is curled and adhesion easily because polarizer according to the present invention has, and has therefore seldom found misalignment when adhering to.
In addition, when use cellulose acylate film of the present invention replace Japanese Unexamined Patent Publication No 11-316378 embodiment 1 be applied to the CAM of liquid crystal layer the time, obtained to have the excellent compensate film that very little humidity is curled.
When using cellulose acylate film of the present invention to replace the CAM that is applied to liquid crystal layer of the embodiment 1 of Japanese Unexamined Patent Publication No 7-333433 to compensate filter coating, obtained to have the excellent compensate film that very little humidity is curled with preparation.
With polarizer of the present invention or postpone polarization and be applied to the LCD in the embodiment 1 of Japanese Unexamined Patent Publication No 10-48420, described; The optical anisotropic layer of in the embodiment 1 of Japanese Unexamined Patent Publication No 9-26572, describing that comprises the disc-like liquid crystal molecule; The alignment films of in Fig. 2 to 9 of Japanese Unexamined Patent Publication No 2000-154261, describing that is coated with polyvinyl alcohol, 20 inches VA type LCDs; The IPS type LCD of describing among 20 inches OCB type LCDs in Figure 10 to 15 of Japanese Unexamined Patent Publication No 2000-154261, describing and Figure 11 of Japanese Unexamined Patent Publication No 2004-12731.As a result, prepared and had the excellent LCD that very little humidity is curled.
(3) preparation of low-reflection film
Use cellulose acylate film of the present invention, according to " Kokai Giho of Japan Institute ofInvention ﹠amp; Innovation " the embodiment 47 preparation low-reflection films of (Kogi No.2001-1745).The film that obtains is carried out the curling measurement of above-mentioned humidity.Use low-reflection film of the present invention as the situation of preparation polarizer, obtain good result.In addition, low-reflection film of the present invention is applied to the outermost layer of the LCD of description in the embodiment 1 of Japanese Unexamined Patent Publication No 10-48420; 20 inches VA type LCDs in Fig. 2 to 9 of Japanese Unexamined Patent Publication No 2000-154261, describing; The IPS type LCD of describing among 20 inches OCB type LCDs in Figure 10 to 15 of Japanese Unexamined Patent Publication No 2000-154261, describing and Figure 11 of Japanese Unexamined Patent Publication No 2004-12731, and these devices are estimated.As a result, obtain excellent LCD.

Claims (15)

1. cellulose acylate film, wherein the acidylate group satisfies following substitution value:
2.5≤A+B＜3.0, and
1.25≤B＜3.0，
Wherein A represents degree of substitution with acetyl group, and B represents total substitution value of propiono, bytyry, valeryl and caproyl,
And when at glass transition temperature Tg+10 this film of ℃ uniaxial tension, its elongation at break is equal to or greater than 50%.
2. according to the cellulose acylate film of claim 1, the endothermic peak of wherein said film is equal to or less than 4.0J/g, and this peak appears in the zone that is equal to or higher than glass transition temperature Tg in DSC (differential scanning calorimetry).
3. according to the cellulose acylate film of claim 1; the mist degree of wherein said film is equal to or less than 2.0%; yellowness index (YI value) be equal to or less than 10 and endothermic peak be equal to or less than 4.0J/g, this peak appears in the zone that is equal to or higher than glass transition temperature Tg in DSC (differential scanning calorimetry).
4. according to each cellulose acylate film in the claim 1 to 3, the molecular weight of wherein said film is 20,000 to 100,000.
5. according to each cellulose acylate film in the claim 1 to 4, wherein said film is by the method preparation that may further comprise the steps:
Use screw compression than be 2.5 to 4.5 and L/D be 20 to 50 extruder, the through port mould on coolant carrier, in 190 ℃ to 240 ℃ extrusion temperatures with the resin extruded one-tenth sheet material of acylated cellulose; With
By the described sheet material of cooling curing.
6. according to the cellulose acylate film of claim 5, wherein said method is further comprising the steps of:
The described cellulose acylate film of unstretched state is stretched 1 to 2.5 times at least one direction in the vertical and horizontal of this film.
7. oriented cellulose acylate film, it is to obtain by stretching 1 to 2.5 times at least one direction in the vertical and horizontal of this film according to each not oriented cellulose acylate film in the claim 1 to 5.
8. according to the oriented cellulose acylate film of claim 7, wherein the thickness of this film is 30 to 300 μ m, postpone in the face (Re) be 0 to 500nm and the delay on thickness direction (Rth) be 30 to 500nm.
9. oriented cellulose acylate film according to Claim 8, wherein the fluctuation of the fluctuation of Re and Rth all is equal to or less than 5% on width and length direction.
10. polarizer, it comprises stacked one deck at least according to each not oriented cellulose acylate film in the claim 1 to 4.
11. a compensate film that is used for LCD panel, its comprise film substrate by way of compensation according to each not oriented cellulose acylate film in the claim 1 to 4.
12. an anti-reflective film, its comprise as the anti-reflective film substrate according to each not oriented cellulose acylate film in the claim 1 to 4.
13. a polarizer, it comprises stacked one deck at least according to each oriented cellulose acylate film in the claim 7 to 9.
14. a compensate film that is used for LCD panel, its comprise film substrate by way of compensation according to each oriented cellulose acylate film in the claim 7 to 9.
15. an anti-reflective film, its comprise as the anti-reflective film substrate according to each oriented cellulose acylate film in the claim 7 to 9.
CN2005800319340A 2004-09-24 2005-09-21 Cellulose acylate film, its manufacturing method, drawn cellulose acylate film and its manufacturing method Expired - Fee Related CN101027175B (en)

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