CN1690741A - Method for producing optical compensation film, optical compensation film, polarizing plate, displaying apparatus - Google Patents
Method for producing optical compensation film, optical compensation film, polarizing plate, displaying apparatus Download PDFInfo
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- CN1690741A CN1690741A CN 200510065949 CN200510065949A CN1690741A CN 1690741 A CN1690741 A CN 1690741A CN 200510065949 CN200510065949 CN 200510065949 CN 200510065949 A CN200510065949 A CN 200510065949A CN 1690741 A CN1690741 A CN 1690741A
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Abstract
A method for producing a roll of an optical compensation film, in the effective width of which an angle of the slow axis in the film face with the width direction of the film is within the range of +-1 DEG and an angle of the fast axis in the film face with the length direction of the film is within the range of +-1 DEG , wherein the angle of the fast axis in the film face with the length direction is cyclically varied by a cycle of from 1.5 m to 500 m in the length direction of the film and the minimum amplitude of the variation is within the range of from 0.1 DEG to 1 DEG .
Description
Technical field
The present invention relates to phase retardation film, polaroid and display device, relate in more detail when producing in large quantities or producing continuously, to the phase retardation film that load is little and yield is high of device, also have all display device of even good endurance of light leak is few and yield is high polaroid and contrast.
Background technology
The liquid crystal type display device particularly can be made into the slimming device, so be widely used as the display device of word processor and personal computer etc. because low, the little power consumption of its voltage can directly be connected in the IC circuit.The basic comprising of this liquid crystal indicator for example is in the both sides of liquid crystal cell polaroid to be set.
Consider from aspects such as contrasts, it is the liquid crystal indicator of the above super twisted nematic (STN) of 160 degree that above-mentioned liquid crystal indicator is being developed liquid crystal indicator, the use torsion angle that the use torsion angle is the twisted-nematics (TN) of 90 degree, and the somebody has proposed and TN or the different liquid crystal of STN type.That is to say that TN or STN type liquid crystal cell are a kind of when voltage closes, liquid crystal molecule is parallel to alignment plate, when voltage is opened, liquid crystal molecule carries out directed liquid crystalline type perpendicular to alignment plate, in contrast, also develops other liquid crystal, promptly, liquid crystal molecule is parallel to the type of alignment plate, for example perpendicular to alignment plate when voltage is opened when voltage closes, use the negative isotropic negative type liquid crystal of dielectric, so-called length direction adjusting type liquid crystal.
Above-mentioned length direction adjusting type liquid crystal indicator is for example opened in flat 2-176625 number open the spy.This length direction is adjusted (Vertical Alignment, be called for short VA, sometimes also represent below with VA) the type liquid crystal indicator because be the liquid crystal cell of so-called vertical alignment mode, liquid crystal molecule when voltage closes perpendicular to alignment plate, when opening, voltage is parallel to the alignment plate orientation, it is characterized in that, black show very goodly, the contrast height, compare with the STN type with TN, broad is compared at the visual angle.
But, as large-scale TV,, wish that the requirement of further widening the visual angle also improves thereupon, has used phase retardation film in order to enlarge the visual angle along with the increase of liquid crystal panel.Therefore, along with the expansion of foregoing liquid crystal picture, optical compensation films also more and more develops to the wide cut direction.
To achieve these goals, application to former polymeric membrane is studied, find that common TAC film has certain phase difference value (Rt) at thickness direction, and direction has only very little phase difference value (Ro) in face, for example, in order to improve the visual angle of aforesaid VA type LCD, not necessarily suitable.
Known to overcome the problems referred to above, by cellulose ester membrane is stretched to the fabric width direction when the system film, form in the fabric width direction and to have in the face polymeric membrane of the slow axis polaroid protective film of holding concurrently, obtain the film of phase differential good uniformity.
But in large-scale phase retardation film, the skew of slow axis will cause contrast significantly to reduce in the face of film, in order to ensure display performance, once carry out technological development (for example, with reference to patent documentation 1,2) at the skew of slow axis in the face.
Usually, existing phase retardation film carries out the back with polaroid and pastes as described in the patent documentation 1.Even the above-mentioned phase retardation film that uses is used for the big film of area always, also can the light leak of the polaroid (ellipsoidal polarizing plate) of final band phase retardation film be reduced by when pasting, adjusting the skew of axle with polaroid.
But; polaroid side or at least one side of phase differential side are cut into slices; different with the mode of utilizing bonding agent to paste; the problem that has the phase retardation film of polaroid protective film concurrently is; because by handling with the direct saponification of PVA, it is stacked to utilize the mode of reel-fibrous bundle-reel to carry out, so the skew of the interior slow axis of the face of reel film (former anti-Off イ Le system); directly cause the light leak after polaroidization, result cause afterwards processing with remaining unchanged.
Carry out in the stacked formation in the mode of utilizing reel-fibrous bundle-reel, the technology of the skew of slow axis is open in patent documentation 2 in the involvement aspect.But this technology is only limited to explanation owing to suppressed the distribution of slow axis skew in the face with light leak amount location correlationship, and the demonstration that suppresses in the panel is irregular.In addition, also disclose polymer film and preferably used the low material of pyroconductivity with this phase differential, still, to the not explanation of permanance that improves the viewing angle compensation function.
And, concrete grammar as slow axis skew in the face that is used to suppress the reel film, be to utilize the temperature when stretching to make the film softnessization, eliminate and (for example stretch inequality, with reference to patent documentation 3), in this patent documentation, in fact a control stretching temperature, make low-angle in the angle of the length direction of the maximum direction of index of refraction and long film or the formation of fabric width direction (below, be also referred to as the angle of orientation), long film inner control 3 ℃ with interior scope, by controlling above-mentioned scope, make it use very difficulty at large-scale liquid crystal indicator.
In the past, when thinking direction stretched film beyond the direction of transfer always, with the deviation control of the angle of orientation at 0 °, but, when stating idea in fact in realization, when the direction beyond direction of transfer is carried out stretch processing, utilize present known devices to implement a lot of difficulties.In addition, when utilizing the continuous mode of production of the present invention to produce in batches, the yield when producing in order to improve, need to utilize condition with specific degrees span of control limit of control, consider from the viewpoint of steady production, by with the deviation control of the angle of orientation at 0 °, be difficult to solve this problem in the reality.
Patent documentation 2 spies open the 2002-22943 communique
Patent documentation 3 spies open the 2001-215332 communique
Summary of the invention
Therefore, the objective of the invention is in view of above-mentioned problem, provide a kind of when producing in a large number or producing continuously, the phase retardation film that load is little and yield is high of device, also have the polaroid that light leak is few and yield is high, and contrast evenly reaches the display device of good endurance.
Above-mentioned problem of the present invention realizes by following formation.
1, a kind of manufacture method of drum phase retardation film, to be the angle that forms of the fabric width direction of slow axis and this film in the effective width inner face of drum film be ± 1 ° scope to this method, the angle that the length direction of leading phase shaft and this film forms in the face of this film is the phase retardation film manufacture method of ± 1 ° scope, it is characterized in that, make the interior leading phase shaft of face of aforementioned films and the angle that this film length direction forms, have cycle of 1.5m～500m in this film length direction, and minimum amplitude that should the cycle is set at 0.1 °～1 °.
2, a kind of manufacture method of drum phase retardation film, this method is that the fabric width direction of slow axis and this film forms in the face in the effective width of drum film angle is 45 ± 1 ° a scope, the angle that the length direction of leading phase shaft and this film forms in the face of this film is the phase retardation film manufacture method of 45 ± 1 ° scope, it is characterized in that, make the interior leading phase shaft of face of aforementioned films and the angle that this film length direction forms, have cycle of 1.5m～500 in this film length direction, and minimum amplitude that should the cycle is set at 0.1 °～1 °.
As the manufacture method of 1 or 2 described drum phase retardation films, it is characterized in that 3, the drum polarizing coating makes and reel-fibrous bundle-reel is pasted mutually.
4, as the manufacture method of any one described drum phase retardation film of 1～3, it is characterized in that aforesaid roll tubular phase retardation film carries out stretch processing in the scope of 1.05～2 times of stretching ratios at least one direction of length direction or fabric width direction.
5, as the manufacture method of any one described drum phase retardation film of 1～4, it is characterized in that, control the two ends, the left and right sides of a continuous film, the limit applies tension force in the fabric width direction, this film is transmitted on the limit, utilizes in the drum film manufacturing method that stretching device stretches, and utilizes the left and right sides grasping device of aforementioned stretching device, controlling of film controlled about length (from controlling starting point to the distance of controlling end) is utilized independently, stretched.
6, as the manufacture method of any one described drum phase retardation film of 1～5, it is characterized in that, change about utilizing by at least one side who controls reference position (position of clip overlay is set) or control end position (position that clip is opened is set) in the left and right sides grasping device that makes stretching device, about independently controlling diaphragm about control length.
7, as the manufacture method of any one described drum phase retardation film of 1～6, it is characterized in that, by controlling continuous two ends, the film left and right sides, the fabric width direction is applied the left and right sides length of the unlimited guide rail of mobile usefulness of the grasping device that tension force connects, carry out left and right sides independent variation, about independent controlling diaphragm about control length.
8, as the manufacture method of any one described drum phase retardation film of 1～7, it is characterized in that, in the grasping device of the left and right sides of aforementioned stretching device, this grasping device can about control rate independently.
9, as the manufacture method of any one described drum phase retardation film of 1～8, it is characterized in that, the angle of orientation of the film before on-line determination batches, on the basis of measurement result, the left and right sides grasping device of selecting at least a method to make to select to utilize stretching device with film control length carry out method that independent left and right controls or about the method for left and right sides grasping device speed of independent control stretching device.
10, as the manufacture method of any one described drum phase retardation film of 1～9, it is characterized in that, on-line determination is in the position of controlling the starting position and controlling the left and right sides grasping device of end position, try to achieve the film phase differential that produces when this controls the position, on the basis of measurement result, select at least a method to make, the left and right sides grasping device that utilizes stretching device with film control length carry out about the method for independent control, or about the method for left and right sides grasping device speed of independent control stretching device.
11, a kind of phase retardation film, it utilizes in 1～10 any one described method to make.
As 11 described phase retardation films, it is characterized in that 12, utilizing the interior delay of face (Ro) of following formula (1) expression is 25～300nm.
Formula (1) Ro value=(nx-ny) * d
[in the formula, nx represents the refractive index of its maximum direction of refractive index in the face, and ny represents meet at right angles the refractive index in the face on the direction with nx, and d represents the thickness (nm) of film].
13, as 12 described phase retardation films, it is characterized in that, utilize the delay (Rt) of the thickness direction of general formula (2) expression to be-100～400nm.
Formula (2) Rt value=((nx+ny)/2-nz) * d
[in the formula, nx represents the refractive index of its maximum direction of refractive index in the face, and ny represents meet at right angles the refractive index in the face on the direction with nx, and nz represents the refractive index of film thickness direction, the thickness (nm) that d represents film].
14, a kind of polaroid is characterized in that, it has 11～13 phase retardation films described in any one.
15, a kind of display device is characterized in that, it has 11～13 phase retardation films described in any one.
Described film effective width, being meant can the actual width that uses in the film overall width of film.For example, when being polaroid protective film, carry out annular knurl processing etc. sometimes in the end.It is cut and can not use when this part sticks on the panel at last.The effective width of film is to remove width behind the annular knurl processing part from the film overall width in this case.
The present invention can provide a large amount of productions or when producing continuously, to the phase retardation film that load is little and yield is high that device produces, and the display device that also has light leak is few and yield is high polaroid and contrast evenly to reach good endurance.
Description of drawings
Fig. 1 is the mode chart of angle of orientation distribution of the present invention and angle of orientation variable cycle.
Fig. 2 is the length direction angle of orientation change figure of cellulose ester membrane 101.
Fig. 3 is the length direction angle of orientation change figure of cellulose ester membrane 102.
Fig. 4 is the length direction angle of orientation change figure of cellulose ester membrane 103.
Fig. 5 is the length direction angle of orientation change figure of cellulose ester membrane 104.
Fig. 6 is the length direction angle of orientation change figure of cyclic olefin polymer 203.
Fig. 7 is a formation synoptic diagram of implementing film forming apparatus of the present invention.
Fig. 8 is the formation synoptic diagram of liquid crystal indicator.
Fig. 9 is the formation synoptic diagram of liquid crystal indicator.
Figure 10 is the angle that the fabric width direction of slow axis and film forms in the face in the effective width of roller tubular membrane.
Figure 11 is the fabric width direction angle of orientation change figure in the effective width of roller tubular membrane.
Figure 12 is the angle that the length direction of leading phase shaft and film forms in the face in the effective width of roller film.
The explanation of the minimum amplitude in Figure 13 cycle
Symbol description
1 casting device
6,9 drying devices
7 film take-up mechanisms
8 tenter frame apparatus
The F film
Embodiment
Below, be elaborated to implementing best mode of the present invention, but the present invention is not limited to this.
Phase retardation film of the present invention, to be the fabric width direction of slow axis and this film forms in the face in the effective width of drum film angle be ± 1 ° scope for it, the angle that the length direction of leading phase shaft and this film forms in the face of this film is the phase retardation film of ± 1 ° scope, its manufacture method is characterised in that, make the interior leading phase shaft of face of aforementioned films and the angle that this film length direction forms, have cycle of 1.5m～500m in this film length direction, and minimum amplitude that should the cycle is set at 0.1 °～1 °.Figure 10 is illustrated in the example of the angle that the fabric width direction of slow axis and this film forms in the face in the effective width of drum film, and Figure 12 illustrates the example of the angle that leading phase shaft and length direction form in the face.
What the present inventor studied repeatedly found that, the angle that forms by leading phase shaft in the face that makes film and film length direction is carried out long periodicity ground change (specifically being the length direction than liquid crystal indicator, the also fully long variable cycle of direction of length in the fabric width direction) at particular range, does not have a substantial influence to unevenness of brightness, tone in the display area scope of reality are irregular.Find in addition, like this with have identical axle and change deviation, but the long film of generating period change is not compared, and can reduce to minimum to the influence of polaroid and display device, the requirement of minimizing to creating conditions improves productivity simultaneously.Yield described in the present invention improves, be meant when making length size phase retardation film, improve the yield of long size, the yield reduction that inhibition uses the light leak of the polaroid behind this polarizer to cause, and during as liquid crystal indicator, prevent that the yield that the polaroid light leak causes from reducing.
At this, the direction of described interior slow axis is the maximum direction of the index of refraction in the face, and the angle that described interior slow axis and film web cross direction form is meant fabric width direction with film as datum line (0 °), the angle that slow axis and datum line form.When the film of reel form stretches in the fabric width direction, be datum line with the direction of keeping straight on along transfer direction.
The direction of described interior leading phase shaft be with face in the direction of slow axis quadrature, the angle that described interior leading phase shaft and film length direction form, be meant that film with the reel mode is when the fabric width direction stretches, direction with fabric width direction quadrature, promptly be datum line (0 °) with the length direction, the angle that leading phase shaft and datum line form.
The present invention finds, utilize a kind of drum phase retardation film can solve above-mentioned problem, the angle that the fabric width direction of slow axis and this film forms in the face in the effective width of drum phase retardation film is ± 1 ° a scope, the angle that the length direction of leading phase shaft and this film forms in the face of this film is in ± 1 ° the position related film manufacture method of scope, it is characterized in that, make the interior leading phase shaft of face of aforementioned films and the angle that this film length direction forms, have cycle of 1.5m～500m in this film length direction, and minimum amplitude that should the cycle is set at 0.1 °～1 °.That is to say, the present invention finds, with the deviation control of the angle of orientation 0 ° Time not as the deviation that makes the angle of orientation in particular range and the such phase retardation film of generating period change utilization, can reduce requirement to creating conditions, improve productivity simultaneously, can solve above-mentioned problem under these conditions.
Particularly as this phase retardation film of polaroid protective film; when utilizing reel-fibrous bundle-reel and polarizing coating to paste; merge the consideration that needs of keeping uniform slow axis angle from conforming to the amplitude of polaroid; although the homogeneity of fabric width direction is an important factors, the uniform films that all satisfies aforementioned condition on fabric width direction and length direction is not open fully.
Found that, the reel film is by strictly maintaining whole fabric width direction and length direction with the slow axis of this phase retardation film, the mobility scale of leading phase shaft, do not produce the display characteristic deterioration that the variation of slow axis angle brings even under high temperature drying condition, hot and humid condition, carry out long duration test yet, can obtain being fit to very much the strong ellipsoidal polarizing plate of environmental turbulence.
In addition, also find in reflection-type liquid-crystal display device, utilize 45 ° of useful gradients to stretch, when making λ/4 slab integral type polaroids, fabric width direction and length direction in the film effective width, slow axis is from the scope of film web cross direction at 45 ± 1 ° in the face of film, the angle that slow axis and film length direction form in the face is in 45 ± 1 ° scope, change according to 1.5m～500m cycle in the film length direction, and minimum amplitude that should the cycle is can solve above-mentioned problem for the phase retardation film of feature more than 0.1 ° or 0.1 °.
Below, the present invention is described in detail.
The film that uses in the phase retardation film of the present invention is preferably made easily, has the film of optical homogeneity, optical transparence.As long as have above-mentioned character any can, for example have: the cellulose esters mesentery, the polyester mesentery, the polycarbonate mesentery, poly-polyarylate mesentery, polysulfones (also containing polyethersulfone) mesentery, polyethylene terephthalate, polyester films such as PEN, polyethylene film, polypropylene screen, cellophane, the cellulose diacetate film, the cellulose acetate butyrate film, the polyvinylidene chloride film, polyvinyl alcohol film, ethylidene vinyl alcohol film, styrene-based film, polycarbonate membrane, the norbornene resin mesentery, the polymethylpentene film, the polyetherketone film, polyetherketone acid imide film.Polyamide membrane.Fluororesin film.Nylon membrane.Cyclo-olefin-polymer films.Polymethyl methacrylate film or acrylic film etc., but be not limited to above-mentioned substance.These films preferably use the film that is obtained by solution casting method or fusion legal system film.Wherein, preferred cellulose ester membrane, polycarbonate membrane, polysulfones (containing polyethersulfone), the cyclo-olefin-polymer films used, the present invention considers from each side such as manufacture method, cost, the transparency, homogeneity, cementabilities, special optimum fiber cellulose ester film, cyclo-olefin-polymer films.
At first the cellulose ester membrane that the present invention is preferably used describes.
The manufacturing of cellulose ester membrane
At first, the film-forming method of the cellulose ester membrane that the present invention is used describes (representational example provides solution casting system embrane method).
Dissolution process
This operation is in dissolution kettle, is that stirring cellulose esters limit, limit makes its dissolving in the organic solvent of leading at the good solvent at cellulose esters, forms rubber cement.Dissolving can utilize following the whole bag of tricks to carry out, as: under normal pressure under the temperature below the boiling point of main solvent, carry out, pressurization is carried out, is cooled to subzero and carries out or under high pressure carry out more than the boiling point of main solvent, can use any method to dissolve among the present invention, but, the high-temperature digestion method of more preferably use under the used above condition of main solvent boiling point, dissolving under the pressurized state.Utilize rubber cement filtration, deaeration after filtering material will dissolve, with being pumped into subsequent processing.
In rubber cement, can add the adjuvant that plastifier, antioxidant, ultraviolet light absorber, matting agent, delay adjustment agent etc. have various performances.These adjuvants can add with cellulose esters or solvent when the preparation rubber cement, also can add in the preparation rubber cement or after the preparation.And, also can add thermal stabilizer, antistatic agent, fire retardant, lubricant, finishes etc. such as alkali earth metal salt sometimes.
The curtain coating operation
This operation is by the compression type quantitative gear pump, rubber cement is delivered to adds in the pressing mold, in the curtain coating position, the surface forms minute surface, makes rubber cement go up curtain coating from the metallic cylinder of the metal driving-belt for no reason that adds the pressing mold curtain coating and pass in circulation or rotation (below abbreviation make metal support).Utilize the casting device of mould, preferably can adjust the shape of slit of shank, make the even easily mould that pressurizes of thickness of reel film.Coat hanger die and T pattern tool etc. are arranged in the pressurizing mold, preferably use any.In order to improve film speed, at the pressurizing mold that is provided with on the metal support more than 2 or 2, make the rubber cement amount separately, form lamination and also can.
Use the cellulose ester membrane of wide cut among the present invention.Particularly preferably use the film of amplitude 1.3～4m, more preferably 1.4～2m.When surpassing 4m, transmit difficulty.In addition, the cellulose esters film thickness is different because of application target, considers that from the viewpoint of liquid crystal indicator slimming the film that is processed into is 10～200 μ m, preferred 10～150 μ m, the more preferably scope of 40～100 μ m.Served as when approaching, for example do not reached the needed intensity of protective film for polarizing plate sometimes.When blocked up, Yi Qian cellulose ester membrane loses the advantage of membranization relatively.In order to regulate thickness, can control the liquor charging amount of rubber cement concentration, pump, the joint slit gap of mould, the squeeze pressure of mould, the speed of metal support etc. and make it reach the thickness of hope.In addition, make thickness that uniform method is set and preferably use film thickness detecting device, the feedback information feedback of sequencing is respectively installed above-mentioned, regulate.
The solvent evaporation operation
This operation is to utilize metal support heating reel film, makes organic dissolving evaporation.In order to make organic solvent evaporation, use from the method for reel film cross air blow and/or utilize from the back side of metal support liquid heat transfer method, utilize method that radiation heat conducts heat from the table back side etc., the present invention preferably uses any method.
Stripping process
This operation is on metal support, peels off the reel film that makes organic solvent evaporation on metal support.The reel film of peeling off is delivered to next drying process.When the residual solvent amount of the reel film when peeling off is excessive, be difficult to peel off, on the contrary, when peeling off after the abundant drying on metal support, in the stripping process, the part of reel film is stripped from sometimes.
Improve the method for film speed, comprise the gel casting that residual solvent can be peeled off at most.The poor solvent that adds in rubber cement at cellulose esters is arranged here, form the method for gel after the rubber cement curtain coating; The temperature of reduction metal support makes it the method for gelation etc.When making it gelation on metal support, film strength strengthens, and the residual solvent amount can be peeled off at most.The result peels off fast film speed to improve.In that the residual solvent amount is more when peeling off, the reel film is too soft, and the planarity when influence is peeled off is easy to generate by peeling off surface irregularity or the length direction striped that tension force causes, so should determine to peel off the residual solvent amount by taking into account economic pace and quality.Preferably under the condition of 10～120 quality %, peel off among the present invention.
The locational temperature of peeling off on the metal support preferably is adjusted at 10～40 ℃, more preferably is adjusted into 15～30 ℃.In addition, it is preferred the residual solvent amount of peeling off locational reel film being set at more than 30～120 quality %.Among the present invention, the residual solvent amount can be utilized formulate described later.
When making film on transmitting banded supporter, the rising of speed increases above-mentioned travelling belt vibration.When considering residual solvent amount when peeling off and travelling belt length etc., the preferred 10～120m/ branch of film speed, more preferably 15～100m/ branch.
Among the present invention, will be called average residual quantity of solvent, or be called the residual solvent amount of middle body, in addition, also be called local residual solvent amount sometimes as the residual solvent amount that is called reel film both ends with respect to the residual solvent amount of reel film beam overall.
Drying process
This operation by use drying device that the reel film is transmitted by the deflector roll that is configured to the square dentation alternately and/or with clip with the tentering drying device that the two ends clamping of reel film transmits, make reel film drying.Dry method generally is to the two sides of reel film blowing hot-air, also has to utilize microwave to replace the method that wind heats.Drying makes the planarity of the film of processing be affected easily too hastily.By the baking temperature of integral body preferred 40～250 ℃, more preferably 70～180 ℃.According to the organic solvent that uses, its baking temperature, dry air quantity and drying time can be different, preferably suitably select drying condition according to the kind and the combination thereof of solvent for use.
At the drying process after metallic support dignity is peeled off, the evaporation by solvent is shunk the reel film on two directions.Dry hastily contraction is big more under high-temperature more.Consider to make the gained film have good planarity, preferably under the condition that suppresses this contraction as much as possible, make its drying.From this viewpoint, for example the spy opens the method shown in the clear 62-46625 communique, in whole drying process or a part of operation, make the reel film in the clamping of fabric width direction, it is preferred that the limit keeps the amplitude limit at the fabric width direction two ends of reel film to carry out drying (tentering mode in a straight line), at this moment, can be by the stretching ratio of control reel film.Residual solvent amount, temperature, the delay that control the present invention is fit to.
Among the present invention, for example film residual solvent amount is 5～30 quality %, temperature when film stretches is 60～160 ℃, stretching ratio is 1.05～2 times, preferred 1.05～1.5 times, more preferably in 1.15～1.45 times the scope, utilize stenter to stretch in the fabric width direction at least, can carry out best delay to viewing angle compensation thus.In addition, at this moment the fabric width direction of film (TD direction) is that the direction (direction of slow axis in the face) of refractive index maximum is the nx direction, and length direction (MD direction) is the ny direction, and thickness direction is the nz direction.Length of delay utilizes Abbe refractomecer to try to achieve the mean refractive index of sample.Re-use automatic birefringence meter KOBRA-21ADH (prince's gauging instrument (strain) system), under 23 ℃, the environment of 55%RH, in wavelength 590nm, carry out three-dimensional refractive index and measure, calculate from the measured value of the phase differential that obtains and average index meter and obtain refractive index n x, ny, nz.
By the value substitution following formula that will obtain, can be in the hope of length of delay.
Formula (1) Ro value=(nx-ny) * d
Formula (2) Rt value=(nx+ny)/2-nz} * d
(in the formula, nx is the refractive index of the slow axis direction in the face, and ny is the refractive index of the leading phase shaft direction in the face, and nz is the refractive index of film thickness direction, and d is the thickness of film)
Among the present invention, consider, postpone (Ro) preferred 25～300nm in the face of following formula (1) expression from realizing excellent results of the present invention, and the delay (Rt) of the thickness direction of following formula (2) expression preferred-100～400nm.
In addition, stretched operation can be divided into multistage to carry out, and also can carry out biaxial stretch-formed on curtain coating direction, fabric width direction.In addition, carrying out when biaxial stretch-formed, both can carry out biaxial stretch-formedly simultaneously, also can carry out stage and stretch.In this case, so-called stage for example can be carried out the different stretching of draw direction successively, also the stretching of equidirectional can be divided into multistage, and carries out the ground stretching of any stage in different directions.That is to say, for example also can carry out following stretching step.
Longshore current prolongs direction and is stretched to and is stretched to longshore current along the fabric width direction and prolongs direction and be stretched to longshore current and prolong direction and stretch
Be stretched to along the fabric width direction and be stretched to longshore current along the fabric width direction and prolong direction and be stretched to longshore current and prolong direction and stretch
In the tentering operation, consider that from the viewpoint that improves film uniformity the atmosphere temperature degree of preferred film distributes in the little scope.Temperature Distribution in the tentering operation preferably ± ℃ in, more preferably in ± 2 ℃, most preferably ± 1 ℃ in.Distribute by reducing said temperature, the Temperature Distribution of the fabric width direction of film is diminished.
In above-mentioned tentering operation, coefficient of heat conductivity both can be certain, also can change.Coefficient of heat conductivity is preferably in the scope of 41.9～419 * 103J/m2hr, more preferably in the scope of 41.9～209.5 * 103J/m2hr, most preferably in the scope of 41.9～126 * 103J/m2hr.
Phase retardation film of the present invention is characterised in that, on the fabric width direction and length direction of film effective width, the angle that slow axis and film web cross direction form in the face of film is ± 1 ° a scope, the angle that leading phase shaft and film length direction form in the face of film is ± 1 ° a scope, cycle with 1.5m～500m on the film length direction changes, and minimum amplitude that should the cycle is more than 0.1 ° or 0.1 °.
Utilize Figure 13 that the minimum amplitude in cycle is described.So-called cycle minimum amplitude, be meant when being datum line (0 °) with the film length direction, variable cycle amplitude in the leading phase shaft angle (is meant among Figure 13,1/2 value of the angle of the amplitude 1 in cycle 1, the amplitude in cycle 22, the amplitude in cycle 33 expressions) in, is called minimum amplitude angle (1/2 of angle with smallest value in the angle of the amplitude 1 among Figure 13, amplitude 2, amplitude 3).When tiltedly stretching for 45 °, this datum line is 45 ° of directions.
The angle that slow axis and film web cross direction form in the face of above-mentioned film is preferred ± 0.7 ° in, more preferably ± 0.75 ° in.In addition, the angle that leading phase shaft in the face and film length direction form is preferred ± 0.7 ° in, the film length direction changed with the cycle of 1.5m～500m, and minimum amplitude that should the cycle is 0.1 °～1.0 ° a scope, more preferably 0.3 °～0.7 °, this is favourable to performance and productivity.Particularly the minimum amplitude of angle that leading phase shaft and film length direction form in the face of the film of film length direction 10m and cyclical swing is preferably in above-mentioned scope.
The mensuration of the angle of orientation of length direction, the KOBRA31A that for example prince's gauging instrument (strain) can be made etc. are arranged in the system film line and measure.Under this amplitude of fluctuation becomes big situation, easily all around the temperature and the balance of air quantity of Change Example such as tentering, transmit the lax etc. of tension force or tentering turnover part and control.
For the angle of orientation being controlled at 0 degree, when detecting the deviation of 0.04 degree, must have the temperature before and after the stenter extension section was for example being fed back with interior change tens degree respectively in 1 second.At this moment utilize internal capacity, the thermal capacity of stenter part, make the variation with 100 ℃～114 ℃ of interior realizations in 1 second, thus the temperature of the wind of delivering to the stenter part is set in more than 125 ℃ or 125 ℃, with air quantity be set in common more than 5 times with feed back corresponding.But, in order to improve atmosphere temperature degree, need be blown into the wind that is higher than film temperature, the result can not obtain necessary phase differential, the film of the angle of orientation, and yield first mate degree ground is reduced.When producing 10000m, orientation is with almost having reached in 0.1 °, and the R value of part has greatly changed, and the angle of orientation departs from more than 1 °, just in time is to form in the feedback.
Between clip distance equally also must 1 second with the interior adjustment of carrying out 1mm～100mm degree, no problem usually, but when not adjusting feedback time, also out of control sometimes.
In addition, when in reflection-type liquid-crystal display device, making by 45 ° of λ of forming of tiltedly stretching/4 slab integral type polaroids, on the fabric width direction and length direction of film effective width, make leading phase shaft in the face of film leave the scope of 45 ± 1 ° of film web cross directions, the angle that slow axis and film length direction form in the face of film is 45 ± 1 ° scope and changes with cycle of 1.5m～500 that the minimum amplitude in this cycle is preferably more than 0.1 ° or 0.1 °.Slow axis more preferably leaves the scope of 45 ± 0.7 ° of film web cross directions, preferred especially 45 ± 0.5 ° scope in the face of film.The angle that slow axis and film length direction form in the face of film is 45 ± 0.7 ° scope more preferably, and changes with the cycle of 1.5m～500m, and the minimum amplitude in this cycle is 0.1 °～1 ° a scope, preferred especially 0.3 °～0.7 ° scope.
According to figure the phase retardation film of the present invention with above-mentioned characteristic is described.Figure is an example, but is not limited thereto.
Fig. 1 is the distribution pattern figure of slow axis of the present invention and leading phase shaft.
Fig. 1 is the expression mode chart, interior slow axis of face and film web cross direction angulation distribute ± 1 ° scope, the angle that forms with leading phase shaft and film length direction in the face of the film of slow axis quadrature is ± 1 ° scope and periodically change, and minimum amplitude that should the cycle is to change more than 0.1 ° or 0.1 °.The cycle of the angle that leading phase shaft and film length direction form in the face of film of the present invention is 1.5m or more than the 1.5m, its upper limit is not particularly limited, under the working condition of reality, at phase retardation film 2,500～5, preferred this cycle is more than 1 cycle on the platen roller of 000m.Even during described oblique stretching, this cycle is preferred equally aspect the present invention the 2nd.
As follows as the method that suppresses above-mentioned angle of orientation amplitude as exemplifying out, but be not limited thereto.
The amplitude of the angle of orientation, from aforementioned curtain coating with metal support between the flow process of stenter part, remove to change and transmit the tension force, temperature and air quantity about in the time of can be by drying be poor, or the change of the nozzle exit area of wind is controlled.In addition, in a stenter part, distance, folder power etc. are carried out the inhibition of amplitude between the position by changing tension force, clip, clip.In addition, phoresy in the line, can utilize the axle of cylinder, position to control whole.
The present inventor has carried out found that of research to above-mentioned problem, during leading phase shaft and film length direction form in the face of film angle generating period change, do not need process units, condition to adjust to superprecision, production efficiency and the yield when film is used for polaroid and display device are all good, thereby finish the present invention.
Slow axis is at the film web cross direction in Fig. 2,3 presentation surfaces, the situation of direction not necessarily the time.The angle that leading phase shaft and film length direction form in the face of film must periodically change in this case.
Among the present invention, described fabric width direction stretches, and is meant owing to stretch in the fabric width direction while transmitting, direction in complexity in the drawing process is subjected to stress, comprise said process interior, carry out continuously stretched operation after, the stretching form that prolongs in fabric width direction film size.This situation comprises with the situation of the change in size of direction of transfer and any in the situation about changing.
As mentioned above, under the situation that the fabric width direction stretches, change in the angle of orientation distribution sometimes of fabric width direction.That is to say, relative draw direction, the direction of slow axis departs from sometimes in the face.This is known as buckling phenomenon, that is, for example can observe sometimes under the situation of using the stenter method, after stretching in the fabric width direction, produces convergent force at the film central portion, the end is fixed, consequent phenomenon.In this case, stretch or shrink in the curtain coating direction by making it, in addition adjust the stretching conditions such as pulling force of temperature before and after the tentering, residual solvent, clip, can control buckling phenomenon, the phase differential that less improves the fabric width direction distributes.
When the tentering operation finishes, compare with the MD direction, film produces more deformation in the TD direction.At this, among the present invention, after utilizing the stretching of stenter fabric width direction to finish, in film residual solvent amount is in the atmosphere of 40～150 ℃ of 5～30 quality %, temperature, scope at tension force 30～300N/m, more preferably carrying out cylinder under the condition of the scope of the scope of 57～284N/m, preferred especially 57～170N/m transmits, simultaneously in the residual deformation that relaxes the TD direction, carry out drying, can be formed in thus slow axis forms in the draw direction and face in the full width film angle at ± 1 ° with interior optical compensation films.At this moment, the mitigation of TD direction is important condition, for example, in the scope of said temperature, tension force condition, utilizes the row that rolls into more than 400 to transmit repeatedly, can reach the mobility scale of the above-mentioned slow axis of requirement of the present invention.
Coiling process
This operation is the operation that the reel film after finishing with drying batches as film.Residual solvent amount during dry the end is 2 quality % or below the 2 quality %, preferred 1 quality % or below the 1 quality %, and preferred especially 0.4 quality % or below the 0.4 quality % can obtain the good film of dimensional stability thus.Method for coiling can use the up-coiler of general use, adopt decide calibrated wrench method, decide tensammetry, the method for the control tension force of program Tension Control method that taper tensammetry, internal stress are specific etc., these methods can be used respectively.
The residual solvent amount is represented with following formula.
Residual solvent amount (quality %)=(M-N)/N} * 100
At this moment, M is the quality of the arbitrfary point of reel film, and N is in the quality of 110 ℃ of dryings after 3 hours with M.
By solution casting system embrane method, after curtain coating, carry out in the dry operation, both can make the atmosphere in the drying device be set at air, also can be set at inert gases such as nitrogen or carbon dioxide.But, must the frequent explosion limits danger of considering the evaporating solvent in the dry atmosphere gas.
Cellulose ester membrane and composition thereof
The cellulose of the cellulose esters raw material that uses as the present invention is not particularly limited, and cotton linter, wood pulp, mestha etc. are for example arranged.Can mix with arbitrary proportion by the above-mentioned cellulose esters that obtains in addition.
The number-average molecular weight (Mn) of the cellulose esters that the present invention uses is preferred 80000～200000, and more preferably 100000～200000, preferred especially 150000～200000.
The cellulose esters that the present invention uses, the ratio Mw/Mn of preferable weight-average molecular weight (Mw) and number-average molecular weight (Mn) is 1.4～3.0, more preferably 1.7～2.2 scope.In order further to obtain effect of the present invention, preferably use the cellulose esters of this scope.
The mean molecular weight of cellulose esters and molecular weight distribution can be utilized known method, use high performance liquid chromatography to measure.Number-average molecular weight, the weight-average molecular weight of using said method to calculate are calculated its ratio (Mw/Mn).
Condition determination is as described below.
Solvent: methylene chloride
Chromatographic column: Shodex K806, K805, K803G (clear and electrician's (strain) system, three connect use).
Column temperature: 25 ℃
Sample solution concentration: 0.1 quality %
Detecting device: RI Model 504 (GL サ イ エ Application ス corporate system)
Pump: L6000 (Hitachi (strain) system)
Flow: 1.0ml/min
Calibration curve: use polystyrene standard STK standard polystyrene (eastern ソ-(strain) system), 13 calibration curves that sample obtains between Mw=1000000～500.13 samples that use preferably almost uniformly-spaced.
The cellulose esters that the present invention uses can be by obtaining the cellulosic material acidylate.Acylating agent is under the situation of acid anhydrides (acetic anhydride, propionic andydride, butyric anhydride), uses organic solvents such as acetate class organic acid or methylene chloride, uses sulfuric acid based protic catalyzer to react as catalyzer.(CH for example when acylating agent is acyl chlorides
3COCl, C
2H
5COCl, C
3H
7COCl), use the alkali compounds of amine to react as catalyzer.Concrete employing spy opens the described method of flat 10-45804 communique and synthesizes.
The cellulose esters that the present invention uses is the carboxylate of carbon number about 2～22, the low-grade fatty acid ester of special preferred cellulose.Lower fatty acid in the cellulosic low-grade fatty acid ester, be meant that carbon number is the fatty acid below 6 or 6, for example can use cellulose ethanoate, cellulose propionate, cellulose butylate, cellulose ethanoate phthalate ester etc., or the spy opens flat 10-45804 number, spy and opens flat 8-231761 number, United States Patent (USP) the 2nd, mixed aliphatic esters such as the cellulose ethanoate propionic ester of 319, No. 052 records such as grade, cellulose acetate butyrate.Perhaps, also can preferably use the spy to open 2002-179701, spy opens 2002-265639, spy and opens the ester that the aromatic carboxylic acid described in the 2002-265638 and cellulose form, cellulose acylate.In above-described material, the preferred especially cellulose low-grade fatty acid ester that uses is cellulosic triacetate, cellulose ethanoate propionic ester.These cellulose esters also can mix use.
In the cellulose esters, the hydroxyl reaction of acyl group and cellulosic molecule.Cellulosic molecule is connected to form by a plurality of glucose units, and 3 hydroxyls are arranged in glucose unit.The number that acyl group is derived on these 3 hydroxyls is called degree of substitution.
It is 2.3～2.85 cellulose esters that the cellulose esters that the present invention uses can use total acyl substituted degree.
Beyond cellulosic triacetate, preferred cellulose esters comprises acyl group with carbon number 2～4 as substituting group, and the degree of substitution of acetyl group when the degree of substitution of propiono is Y, satisfies the cellulose esters of following formula as X simultaneously.
(I)2.3≤X+Y≤2.85
(II)1.4≤X≤2.85
(wherein, X is that degree of substitution, the Y of acetyl group are the degree of substitution of propiono and/or bytyry).
Wherein, (total acyl substituted degree=X+Y) is preferred to the cellulose ethanoate propionic ester of 1.9≤X≤2.5,0.1≤Y≤0.9.Not by the part of acyl substituted, the form with hydroxyl exists usually.Above-mentioned substance can utilize known method to synthesize.
These acyl substituted degree can be measured according to the method for stipulating among the ASTM-D817-96.
In the delay and the slow axis characteristic of controlling fiber cellulose ester film, the degree of substitution of the cellulose esters of use and substituent kind are important factors.The present invention preferably uses by making cellulose esters satisfy following formula, can easily obtain as the suitable delay of viewing angle compensation polaroid.
And, make the compound that has two aromatic rings at least described later, cellulose ester membrane 100 mass parts contain 0.01～20 mass parts relatively, can easily obtain having the delay that is fit to as the viewing angle compensation cellulose ester membrane and the film of slow axis characteristic, the present invention preferably uses.
The adjuvant of cellulose ester membrane
Preferred use has the compound of two aromatic rings at least among the present invention.More preferably use to have two aromatic rings at least, and at least two compounds that aromatic ring has planar structure.When manufacturing has the cellulose ester membrane of this compound, this compound and cellulose ester membrane are included in the rubber cement with organic solvent, utilize solution casting system embrane method system film.
Of the present invention have two aromatic rings and at least two compounds that aromatic ring has planar structure at least, also can be the material that two aromatic rings have approximate same planar structure.That is, pi-electron, the pi-electron that the aromaticity heterocycle has or aromatic rings that contains linking group that makes its connection that two aromatic rings have etc. has pi-electron, has at least more than 5 or 5, and it is preferred that maximum has 10 pi-electrons.
In addition, the number of the aromatic rings that described compound has is preferred 2～20, and more preferably 2～12, preferred especially 2～8.Aromatic rings comprises aromatic hydrocarbon ring, aromaticity heterocycle.The aromatic hydrocarbon ring, preferred especially 6 yuan of rings (that is phenyl ring).The aromaticity heterocycle generally is a unsaturated heterocycle.The aromaticity heterocycle, preferred 5 yuan of rings, 6 yuan of rings or 7 yuan of rings, more preferably 5 yuan of rings or 6 yuan of rings.The aromaticity heterocycle generally has maximum two keys.Heteroatom preferred nitrogen atom, oxygen atom and sulphur atom, special preferred nitrogen atom.
Aromaticity heterocycle object lesson has: furan nucleus, thiphene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazoles ring, furazan ring, triazole ring, pyranoid ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-three azine rings.Aromatic rings, preferred phenyl ring, furan nucleus, thiphene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyrazine ring and 1,3,5-three azine rings.
The bonding relation of at least two aromatic rings can be according to the situation of (a) formation condensed ring; (b) utilize the situation of singly-bound Direct Bonding; (c) situation by the linking group bonding; And the situation of (d) carrying out bonding classify (because aromatic rings does not form the spiral shell key) by linking group with pi-electron.But, (b) or under the situation (c), must have planar structure by two aromatic rings.
Condensed ring (condensed ring of plural aromatic rings) object lesson as (a) has: the indenes ring, naphthalene nucleus, azulenes, the fluorenes ring, phenanthrene ring, anthracene nucleus, the acenaphthylene ring, the diphenylene ring, aphthacene, the pyrene ring, indole ring, the iso-indoles ring, the coumarone ring, the benzothiophene ring, indolizine ring benzoxazole ring, the benzothiazole ring, the benzimidazole ring, the benzotriazole ring, purine ring, the indazole ring, the chromene ring, the quinoline ring, the isoquinoline ring, the quinolizine ring, the quinazoline ring, the cinnolines ring, quinoxaline ring, the phthalazines ring, the pyridine ring of talking endlessly, the carbazole ring, acridine, the phenanthridines ring, the xanthene ring, the azophenlyene ring, phenothiazine ring phenoxthine ring phenoxazine ring and thianthrene ring.Preferred naphthalene nucleus, azulenes, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring.
(b) singly-bound, the bonding between the carbon atom of preferred two aromatic rings.Connect two aromatic rings with plural singly-bound, can between two aromatic rings, form aliphatics ring or non-aromaticity heterocycle.
(c) or linking group (d) or have the linking group of pi-electron, the carbon atom bonding of also preferred and two aromatic rings.The preferred alkylidene of linking group, alkylene group, alkynylene ,-CO-,-O-,-NH-,-S-or its combination.The linking group that is made of combinations thereof is expressed as follows.In addition, concern and to put upside down about following linking group listed.For example, can enumerate-CO-O-,-CO-NH-,-alkylidene-O-,-NH-CO-NH-,-NH-CO-O-,-O-CO-O-,-O-alkylidene-O-,-the CO-alkylene group-,-CO-alkylene group-NH-,-CO-alkylene group-O-,-alkylidene-CO-O-alkylidene-O-CO-alkylidene ,-O-alkylidene-CO-O-alkylidene-O-CO-alkylidene-O-,-O-CO-alkylidene-CO-O-,-the NH-CO-alkylene group-,-the O-CO-alkylene group-etc., particularly with aromatic rings or the direct-connected group of aromatic heterocycle, preferred-CO-or alkylene group.
Aromatic rings and linking group can have substituting group.But substituting group must be the structure that two aromatic rings is not had steric hindrance,, has planar structure that is.Because substituent kind and position problems can appear in steric hindrance.Substituent kind, the substituting group that volume is high in the solid space (for example tertiary alkyl) is easy to generate steric hindrance, and in addition, (being the ortho position under the phenyl ring situation) produces when replacing in the position adjacent with the key of aromatic rings, because be easy to generate steric hindrance, so substituent position is preferably avoided.
Comprise in the substituting group object lesson: halogen atom (F, Cl, Br, I), hydroxyl, carboxyl, cyano group, amino, nitro, sulfo group, carbamyl, sulfamoyl, uride, alkyl, alkenyl, alkynyl, aliphatic acyl radical, aliphatics acyloxy, alkoxy, alkoxy carbonyl, alkoxycarbonyl amino, alkyl sulfenyl, alkyl sulphonyl, aliphatic amide base, aliphatics sulfoamido, aliphatics substituted-amino.Aliphatics substituted-amino formoxyl, aliphatics replace sulfamoyl, aliphatics replaces uride base and non-aromaticity heterocyclic group.
The carbon number of alkyl preferred 1～8.Compare chain-like alkyl more preferably with cyclic alkyl, preferred especially straight chain shape alkyl.Alkyl can also have substituting group (for example hydroxyl, carboxyl, alkoxy, alkyl-substituted amino).The object lesson of alkyl (comprising substituted alkyl) can be enumerated methyl, ethyl, normal-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxy ethyl and 2-diethylamino ethyl.The carbon number of alkenyl preferred 2～8.Compare more preferably straight chain shape alkenyl, special preferred straight chain shape alkenyl with the closed chain thiazolinyl.Alkenyl also can have substituting group.Alkenyl for example has vinyl, allyl and 1-hexenyl.The carbon number of alkynyl preferred 2～8.Compare with the ring-type alkynyl, more preferably chain alkynyl, especially preferably straight chain shape alkynyl.Alkynyl also can have substituting group.The alkynyl object lesson has: ethinyl, 1-butynyl and 1-hexin base.
The carbon number of aliphatic acyl radical preferred 1～10.The aliphatic acyl radical example has acetyl group, propiono and bytyry.The carbon number of aliphatics acyloxy preferred 1～10.The aliphatics acyloxy for example has acetoxyl group.The carbon number of alkoxy preferred 1～8.Alkoxy also can also have substituting group (for example alkoxy).In (containing alkoxy) example of alkoxy methoxyl, ethoxy, butoxy and methoxy ethoxy are arranged.The carbon number of alkoxy carbonyl group preferred 2～10.Methoxycarbonyl and ethoxy carbonyl are arranged in the example of alkoxy carbonyl.The carbon number of alkoxycarbonyl amino preferred 2～10.Methoxycarbonyl amino and ethoxy carbonyl amino are arranged in the example of alkoxycarbonyl amino.
The carbon number of alkylthio group preferred 1～12.The example of alkylthio group has methyl sulphur, ethyl sulphur and octyl group sulphur.Preferred 1～8 of the carbon number of alkyl sulphonyl.The example of alkyl sulphonyl has mesyl and ethane sulfonyl.The carbon number of aliphatic amide base preferred 1～10.The example of aliphatic amide base has acetamide.The sulfa carbon number of aliphatics preferred 1～8.The sulfa example of aliphatics has first sulfanilamide (SN), fourth sulfanilamide (SN) and positive hot sulfanilamide (SN).The carbon number of aliphatics substituted-amino preferred 1～10.The example of aliphatics substituted-amino has dimethylamino, diethylamino and 2-carboxy ethyl amino.The carbon number preferred 2～10 of aliphatics substituted-amino formoxyl.The example of aliphatics substituted-amino formoxyl has methylamino formoxyl and diethylamino formoxyl.Aliphatics replaces the carbon number preferred 2～10 of uride base.The example that aliphatics replaces sulfamoyl has methyl sulfamoyl and diethyl amino sulfonyl.The example that aliphatics replaces the uride base has the methyl uride.The example of non-aromaticity heterocycle has piperidyl and morpholinyl.
The molecular weight of these compounds preferred 300～800.Boiling point is preferred more than 260 ℃ or 260 ℃.Can use commercially available determinator (for example TG/DTA100, セ イ コ-Electronics Industry Company's system) to measure boiling point.Enumerate concrete example below, but be not limited thereto.
A-1??????????????????????????????????A-2
A-3??????????????????????????????????A-4
A-5??????????????????????????????????A-6
A-7
A-8
A-9
Change 2
A-1????????????????????????????????A-2
??????????????
A-3????????????????????????????????A-4
A-5????????????????????????????????A-6
??
A-7
A-8
A-9
Change 3
A-15
A-16
A-17???????????????????????????????????????????????A-18
A-19
A-20
A-21
Change 4
A-22
A-23
A-24
A-25
A-26
A-27
A-28???????????????????????????????????A-29
??
Change 5
A-30???????????????????????????????????A-31
??????????????
A-32
A-33
A-34
A-35
A-36?????????????????????????????????A-37
???
A-38
Change 6
A-39
A-40
A-41
A-42
A-43??????????????????????A-44
Change 7
A-45
A-46
A-47?????????????????????????????????????A-48
??????????????????
A-49?????????????????????????????????????A-50
A-51
Change 8
A-52???????????????????????????????????A-53
??
A-54
A-55
A-56???????????????????????????????????A-57
A-58???????????????????????????????????A-59
???????????????????????
A-60???????????????????????????????????A-61
A-62???????????????????????????????????A-63
????????????????????????
Change 9
A-64???????????????????????????????????????????A-65
????????????????????????
A-66???????????????????????????????????????????A-67
A-68
A-69
A-70???????????????????????????????????????????A-71
A-72???????????????????????????????????????????A-73
??????????????????????????
Change 10
A-74??????????????????????????????????A-75
A-76??????????????????????????????????A-77
??
A-78??????????????????????????????????A-79
???????????????
A-80
A-81??????????????????????????????????A-82
A-83??????????????????????????????????A-84
Change 11
A-85
A-86??????????????????????????????????????????????????????????A-87
A-88
A-89
A-90??????????????????????????????????????????????????????????A-91
???????????????????????????
A-92
Change 12
A-93
A-94
And the present invention uses has compound that two aromatic rings and at least two aromatic rings have planar structure except that above-mentioned, the also preferred compound with triphenylene basic ring that uses following general formula (1) to represent at least.
Change 13
General formula (1)
In the general formula (1), R
1, R
2, R
3, R
4, R
5And R
6Represent independently respectively hydrogen atom, halogen atom, nitro, sulfo group, fat-based, aromatic radical, heterocyclic radical ,-O-R
11,-S-R
12,-CO-R
13,-O-CO-R
14,-CO-O-R
15,-O-CO-O-R
16,-NR
17-R
18,-CO-NR
19-R
20,-NR
21-CO-R
22,-O-CO-NR
23-R
24,-SiR
25R
26R
27,-O-SiR
28R
29R
30,-S-CO-R
31,-O-SO
2-R
32,-SO-R
33,-NR
34-CO-O-R
35,-SO
2-R
36Or-NR
37-CO-NR
38R
39R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
18, R
19, R
20, R
21, R
22, R
23, R
24, R
25, R
26, R
27, R
28, R
29, R
30, R
31, R
32, R
33, R
34, R
35, R
36, R
37, R
38, R
39Represent hydrogen atom, fat-based, aromatic radical or heterocyclic radical respectively independently; And R
1And R
2, R
3And R
4Or R
5And R
6Bonding forms ring mutually.
R
1, R
2, R
3, R
4, R
5And R
6Preferably-O-R
11,-S-R
12,-O-CO-R
14,-O-CO-O-R
16,-NR
17-R
18,-NR
21-CO-R
22Or-O-CO-NR
23-R
24More preferably-O-R
11,-S-R
12,-O-CO-R
14,-O-CO-O-R
16Or-O-CO-NR
23-R
24Especially preferably-O-R
11,-O-CO-R
14Most preferably-O-CO-R
14
R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
18, R
19, R
20, R
21, R
22, R
23, R
24, R
25, R
26, R
27, R
28, R
29, R
30, R
31, R
32, R
33, R
34, R
35, R
36, R
37, R
38And R
39Preferred hydrogen atom, fat-based, aromatic radical;-O-CO-R
14R
14Aromatic radical most preferably.In addition, R in the general formula (1)
1, R
2, R
3, R
4, R
5And R
6Preferred identical group.
Among the present invention, fat-based is meant alkyl, alkenyl, alkynyl, substituted alkyl.Substituted alkenyl base and substituted alkynyl.Alkyl can be ring-type (naphthenic base).In addition, alkyl can have branch.The carbon number of alkyl is preferred 1～30, and more preferably 1～20, most preferably 1～10.Alkyl for example has: methyl, ethyl, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, tertiary pentyl, hexyl, octyl group, uncle's octyl group, dodecyl and tetracosyl.Alkenyl also can be ring-type (a ring grease thiazolinyl).In addition, alkenyl also can have branch.Alkenyl also can have two or more pairs of keys.
The carbon number of alkenyl is preferred 2～30, and more preferably 2～20, most preferably 2～10.Non-limiting examples of alkenyls has vinyl.Allyl and 3-heptenyl.Alkynyl can be ring-type (cycloalkynyl radical).In addition, alkynyl can have branch.Alkynyl also can have plural triple bond.The carbon number of alkynyl is preferred 2～30, and more preferably 2～20, most preferably 2～10.Alkynyl for example has ethinyl, 2-propynyl, 1-pentynyl and 2, the hot diynyl of 4-.
The substituting group of substituted alkyl, substituted alkenyl base and substituted alkynyl for example have halogen atom, nitro, sulfo group, aromatic radical, heterocyclic radical ,-O-R
41,-S-R
42,-CO-R
43,-O-CO-R
44,-CO-O-R
45,-O-CO-O-R
46,-NR
47R
48,-CO-NR
49R
50,-NR
45-CO-R
52,-O-CO-NR
53R
54,-SiR
55R
56R
57R
58And-O-SiR
59R
60R
61R
62R
41, R
42, R
43, R
44, R
45, R
46, R
47, R
48, R
49, R
50, R
51, R
52, R
53, R
54, R
55, R
56, R
57, R
58, R
59, R
60, R
61And R
62Represent hydrogen atom, fat-based, aromatic radical or heterocyclic radical respectively independently.
The moieties of substituted alkyl is identical with abovementioned alkyl.The example of substituted alkyl has: benzyl, phenethyl, 2-methoxy ethyl, ethoxyl methyl, 2-(2-methoxy ethoxy) ethyl, 2-hydroxyethyl, hydroxymethyl, 2-carboxy ethyl, carboxyl methyl, ethoxy carbonyl methyl, 4-acryloxy butyl, trichloromethyl and perfluor amyl group.The alkenyl part of substituted alkenyl base is identical with above-mentioned alkenyl.Styryl and 4-methoxyl-styrene are arranged in the example of substituted alkenyl base.The alkynyl part of substituted alkynyl is identical with above-mentioned alkynyl.The example of substituted alkynyl has: 4-butoxy phenyl ethinyl, 4-propylbenzene ethyl-acetylene base and trimethyl silyl ethinyl.
Aromatic radical is meant aryl and substituted aryl among the present invention.The carbon number of aryl is preferred 6～30, and more preferably 6～20, most preferably 6～10.Phenyl, 1-naphthyl and 2-naphthyl are arranged in the example of aryl.The substituent example of substituted aryl has: halogen atom, nitro, sulfonic group, fat-based, aromatic radical, heterocyclic radical ,-O-R
71,-S-R
72,-CO-R
73,-O-CO-R
74,-CO-O-R
75,-O-CO-O-R
76,-NR
77R
78,-CO-NR
79R
80,-NR
81-CO-R
82,-O-CO-NR
83R
84,-SiR
85R
86R
87R
88And-O-SiR
89R
90R
91R
92
R
71, R
72, R
73, R
74, R
75, R
76, R
77, R
78, R
79, R
80, R
81, R
82, R
83, R
84, R
85, R
86, R
87, R
88, R
89, R
90, R
91And R
92Represent hydrogen atom, fat-based, aromatic radical or heterocyclic radical respectively independently.
The aryl moiety of substituted aryl is identical with above-mentioned aryl.The example of substituted aryl has: right-xenyl, 4-phenylacetylene base phenyl, the 2-methoxyphenyl, the 3-methoxyphenyl, the 4-methoxyphenyl, the 2-ethoxyl phenenyl, the 3-ethoxyl phenenyl, the 4-ethoxyl phenenyl, 2-propoxyl group phenyl, 3-propoxyl group phenyl, 4-propoxyl group phenyl, the 2-butoxy phenyl, the 3-butoxy phenyl, the 4-butoxy phenyl, the own oxygen base of 2-phenyl, the own oxygen base of 3-phenyl, the own oxygen base of 4-phenyl, the 2-octyloxyphenyl, the 3-octyloxyphenyl, the 4-octyloxyphenyl, 2-dodecyloxy phenyl, 3-dodecyloxy phenyl, 4-dodecyloxy phenyl, 2-lignocerane oxygen base phenyl, 3-lignocerane oxygen base phenyl, 4-lignocerane oxygen base phenyl, 3, the 4-Dimethoxyphenyl, 3,4-diethoxy phenyl, 3,4-two own oxygen base phenyl, 2, the 4-Dimethoxyphenyl, 2,4-diethoxy phenyl, 2,4-two own oxygen base phenyl, 3, the 5-Dimethoxyphenyl, 3, the 5-Dimethoxyphenyl, 3,5-two own oxygen base phenyl, 3,4, the 5-trimethoxyphenyl, 3,4,5-triethoxy phenyl, 3,4,5-three own oxygen base phenyl, 2,4, the 6-trimethoxyphenyl, 2,4,6-triethoxy phenyl, 2,4,6-three own oxygen base phenyl, the 2-fluorophenyl, the 3-fluorophenyl, the 4-fluorophenyl, the 2-chlorphenyl, the 3-chlorphenyl, the 4-chlorphenyl, the 2-bromophenyl, the 3-bromophenyl, the 4-bromophenyl, 3, the 4-difluorophenyl, 3, the 4-dichlorophenyl, 3, the 4-dibromo phenyl, 2, the 4-difluorophenyl, 2, the 4-dichlorophenyl, 2, the 4-dibromo phenyl, 3, the 5-difluorophenyl, 3, the 5-dichlorophenyl, 3, the 5-dibromo phenyl, 3,4, the 5-trifluorophenyl, 3,4, the 5-trichlorophenyl, 3,4,5-tribromo phenyl, 2,4, the 6-trifluorophenyl, 2,4, the 6-trichlorophenyl, 2,4,6-tribromo phenyl, pentafluorophenyl group, five chlorophenyl, penta-bromophenyl, the 2-iodophenyl, the 3-iodophenyl, the 4-iodophenyl, the 2-formylphenyl, the 3-formylphenyl, the 4-formylphenyl, the 2-benzoyloxy phenyl, the 3-benzoyloxy phenyl, the 4-benzoyloxy phenyl, the 2-carboxyl phenyl, the 3-carboxyl phenyl, the 4-carboxyl phenyl, neighbour-tolyl, between-tolyl, right-tolyl, the 2-ethylphenyl, the 3-ethylphenyl, the 4-ethylphenyl, 2-(2-methoxy ethoxy) phenyl, 3-(2-methoxy ethoxy) phenyl, 4-(2-methoxy ethoxy) phenyl, 2-ethoxy carbonyl phenyl, 3-ethoxy carbonyl phenyl, 4-ethoxy carbonyl phenyl, 2-benzoyloxy phenyl, 3-benzoyloxy phenyl and 4-benzoyloxy phenyl.
Heterocycle can have substituting group among the present invention.The heterocycle of heterocyclic radical is 5 yuan of rings or 6 yuan of rings preferably.Also can the condensation cycloaliphatic ring on the heterocycle of heterocyclic radical, aromatic rings or other heterocycle.The heteroatoms of heterocycle for example has B, N, O, S, Se and Te.Heterocyclic radical for example has pyrrolidine ring, morpholine ring, 2-ボ ラ 1,3-two oxa-s penta ring and 1,3-thiazoles alkane ring.Unsaturated heterocycle for example has imidazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, Ben Bing trioazole ring, benzo selenazoles ring, pyridine ring, pyrimidine ring and quinoline ring.The substituent example of heterocycle is identical with the substituent example of substituted aryl.
Molecular weight preferred 300～2000 with compound of triphenylene basic ring.The boiling point of compound is preferred more than 260 ℃ or 260 ℃.Can use commercially available determinator (for example TG/DTA100, セ イ コ-Electronics Industry Company's system) to measure boiling point.The object lesson of R of following general formula (2) that the substituting group correspondence of the R1～R6 of above-mentioned general formula (1) has the compound of 6 identical triphenylene basic rings is expressed as follows.
Change 14
General formula (2)
As R; for example have: (B-1) fluorine; (B-2) chlorine; (B-3) bromine; (B-4) formyl; (B-5) benzoyl; (B-6) carboxyl; (B-7) butyl amino; (B-8) dibenzyl amino; (B-9) trimethylsiloxy; (B-10) 1-pentynyl (1-ペ Application チ ニ Le); (B-11) ethoxy carbonyl; (B-12) 2-hydroxyl-oxethyl carbonyl; (B-13) phenyloxycarbonyl; (B-14) N-phenyl amino formyl; (B-15) N; N-diethylamino formyl; (B-16) 4-methoxybenzoyl oxygen base; (B-17) N-phenyl amino formyloxy; (B-18) hexyl oxygen base; (B-19) the own oxygen base of 4-benzoyloxy; (B-20) ethoxy; (B-21) benzoyloxy; (B-22) between-dodecyloxy phenyl sulphur; (B-23) uncle-octyl group sulphur; (B-24) right-fluoro benzoyl sulphur; (B-25) isobutyryl sulphur; (B-26) right-methylbenzene sulfinyl; (B-27) second sulfinyl; (B-28) benzenesulfonyl; (B-29) mesyl; (B-30) 2-methoxy ethoxy; (B-31) propoxyl group; (B-32) 2-hydroxyl-oxethyl; (B-33) 2-carboxyl ethoxy; (B-34) 3-heptene oxygen base; (B-35) 2-phenyl ethoxy; (B-36) trichlorine methoxyl; (B-37) 2-propenyloxy group; (B-38) 2, hot two alkynyloxy groups of 4-; (B-39) perfluor amoxy; (B-40) ethoxycarbonyl methoxy; (B-41) right-methoxyl phenoxy group; (B-42) between-ethoxy phenoxy; (B-43) neighbour-chlorophenoxy; (B-44) between-the dodecyloxy phenoxy group; (B-45) pyridine oxygen base; (B-46) phenyl-pentafluoride formyloxy; (B-47) right-own oxygen base benzoyloxy; (B-48) 1-Naphthoyloxy; (B-49) 2-Naphthoyloxy; (B-50) 5-imidazoles carbonyl oxygen base; (B-51) neighbour-phenyloxycarbonyl benzoyl oxygen; (B-52) between-(2-methoxy ethoxy) benzoyloxy; (B-53) between-the carboxyl benzoyloxy; (B-54) right-formyl benzoyloxy; (B-55) between-the ethoxy carbonyl benzoyloxy; (B-56) right-pivaloyl benzoyloxy; (B-57) propiono oxygen; (B-58) phenyl acetoxyl group; (B-59) cinnamoyl oxygen base; (B-60) hydroxyl acetoxyl group; (B-61) ethoxy carbonyl acetoxyl group; (B-62) between-butoxy phenyl propine acyloxy; (B-63) propine acyloxy; (B-64) trimethyl silyl propine acyloxy; (B-65) 4-octene acyloxy (4-オ Network テ ノ イ Le オ キ シ); (B-66) 3-hydroxypropyn oxygen base; (B-67) 2-methoxy ethoxy acetoxyl group; (B-68) perfluor butyryl acyloxy; (B-69) mesyloxy; (B-70) right-tosyloxy; (B-71) triethylsilyl; (B-72) between-phenoxy butoxy base carbonylamino; (B-73) hexyl; (B-74) phenyl; (B-75) 4-pyridine radicals; (B-76) benzyloxycarbonyloxy base; (B-77) between-the chlorobenzene formamide; (B-78) 4-toluidine etc.
In the substituting group of the R1～R6 of above-mentioned general formula (1), have 5 hydrogen, the instantiation of the R of the following relatively general formula of the compound of the triphenylene basic ring of 6 identical R (3) is expressed as follows:
Change 15
General formula (3)
As R, for example have: (B-79) nitro, (B-80) sulfo group, (B-81) formyl, (B-82) carboxyl, (B-83) methoxycarbonyl, (B-84) benzyloxycarbonyl, (B-85) phenyloxycarbonyl.
The R of above-mentioned general formula (1)
1Be hydroxyl, R
2～R
65 substituting groups be compound with triphenylene basic ring of identical R, the instantiation of the R corresponding with following general formula (4) is expressed as follows:
Change 16
General formula (4)
As R, for example have: (B-86) butoxy, (B-87) own oxygen base, (B-88) dodecyloxy, (B-89) hexyl acyloxy, (B-90) carboxyl methoxyl.
And, as the R of above-mentioned general formula (1)
1～R
5Other example, following B-91～B100 is arranged.
Change 17
B-91??????????????????????????????????B-92
???????
B-93?????????????????????????????????B-94
??
B-95
B-96
Change 18
B-97??????????????????????????B-98
B-99
B-100
From the viewpoint that prevents to leach, contained in the compound have two aromatic rings and at least two additions of compound in rubber cement that aromatic rings has planar structure at least, preferably in the rubber cement of cellulose esters, cooperate 0.4～10 quality %, the more preferably scope of 1.5～10 quality %.In addition, preferred 0.01～20 mass parts of relative cellulose esters 100 mass parts of the amount that in cellulose ester membrane, contains, more preferably 5～20 quality %, preferred especially 8～20 quality %.
The cellulose ester membrane that uses in the liquid crystal indicator that the present invention relates to preferably contains in cellulose ester membrane and prevents anti aging dopes such as the antioxidant that wears out or free radical scavenger.
Above-mentioned anti aging dope preferably uses the hindered phenol based compound, for example have: 2,6-di-t-butyl-p-Cresol, [3-(3 for pentaerythrite-four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol-two [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], 1, [3-(3 for 6-hexanediol-two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2,4-pair-(n-octyl sulphur)-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1,3,5-three azines], 2, [3-(3 for 2-sulfo--di ethylene bis, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide (ヒ De ロ シ Application Na マ ミ De)), 1,3,5-trimethyl-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-isocyanuric acid esters etc.Preferred especially 2,6-di-t-butyl-paracresol, pentaerythrite-four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol-two [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester].In addition, also can share N, hydrazines such as N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propiono] hydrazine are that phosphorus such as metal inert agents and three (2, the 4-di-tert-butyl-phenyl) phosphate are processing stabilizers.The addition of these compounds, relatively cellulose esters is in the preferred 1ppm of mass ratio～1.0%, more preferably 10～1000ppm,
In addition, be subjected to ultraviolet the influence and wear out, except that above-mentioned aging resister, preferably contain the ultraviolet ultraviolet light absorber that cuts off or weaken the irradiating liquid crystal display device in order to prevent cellulose ester membrane of the present invention.Ultraviolet light absorber preferably has the excellent absorption ability to the ultraviolet ray below the wavelength 370nm, and considers from liquid crystal expressivity aspect, the material of the visible light that a small amount of absorbing wavelength 400nm is above.For example have: dihydroxy benaophenonel based compound, benzotriazole based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, nickel complex salt based compound etc.Particularly preferred ultraviolet light absorber is benzotriazole based compound or benzophenone based compound.Wherein, consider preferred benzotriazole cpd from cellulose esters being produced unnecessary painted few this respect.For example, the チ ヌ PVC Application 109 of preferred use チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ corporate system, チ ヌ PVC Application 171, チ ヌ PVC Application 326, チ ヌ PVC Application 327, チ ヌ PVC Application 328 etc., low-molecular-weight ultraviolet light absorber is identical with plastifier, on the reel film, separate out in the system film according to use amount, because volatilization sometimes is so its addition is 0.01～5 quality %, preferred 0.13～3 quality % to cellulose esters.In addition, sometimes these ultraviolet light absorbers also with have two aromatic rings useful at least to the present invention, and the compound that at least two aromatic rings have planar structure repeats mutually.
Preferably contain particulate among the present invention in cellulose ester membrane, particulate for example preferably makes it contain inorganic particles play cross-linked polymer particulates such as silicon dioxide, titania, aluminium oxide, zirconia, lime carbonate, porcelain earth, talcum powder, sintering calcium silicate, afwillite, alumina silicate, magnesium silicate, calcium phosphate.Wherein, because silicon dioxide can reduce the turbidity of film, so preferred.The mean grain size of 2 particles of particulate is in the scope of 0.01～1.0 μ m, preferred 0.005～0.3 quality % of the relative cellulose esters of its content.Most cases utilizes organism to carry out surface treatment to silica-based fine particles, and such material can reduce the turbidity of film, so preferably use.Carrying out the preferred organism of surface treatment for example has: halogenated silanes class, alkoxyl silicone alkanes (the alkoxyl silicone alkanes that particularly has methyl), silazane, siloxane etc.The mean grain size of particulate is big, and coarse effect is strong, and on the contrary, mean grain size is little, and the transparency is good, thereby the mean grain size of the primary particle of particulate is preferably 5～50nm, more preferably 7～16nm.These particulates preferably exist as agglutinator in cellulose ester membrane usually, make the cellulose ester membrane surface form the concavo-convex of 0.01～1.0 μ m.Silicon dioxide microparticle for example has: the AEROSIL of ア エ ロ ジ Le corporate system (ア エ ロ ジ Le) 200,200V, 300, R972, R972V, R974, R202, R812, OX50, TT600 etc.Preferred AEROSIL (ア エ ロ ジ Le) 200V, R972, R972V, R974, R202, R812.These particulates can two or more share.When two or more share, can use with ratio mixing arbitrarily.In this case, the particulate that mean grain size or material are different can use AEROSIL (ア エ ロ ジ Le) 200V and R972V 0.1: 99.9～99.9: 0.1 scope with mass ratio.Among the present invention, when the preparation rubber cement, can contain particulate and cellulose esters, other adjuvant and organic solvent simultaneously, disperse.Under the state that described cellulose ester solution so fully disperses particularly preferably in particle dispersion liquid, the preparation rubber cement.For disperse particles, preferably be immersed in the organic solvent in advance after, utilize dispersion machine (high pressure diverting device) fully to disperse with high shear force.Preferably after it, be dispersed in the organic solvent of volume, itself and cellulose ester solution are mixed, be mixed and made into rubber cement with the series connection stirring machine.In this case, also can add ultraviolet light absorber and make UVA liquid particle dispersion liquid.
Above-mentioned aging resister, ultraviolet light absorber and/or particulate, can be when cellulose ester solution be prepared and cellulose esters or solvent add together, also can be in the solution preparation or the preparation back add.
To making the useful organic solvent of rubber cement of the present invention, so long as simultaneously the dissolving cellulos ester, have just can the using of compound, other adjuvant that at least 2 aromatic rings and at least two aromatic rings have planar structure, be not particularly limited.For example, for example have: methylene chloride as chlorine-based organic solvent; As the chlorine-free organic solvent, for example have: methyl acetate, ethyl acetate, pentyl acetate, acetone, tetrahydrofuran, 1,3-two oxa-s penta ring, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2 tfifluoroethyl alcohol, 2,2,3,3-hexafluoro-1-propyl alcohol, 1,3-two fluoro-2-propyl alcohol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propyl alcohol, 1,1,1,3,3,3-hexafluoro-2-propyl alcohol, 2,2,3,3,3-five fluoro-1-propyl alcohol, nitroethane etc. can preferably use methylene chloride, methyl acetate, ethyl acetate, acetone.Preferred especially methyl acetate.
In the rubber cement of the present invention, except that above-mentioned organic solvent, preferably contain the alcohol of the carbon number 1～4 of 1～40 quality %.When the ratio of alcohol in the rubber cement raise, reel film generation gelation was peeled off from metal support easily, and in addition, the ratio of alcohol also has the effect that promotes cellulose esters dissolving in chlorine-free organic solvent system after a little while.As the alcohol of carbon number 1～4, methyl alcohol, ethanol, n-propanol, isopropyl alcohol are for example arranged.Normal butyl alcohol, sec-butyl alcohol, the tert-butyl alcohol.Wherein, lower from stability, the boiling point of rubber cement, drying property good and consideration such as avirulence, preferred alcohol.
The concentration of the cellulose esters in the rubber cement is adjusted to 15～40 quality % scopes, rubber cement viscosity is adjusted to 100～500 pool (P) scopes, can obtain having the quality of good face, is preferred.
Can add plastifier in the rubber cement that the present invention relates to.As plastifier, for example preferably using phosphate is that plastifier, phthalate ester are that plastifier, ethyl glycolate are that plastifier, citrate are plastifier etc.As phosphate is plastifier, for example has: triphenyl, tricresyl alkaliine, cresols diphenyl phosphoester, octyl group diphenyl phosphoester, diphenyl xenyl phosphate, trioctylphosphine phosphate, Tributyl phosphate ester etc.; As phthalate ester is plastifier, for example has: diethyl phthalate, DMEP, repefral, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, dibenzyl phthalate; As citrate, for example have: acetyl triethyl citrate, acetyl tributyl citrate; As ethyl glycolate is plastifier, for example has: in addition alkyl phthaloyl alkyl alcohol acid esters, also has butyl oleate, ricinoleic acid methyl ethyl ester, decanedioic acid (セ バ チ Application) dibutyl ester, triglycerin acetic acid esters etc.Can preferably use ethyl glycolate among the present invention is plastifier, the alkyl of phthaloyl alkyl alcohol acid esters, and it is 1～8 alkyl that carbon number is for example arranged.Preferred ethyl glycolate is a plastifier, for example have: methyl phthalyl methyl glycollate, the ethyl methyl phthallyl ethyl glycollate, propyl group phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl group phthalyl glycollic acid monooctyl ester, the methyl methyl phthallyl ethyl glycollate, ethyl phthalyl methyl glycollate, ethyl phthalyl propyl glycolate, the propyl group methyl phthallyl ethyl glycollate, methyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycollate, the butyl methyl phthallyl ethyl glycollate, propyl group phthalyl butyl glycolate, butyl phthalyl propyl glycolate, methyl phthalyl glycollic acid monooctyl ester, ethyl phthalyl glycollic acid monooctyl ester, octyl group phthalyl methyl glycollate, octyl group methyl phthallyl ethyl glycollate etc., preferable methyl phthalyl methyl glycollate, the ethyl methyl phthallyl ethyl glycollate, propyl group phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl group phthalyl glycollic acid monooctyl ester, preferred especially ethyl methyl phthallyl ethyl glycollate.Alkyl also can make above-mentioned phthalyl alkyl glycolate ester mix two or more uses.
Consider the addition of alkyl phthalic acyl alkyl glycolate ester, preferred 1～10 quality % of cellulose esters relatively from the reduction of bonding force and by the inhibition aspect that immerses film.Among the present invention, also can make the plastifier and the alkyl phthalic acyl alkyl glycolate ester of above-mentioned other be mixed together use.
Cyclo-olefin-polymer films
The cyclo-olefin-polymer films that the present invention is used describes below.
The cyclic olefin polymer that the present invention uses is made of the fluoropolymer resin that contains the ester ring type structure.
Preferred cyclic olefin polymer obtains cyclic olefin polymerization or copolymerization.Cyclic olefin for example has: norborene, bicyclopentadiene, Fourth Ring 12 (carbon) alkene, ethyl Fourth Ring 12 (carbon) alkene, ethylidene Fourth Ring 12 (carbon) alkene, Fourth Ring [7.4.0.110,13.02,7] and-13-2,4,6, the unsaturated hydrocarbon and the derivant thereof of multiring structures such as 11-tetraene; Cyclobutane, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methyl butyl)-1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydrochysene-4, the unsaturated hydrocarbon of single ring architectures such as 7-methanol-based-1H-indenes, cycloheptene, cyclopentadiene, cyclohexadiene and derivant thereof etc.Substituting group can have polar group in these cyclic olefins.The preferred hydroxyl of polar group, carboxyl, alkoxy, epoxy radicals.Glycidyl, carboxyl, carbonyl, amino, ester group, acid anhydride etc., preferred especially ester group, carboxyl or acid anhydride.
Preferred cyclic olefin polymer can be the material that the monomer addition copolymerization beyond the cyclic olefin obtains.Monomer that can addition copolymerization for example has ethene or alpha-olefins such as ethene, propylene, 1-butylene, 1-amylene; 1,4-hexadiene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 1, diene such as 7-octadiene etc.
Cyclic olefin can utilize polyaddition reaction or transposition ring-opening polymerization to obtain.In the presence of catalyzer, carry out polymerization.As the addition polymerization catalyzer, the polymerization catalyst of vfanadium compound and organo-aluminum compound formation etc. is for example arranged.As ring-opening polymerization catalyst, for example have: the polymerization catalyst that metal halide, nitrate or acetylacetonate compound such as ruthenium, rhodium, palladium, osmium, iridium, platinum and reductive agent constitute; The perhaps polymerization catalyst that constitutes of metal halide such as titanium, vanadium, zirconium, tungsten, molybdenum or acetylacetonate compound and organo-aluminum compound etc.Polymerization temperature, pressure etc. are not particularly limited, and is common under-50 ℃～100 ℃ polymerization temperature, 0～490N/cm
2Polymerization pressure under carry out polymerization.
The cyclic olefin polymer that the present invention uses preferably after cyclic olefin polymerization or copolymerization, carries out hydrogenation reaction, and the unsaturated link in the molecule is become saturated bond.In the presence of known hydrogenation catalyst, be blown into hydrogen and carry out hydrogenation reaction.As hydrogenation catalyst, for example have: cobalt acetate ,/even series catalysts that the composition of the transistion metal compound/alkyl metal cpd of aluminium triethyl, acetopyruvic acid nickel/triisobutyl aluminium, dichloride triscyclopentadienyl titanium (チ ノ セ Application)/n-BuLi, titanocene dichloride (ジ Le コ ノ セ Application)/s-butyl lithium, four titanium butoxide acid esters/dimethyl magnesium class constitutes; Heterogeneous system metallic catalysts such as nickel, palladium, platinum; Nickel/silicon dioxide, nickel/zeyssatite, nickel/aluminium oxide, palladium/carbon, palladium/silicon dioxide, palladium/zeyssatite, palladium/alumina type metallic catalyst loaded on unevenness solid supported catalyst that forms on the carrier etc.
Perhaps, cyclic olefin polymer for example also has following norbornene polymer.Aforementioned norbornene-based polymer, preferably contain the norborene skeleton as repetitive, its object lesson can preferably use the spy to open clear 62-252406 communique, the spy opens clear 62-252407 communique, Te Kaiping 2-133413 communique, the spy opens clear 63-145324 communique, the spy opens clear 63-264626 communique, Te Kaiping 1-240517 communique, special public clear 57-8815 communique, Te Kaiping 5-39403 communique, Te Kaiping 5-43663 communique, Te Kaiping 5-43834 communique, Te Kaiping 5-70655 communique, Te Kaiping 5-279554 communique, Te Kaiping 6-206985 communique, Te Kaiping 7-62028 communique, Te Kaiping 8-176411 communique, the material of record in the Te Kaiping 9-241484 communique etc., but be not limited thereto.In addition, these can use separately, also can mix two or more uses.
Among the present invention, in the aforementioned norbornene-based polymer, preferably contain repetitive with any one expression in the following structural formula (I)～(IV).
Change 19
(I)
(II)
(III)
(IV)
In the aforementioned structural formula (I)～(IV), A, B, C and D represent the organic group of hydrogen atom or 1 valency respectively independently.
In addition, in the aforementioned norbornene-based polymer, preferably with following structural formula (V) or (VI) expression compound at least a and can carry out metathesis polymerization with the unsaturated cyclic compounds of its copolymerization, make the polymkeric substance that obtains carry out hydrogenation and obtain the hydrogenation polymkeric substance.
Change 20
(V)
(VI)
A, B, C and D represent the organic group of hydrogen atom or 1 valency respectively independently in the aforementioned structural formula.
Wherein, above-mentioned A, B, C and D are not particularly limited, but preferred hydrogen atom, halogen atom, any monovalent organic radical group, or are connected with organic group by at least two valency linking groups, and these can be the same or different.In addition, A or B and C or D can form monocycle or multiring structure.Wherein, above-mentioned at least two valency linking groups contain with oxygen atom, sulphur atom, nitrogen-atoms to be the heteroatoms of representative, ether, ester, carbonyl, polyurethane, acid amides, thioether etc. for example to be arranged, but be not limited thereto.In addition, also can replace above-mentioned organic group again by above-mentioned linking group.
In addition, can be that other monomer of monomer copolymerization for example can use: the alpha-olefin of carbon numbers 2～20 such as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 1-dodecane alkene, 1-tetradecane alkene, 1-hexadecane alkene, 1-octadecane alkene, 1-eicosylene, and derivant with norborene; Cyclobutane, cyclopentene, cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydrochysene-4,7-methanol-based-cycloolefin and derivants thereof such as 1H-indenes; 1,4-hexadiene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 1, non-conjugated dienes such as 7-octadiene etc.Wherein, preferred alpha-olefin, special optimal ethylene.
Wherein, can be that other monomer of monomer copolymerization can be distinguished separately and uses with norborene, also can two or more mixing use.Make the norborneol alkene monomer and can be that other monomer of monomer copolymerization is when carrying out addition copolymerization with norborene, to structural unit from the norborneol alkene monomer in the addition copolymer, suitably select with ratio from the structural unit of other monomer that can copolymerization, by quality ratio, be generally 30: 70～99: 1, preferred 50: 50～97: 3, more preferably 70: 30～95: 5.
When remaining in unsaturated link in the polymer molecular chain and making it saturated, consider that from light aging resisting and the aging viewpoint of weatherability hydrogenation rate is more than 90% or 90%, more than preferred 95% or 95%, more than preferred especially 99% or 99% by hydrogenation reaction.
In addition, the cyclic olefin polymer that the present invention uses for example has: the thermoplasticity saturated norbornene that the spy opens flat 5-2108 communique paragraph numbering [0014]～[0019] record is a resin, the spy opens the thermoplastic norbornene based polymer of 2001-277430 communique paragraph numbering [0015]～[0031] record, the thermoplastic norbornene that the spy opens [0008]～[0045] record of 2003-14901 communique paragraph numbering is a resin, the spy opens the norbornene resin composition of 2003-139950 communique paragraph numbering [0014]～[0028] record, the spy opens the norbornene resin of 2003-161832 communique paragraph numbering [0029]～[0037] record, the spy opens the norbornene resin of 2003-195268 communique paragraph numbering [0027]～[0036] record, the spy opens the fluoropolymer resin that contains the ester ring type structure of 2003-211589 communique paragraph numbering [0009]～[0023] record, the spy opens the norbornene-based polymer resin of 2003-211588 communique paragraph numbering [0008]～[0024] record or alicyclic vinyl ring type hydrocarbon polymer resin etc.
The molecular weight of the cyclic olefin polymer that the present invention uses, can suitably select according to the purpose of using, utilize cyclohexane solution (using toluene solution when fluoropolymer resin does not dissolve), adopt the gel permeation chromatography molecular weight, the weight-average molecular weight that is converted into polyisoprene or polystyrene is generally 5000～500000, during preferred 8000～200000, more preferably 10000～100000 scope, the physical strength of formed body and processing and forming can reach good balance, are preferred.
In addition, when relative cyclic olefin polymer 100 mass parts, during the antioxidant of the low volatility of cooperation 0.01～5 mass parts, can prevent polymer unwinds or variable color effectively during processing and forming.
As antioxidant, the vapour pressure in the time of preferred 20 ℃ is 10
-5Below the Pa, preferred especially 10
-8The antioxidant that Pa is following.Vapour pressure is higher than 10
-5The antioxidant of pa, its problem are, foam when extrusion modling, and perhaps when high temperature exposure, antioxidant is from the surface volatilization of moulding product.
The operable antioxidant of the present invention for example has following material, also can mix wherein one or more of use.
Hindered phenol is 2, the 6-di-tert-butyl-4-methy phenol, 2, the 6-DI-tert-butylphenol compounds, 4-hydroxymethyl-2, the 6-DI-tert-butylphenol compounds, 2,6-di-t-butyl-α-methoxyl-right-dimethyl-phenol, 2, the 4-di-tert-pentyl phenol, the tert-butyl group--cresols, the 4-tert-butyl phenol, styrenated phenol, 3-t-Butyl-4-hydroxyanisole, 2,4-dimethyl-6-tert-butyl phenol, octadecyl-3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonate ester (Off オ ス Off オ ネ one ト)-diethylester, 4,4 '-bis-phenol, 4,4 '-two-(2, the 6-DI-tert-butylphenol compounds), 2,2 '-methylene-two-(4-methyl-6-tert butyl phenol), 2,2 '-methylene-two-(4-methyl-6-Alpha-Methyl cyclohexylphenol), 4,4 '-methylene-two-(2-methyl-6-tert butyl phenol), 4,4 '-methylene-two-(2, the 6-DI-tert-butylphenol compounds), 1,1 '-methylene-two-(2,6-di-t-butyl naphthols), 4,4 '-butylidene-two-(2,6-di-t-butyl-metacresol), 2,2 '-sulfo--two-(4-methyl-6-tert butyl phenol), two-orthoresol sulfide, 2,2 '-sulfo--two-(2-methyl-6-tert butyl phenol), 4,4 '-sulfo--two-(3 methy 6 tert butyl phenol), 4,4 '-sulfo--two-(2,3-di-sec-amyl phenol), 1,1 '-sulfo--two-(beta naphthal), 3,5-di-tert-butyl-4-hydroxyl benzyl ether, 1,6 hexanediols-two-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2,4-pair-(n-octyl sulfo-)-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1,3,5-three azines, 2, [3-(3 for 2-sulfo--di ethylene bis, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2,2-thiobis (4-methyl-6-tert butyl phenol), N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide (ヒ De ロ シ Application Na マ ミ De), two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester) calcium, 1,3,5-trimethyl-2,4,6-three-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, triethylene glycol-two [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], 1,3,5-trimethyl-2,4,6-three (3,5 di-t-butyls-4 hydroxybenzyl) benzene, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-the fulminuric acid ester, pentaerythrite-four [3-(3,5-di-t-butyl-4-hydroxy diphenyl (ジ エ ニ Le) propionic ester] etc.
Amino phenols; normal-butyl-para-aminophenol, positive bytyry-para-aminophenol, positive pelargonyl group-para-aminophenol, positive lauroyl-para-aminophenol, positive stearyl-para-aminophenol, 2,6-di-t-butyl-alpha-alpha-dimethyl, amino-p-Cresol etc.
Quinhydrones system, quinhydrones, 2,5 di tert butylhydroquinone, 2,5 di tert amlyl hydroquinone, MEHQ hydroquinone monomethyl ether, quinhydrones single-benzyl ether etc.
Phosphate system, triguaiacyl phosphate, three (3, the 4-di-tert-butyl-phenyl) phosphates, three (nonyl phenyl) phosphate, four (2, the 4-di-tert-butyl-phenyl)-4,4 '-diphenylene phosphate, 2-ethylhexyl octyl phosphate etc.
In addition, also have 2-mercaptobenzothiazole zinc salt, two catechol borate-two-neighbours-tolyl guanidinesalt, nickel-dimethyldithiocarbamate, nickel-pentamethylene dithiocarbamate, mercaptobenzimidazole, zinc salt of 2 mercaptobenzimidazole etc.
Cyclo-olefin-polymer films can contain the adjuvant that generally cooperates as required in plastic foil.Above-mentioned adjuvant for example has thermal stabilizer, fast light stabilizing agent, ultraviolet light absorber, antistatic agent, lubricant, plastifier and filling agent etc., and its content can be selected in the scope that does not influence purpose of the present invention.
The fusion The tape casting
The forming method of cyclo-olefin-polymer films is not particularly limited, and can utilize any in the heating and melting method of forming, the solution casting method.The heating and melting method of forming can be categorized as extrusion moulding, extrinsion pressing, blow molding method, injection moulding, the blowing method of forming, drawing and forming method etc. in more detail.In order to obtain good films such as physical strength, surface accuracy, preferred extrusion moulding, blow molding method and extrinsion pressing, most preferably extrusion moulding in the said method.Condition of molding is suitably selected according to application target and forming method, and when utilizing the heating and melting method of forming, cylinder temperature is generally 150～400 ℃, and preferred 200～350 ℃, more preferably 230～330 ℃ scope.Cross when low when resin temperature, mobile variation produces fault and warpage on the film, when resin temperature is too high, because the thermal decomposition meeting of resin produces space and silver color spot, bad moulding such as film jaundice perhaps occur.The thickness of film is generally 5～300 μ m, preferred 10～200 μ m, the more preferably scope of 20～100 μ m.When thickness is crossed when thin, operating difficulties when stacked, when blocked up, lengthening drying time after stacked, productivity descends.
Cyclo-olefin-polymer films, its moistened surface tension force is preferably 40mN/m or more than the 40mN/m, more preferably 50mN/m or more than the 50mN/m, especially preferred 55mN/m or more than the 55mN/m, when moistened surface tension force during in above-mentioned scope, the bonding strength of film and polarizing coating improves, and in order to adjust surperficial wetting tension, for example can carry out Corona discharge Treatment, blowing ozone, ultraviolet irradiation, flame treatment, chemicals processing, other known surface treatment.
Reel film before stretching, its thickness are necessary for that 50～500 μ m left and right sides are thick, and thickness is irregular the smaller the better, whole in ± 8%, in preferred ± 6%, more preferably ± 4% in.
When above-mentioned cyclo-olefin-polymer films is made phase retardation film of the present invention, identical with cellulose ester membrane, can make by the reel film is stretched in the single shaft direction at least.In addition, substantial uniaxial tension after for example stretching in the scope that does not influence molecular orientation, also can carry out making stretch on the single shaft direction of molecular orientation biaxial stretch-formed.In addition, film is stretched at specific direction, then, stretching, the necessary interior phase differential that reaches on the thickness direction of face can be provided with aforementioned draw direction craspedodrome direction.When stretching, preferably use aforementioned tenter frame apparatus etc.
Stretching ratio is 1.3～10 times, preferred 1.5～8 times, and the delay that can obtain wishing in this scope.Cross when low when stretching ratio, the absolute value of delay does not raise, and does not form specific value, when too high, breaks sometimes.
Usually, at Tg-20 ℃ of the resin that constitutes the reel film～Tg+50 ℃, stretch in the scope of preferred Tg-15 ℃～Tg+40 ℃.Draft temperature is low excessively, breaks, and is too high, because molecule is not orientated, so the phase retardation film that can not obtain wishing.
The film that obtains like this makes molecular orientation by stretching, can make it have the interior maximum-delay of the scope of the invention.Delay can be by stretching head-pulley film delay and the thickness of stretching ratio, draft temperature, stretch orientation film control.Reel film before stretching is under the situation of specific thicknesses, and it is big that the absolute value of its delay of film that stretching ratio is big more tends to become more, so by changing stretching ratio, can obtain the stretch orientation film of desired delay.
The error that postpones is more little preferred more, stretch orientation film of the present invention, the error of the delay of its wavelength 589nm usually ± 50nm or ± below the 50nm, preferred ± 30nm or ± below the 30nm, more preferably ± 15nm or ± below the 15nm, most preferably ± 10nm or ± the following little error of 10nm.
Error or the thickness of delay in face is irregular, can make the stress that is applied on the reel film when stretching even by using the preceding reel film of little stretching, and it is diminished., plant at the uniform temperature branch for this reason, preferred temperature is controlled at ± 5 ℃ with interior, more preferably ± 2 ℃ with interior, preferred especially ± 0.5 ℃ to stretch under the interior environment.
Polaroid and liquid crystal indicator
Film of the present invention by guaranteeing its suitable delay, slow axis characteristic and leading phase shaft characteristic, can be used as polaroid protective film in use, simultaneously, can be maintained as the stable performance that optical compensation films had that enlarges the liquid crystal indicator visual angle.
Below polaroid of the present invention is described.
Polaroid of the present invention can utilize general method to make.For example, phase retardation film of the present invention is carried out after the alkali soap processing, dipping stretches in iodine solution, makes polarizing coating, on its two sides, and the method for pasting with fully saponified type polyvinyl alcohol water solution.So-called alkali soap processing is meant in order to make the aqueous adhesive wetting state good, improves cohesive, and the processing that film immersion is carried out in the strong base solution of high temperature.
In addition, in the polaroid of the present invention, it is preferred that the almost parallel mode of draw direction of light transmission axle and the phase retardation film of fitting with the aforementioned polariscope fabric width direction when casting film that contains the polariscope of bitintability material is fitted.In addition, among the present invention, so-called quadrature, as mentioned above, quadrature almost between the expression axle, in addition, and so-called direction unanimity, the direction between the expression axle is almost parallel.
Can use existing known as the polariscope that uses in the polaroid of the present invention.For example, make the film that the hydrophilic polymer of polyvinyl alcohol is constituted, handle with iodine class bitintability dyestuff, use the back that stretches, and perhaps the vinyl chloride plastic film is handled, and makes its orientation back use.The polariscope permanance that obtains like this is low, in long-term the use, and the performance generation deterioration of polariscope, so, films such as cellulose esters (polaroid protective film) are fitted in the both sides of this polariscope.
At this moment, at least simultaneously use phase retardation film of the present invention in the polaroid protective film.Another side can use other film.For example; also can use the film that is used for phase retardation film manufacturing of the present invention on the one side in addition; cellulose ester membrane (the KC8UX2MW of market sale; KC4UX2MW; KC5UN (コ ニ カ ミ ノ Le オ プ ト (strain) system)) and cyclic olefin polymer film (the concrete ゼ オ ネ Star Network ス that has Japanese ゼ オ Application (strain) to make; ゼ オ ノ ア; the ア one ト Application that JSI (strain) makes; the ア ペ Le (APL8008T that Mitsui Chemicals (strain) is made; APL6509T; APL6013T; APL5014DP; APL6015T) etc.), can as face side an other side polaroid protective film.On the polaroid protective film that the face side of display device is used, have outside antiglare layer or the blank hard overlay, it all is preferred also having anti-reflection layer, antistatic backing, stain-proofing layer.Preferably utilize methods such as coating, sputter, CVD, atmospheric pressure plasma CVD, vacuum evaporation that anti-reflection layer (silicon oxide layer, titanium oxide layer), antistatic backing, stain-proofing layer are set.
By polaroid of the present invention is installed on the display device, can make the good display device of the present invention of various visualitys.Phase retardation film of the present invention, it is preferred adopting the LCD with various type of drive such as reflection-type, infiltration type, semi-transmission type LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS types.In addition, phase retardation film of the present invention has good planarity, preferably uses in various display device such as plasma scope, an active display, OLED display, inorganic EL display, electronic paper.Particularly adopt more than picture 30 types, particularly the display device of the big picture of 30 types～54 types can obtain the picture periphery and not turn black, and its effect can keep for a long time, particularly utilizes VA type liquid crystal indicator, has significant effect.In addition, color spot, glitter or to involve irregular phenomenon few, it is not tired to observe eyes for a long time yet.
Embodiment
The present invention will be described below by embodiment, but the present invention is not limited thereto again.
The assay method of Ro, Rt, slow axis direction
Use Abbe refractomecer (4T), measure the mean refractive index of film constituent material.In addition, use the thickness of the micrometer mensuration film of market sale.
Use automatic birefraction meter KOBRA-21ADH (prince's gauging instrument (strain) system), the film after under 23 ℃, the environment of 55%RH, placing 24 hours, under equivalent environment, measure the delay of wavelength film under 590nm.Import above-mentioned mean refractive index and thickness, obtain postponing in the face value of the delay (Rt) of (Ro) and thickness direction.On the direction of slow axis, also measure simultaneously, measure the angle of orientation.
The angle of orientation change of length direction
The angle of orientation change of length direction, the position of film end is left in decision, at the length direction of growing the size film at interval, at the position sample of fabric width direction, measure with automatic birefraction meter KOBRA-21ADH (prince's gauging instrument (strain) system) near end 30cm with 15cm.The section of sample or datum line and long size film vertically need strict conformance, must correctly be arranged on the support.
The manufacturing of phase retardation film
(the manufacturing of cellulose ester membrane 101: the present invention)
Particle dispersion liquid
Particles A EROSIL R972V (ア エ ロ ジ Le (strain) system) 11 mass parts
Ethanol 89 mass parts
In dissolver,, after the mixing, disperse with マ Application ト Application go one リ Application with above stirring 50 minutes.
The particulate annex solution
Add following cellulose esters in the dissolution kettle of having added methylene chloride, heating is dissolved it fully, and the long-pending filter paper No.244 of peace that uses the long-pending filter paper (strain) of peace to make afterwards filters it.Cellulose ester solution after the abundant agitation and filtration in limit, the limit is simultaneously to wherein slowly adding particle dispersion liquid.Disperse with ア ト ラ イ one again.Off ア イ Application メ Star ト NF with the smart line of Japan (strain) system filters it, makes the particulate annex solution.
Methylene chloride 99 mass parts
Cellulose esters (degree of substitution with acetyl group 2.08, propiono degree of substitution 0.8, Mn=110000, Mw/Mn=1.9) 4 mass parts
Particle dispersion liquid 11 mass parts
Prepare the main rubber cement liquid of following composition.At first, in the dissolved under pressure still, add methylene chloride and ethanol.In the dissolved under pressure still that adds solvent, put into cellulose esters while stirring, be heated, stir on the limit, and dissolve fully on the limit, adds plastifier and ultraviolet light absorber again, makes its dissolving.The long-pending filter paper No.244 of peace that uses the long-pending filter paper (strain) of peace to make filters it, prepares main rubber cement.
Add main rubber cement liquid 100 mass parts and particulate annex solution 2 mass parts, with online mixer (mixer in the eastern レ silent oscillation pipe, Hi-Mixer, SWJ) mix fully, use the travelling belt casting device of film forming apparatus shown in Figure 7 then, curtain coating equably on the stainless steel band supporter of wide 2m.On the stainless steel band supporter, make solvent evaporation, make solvent residual amount reach 110%, peel off from the stainless steel band supporter.Apply tension force when peeling off, making length direction (MD) stretching ratio is 1.0 times, drying is carried out with the 1st arid region 6 in stretching limit, limit, then, utilize stenter portion 8 clamping reel film both ends, stretch under the condition when stretching beginning under 130 ℃ of the residual solvent amount 20 quality %, temperature, make the stretching ratio of fabric width direction (TD) reach 1.3 times.At this moment, adjust the tentering built-in temperature by the left and right sides temperature balance in the tenter frame apparatus, air balance, adjust clip interval and clip tension force, the angle of orientation that the maximal value that makes the angle of orientation that slow axis and film web cross direction form in the face of film forms for leading phase shaft in-0.4 °, the face of film and film length direction for+0.4 °, minimum value is in ± 0.4 °, angle of orientation variable cycle is 115m, and the minimum amplitude in this cycle is 0.3 °.After the stretching, under the condition that keeps its width, keep the several seconds, after making the tension force mitigation of fabric width direction, remove the width clamping, again it was transmitted 30 minutes in being set at 125 ℃ the 2nd arid region 9, carry out drying, make have wide 1.5m, the volume of the annular knurl of the wide 1cm in end, high 8 μ m is long by 3, the cellulose ester membrane 101 of 000m, thickness 80 μ m.
The composition of main rubber cement liquid
Methylene chloride 300 mass parts
Ethanol 52 mass parts
Cellulose esters (degree of substitution with acetyl group 2.08, propiono degree of substitution 0.8, Mn=110000, Mw/Mn=1.9) 100 mass parts
Triphenyl phosphate 9.5 mass parts
Ethyl methyl phthallyl ethyl glycollate 2.2 mass parts
チ ヌ PVC Application 109 (チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ corporate system) 1.3 mass parts
チ ヌ PVC Application 171 (チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ corporate system) 0.6 mass parts
The cellulose ester membrane 101 that obtains is shown in Fig. 2 in the angle of orientation change of length direction, the angle of orientation change of the fabric width direction in the effective width is shown in Figure 11.
(the manufacturing of cellulose ester membrane 102: the present invention)
Identical with cellulose ester membrane 101, adjust the tension force of length, clip interval and the clip of tenter frame apparatus, the maximal value of the angle of orientation that the maximal value that makes the angle of orientation that slow axis and film web cross direction form in the face of film forms for leading phase shaft in-0.7 °, the face of film and film length direction for+0.7 °, minimum value for+0.7 °, minimum value for-0.7 °, angle of orientation variable cycle are that the minimum amplitude in 320m, this cycle is 0.7 °, obtain cellulose ester membrane 102.
The cellulose ester membrane 102 that obtains is shown in Fig. 3 in the angle of orientation change of length direction.
(the manufacturing of cellulose ester membrane 103: the present invention)
Identical with cellulose ester membrane 101, utilize the stenter portion 8 of figure, to the fabric width direction under the condition of 155 ℃ of draft temperatures, stretch 1.30 times, stretch in 45 ° of directions, at this moment, adjust the tension force of length, clip interval and the clip of tenter frame apparatus, the maximal value of the angle of orientation that the fabric width direction forms is that 45.3 °, minimum value are that the maximal value of the angle of orientation that slow axis and film web cross direction form in 44.7 ° of faces that make film is that 45.3 °, minimum value are 44.7 °, angle of orientation variable cycle is 140m, the minimum amplitude in this cycle is+0.3 °, obtains cellulose ester membrane 103.
The cellulose ester membrane 103 that obtains is shown in Fig. 4 in the angle of orientation change of length direction.
(the manufacturing of cellulose ester membrane 104: comparative example)
Identical with cellulose ester membrane 101, adjust the tension force of length, clip interval and the clip of tenter frame apparatus, the maximal value that makes the angle of orientation that slow axis and film web cross direction form in the face of film is-1.4 ° for+1.4 °, minimum value, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is that+1.4 °, minimum value are-1.4 °, angle of orientation variable cycle is 120m, the minimum amplitude in this cycle is 1.4 °, obtains cellulose ester membrane 104.
The cellulose ester membrane 104 that obtains is shown in Fig. 5 in the angle of orientation change of length direction.
(the manufacturing of cellulose ester membrane 105: comparative example)
Identical with cellulose ester membrane 101, with the timing setting of feedback is 0.05 second cycle, air quantity in the drying process is set to 5 times, control, the maximal value of making the angle of orientation is-0.04 degree for+0.04 degree, minimum value, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is that+0.04 degree, minimum value are-0.04 degree, and angle of orientation variable cycle is the film of 103m.But in the manufacturing of long size film,, carry out temperature control and have little time from surpassing 1000m, surpass 1100m, the air quantity of drying process and the fluctuation of temperature strengthen, and near 1100m, obtain the film (angle of orientation change is shown in Figure 11) that angle of orientation deviation surpasses 3 degree.And from surpassing 1000m, the phase differential change is at 20nm or more than the 20nm in the face.
(manufacturing of cellulose ester membrane 106)
Identical with 101, the feedback interval of the angle of orientation is set at 1.5s, the left and right sides clip of stenter is adjusted at interval, the maximal value of the interior slow axis of face of film and the angle of orientation that the film web cross direction forms is spent for-0.7 for+0.7 degree, minimum value, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is that+0.7 degree, minimum value are-0.7 degree, angle of orientation variable cycle is 2m, obtains cellulose ester membrane 106.
(manufacturing of cellulose ester membrane 107)
Identical with 101, the feedback interval of the angle of orientation is set at 3.5s, be provided with and adjust the clip position of the left and right sides clip of stenter, the maximal value of the interior slow axis of face of film and the angle of orientation that the film web cross direction forms is spent for-0.7 for+0.7 degree, minimum value, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is that+0.7 degree, minimum value are-0.7 degree, angle of orientation variable cycle is 10m, obtains cellulose ester membrane 107.
(manufacturing of cellulose ester membrane 108)
Identical with 101, the feedback interval of the angle of orientation is set at 7s, the clip opener of the left and right sides clip of stenter is provided with the position adjustment, the maximal value of the interior slow axis of face of film and the angle of orientation that the film web cross direction forms is spent for-0.7 for+0.7 degree, minimum value, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is that+0.7 degree, minimum value are-0.7 degree, angle of orientation variable cycle is 5m, obtains cellulose ester membrane 108.
(manufacturing of cellulose ester membrane 109)
Identical with 101, the feedback interval of the angle of orientation is set at 10s, the track length of the left and right directions of stenter is changed, the air quantity adjustment of drying process is spaced apart 10s, the maximal value of the interior slow axis of face of film and the angle of orientation that the film web cross direction forms is spent for-0.7 for+0.7 degree, minimum value, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is that+0.7 degree, minimum value are-0.7 degree, and angle of orientation variable cycle is 50m, obtains cellulose ester membrane 109.
(manufacturing of cellulose ester membrane 110)
Identical with 101, the feedback interval of the angle of orientation is set at 10s, change the track space behind the stenter respectively and transmit tension force, make the air quantity adjustment of drying process be spaced apart 10s, the maximal value of the interior slow axis of face of film and the angle of orientation that the film web cross direction forms is spent for-0.7 for+0.7 degree, minimum value, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is that+0.7 degree, minimum value are-0.7 degree, and angle of orientation variable cycle is 70m, obtains cellulose ester membrane 110.
(manufacturing of cellulose ester membrane 111)
Identical with 101, the feedback interval of the angle of orientation is set at 10s, change the position of the clip nose pile of the clip open site of stenter left and right sides clip and left and right sides clip respectively, make the air quantity adjustment of drying process be spaced apart 10s, the maximal value of the interior slow axis of face of film and the angle of orientation that the film web cross direction forms is spent for-0.7 for+0.7 degree, minimum value, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is that+0.7 degree, minimum value are-0.7 degree, angle of orientation variable cycle is 70m, obtains cellulose ester membrane 111.
(the manufacturing of cellulose ester membrane 201: the present invention)
According to following main points, make the cyclo-olefin-polymer films that the fabric width direction stretches.
(manufacturing of cyclo-olefin-polymer films)
Under nitrogen atmosphere, at room temperature in 500 parts of the cyclohexanes after dehydration 1.2 parts of 1-hexenes, 0.15 part of dibutyl ethers, triisobutyl aluminium is put into reactor for 0.30 part, remain on 45 ℃ after the mixing, simultaneously three ring [4.3.0.12,5] last of the ten Heavenly stems-3,7-diene (bicyclopentadiene, hereinafter to be referred as DCP) 20 parts, 1,4-methanol-based-1,4,4a, 140 parts of 9a-tetrahydrochysene fluorenes (hereinafter to be referred as MTF), and the norborene of 40 parts of formations of 8-methyl-Fourth Ring [4.4.0.12,5.17,10] 12-3-alkene (hereinafter to be referred as MTD) is a monomer mixture, and 40 parts of tungsten hexachlorides (0.7% toluene solution), added to make its polymerization continuously with 2 hours.In polymeric solution, add 0.52 part of 1.06 parts of butyl glycidyl ethers and isopropyl alcohol, make the polymerization catalyst deactivation, stop polyreaction.
Then, to 100 parts of the reaction solutions that contains ring-opening polymerization polymer that obtain, add 270 parts of cyclohexanes, add 5 parts of nickel-alumina catalyzer (day wave chemical company's system) again as hydrogenation catalyst, utilize hydrogen to be forced into 5MPa, heat while stirring to 200 ℃ of temperature, make its reaction 4 hours, obtain containing the hydropolymer reaction solution of 20% DCP/MTF/MTD ring-opening polymerization polymer.Remove by filter after the hydrogenation catalyst, with soft polymer (Network ラ レ corporate system; セ プ ト Application 2002) and antioxidant (チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ corporate system; イ Le ガ ノ Star Network ス 1010) is added into respectively in the resulting solution, makes its dissolving (100 parts in every polymkeric substance all is 0.1 part).Then, utilize cylinder type concentrate drying machine (Hitachi's system), from solution, remove desolvate cyclohexane and other volatile ingredient, under molten condition, with molten condition hydropolymer is extruded with the long fibre shape, be cut into particle after the cooling and reclaimed from extruder.Norborene class residual the solution after polymerization is formed the copolymerization ratio that (utilizing vapor-phase chromatography) calculates each the norborneol alkene monomer in the polymkeric substance, obtains DCP/MTF/MTD=10/70/20, no better than the composition of synthetic afterproduct.The weight-average molecular weight (Mw) of the hydrogenation additive of this ring-opening polymerization polymer is 31,000, and molecular weight distribution (Mw/Mn) is 2.5, hydrogenation rate is 99.9%, and Tg is 134 ℃.
Use the hot-air drier that is communicated with air, drying is 2 hours under 70 ℃, makes the ring-opening polymerization polymer hydrogenation additive particles that obtains remove moisture.Then, use the T pattern tool of clothes hanger type with kerf width 1400mm the minor axis extruder (Mitsubishi Heavy Industry Ltd.'s system: screw diameter 90mm, T pattern tool otch parts material as tungsten carbide, with the peel strength 44N of molten resin), aforementioned particles is melt extruded moulding, make the cyclic olefin polymer film of thick 80 μ m.The Ro of this film is that 45mm, Rt are 90nm.In the testing laboratory below grade 10,000 or 10,000, under the condition of molding of 240 ℃ of molten resin temperatures, 240 ℃ of T pattern tool temperature, carry out extrusion molding.With the film that obtains midway at drying process, use the tenter frame apparatus identical with Fig. 7 stenter portion 8, under 155 ℃ of draft temperatures, carry out 1.50 times of stretchings in the fabric width direction, at this moment, adjust the length of tenter frame apparatus, the tension force of clip interval and clip, making the interior slow axis of face of film and the maximal value of the angle of orientation that the film web cross direction forms is 0.4 °, minimum value is-0.4 °, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is 0.4 °, minimum value is-0.4 °, angle of orientation variable cycle is 115m, the minimum amplitude in this cycle is 0.4 °, obtains cellulose ester membrane 201.
(the manufacturing of cellulose ester membrane 202: the present invention)
Identical with cyclic olefin polymer film 201, use the tenter frame apparatus identical with the stenter of Fig. 7, under 155 ℃ of draft temperatures, fabric width direction 45 degree directions are stretched 1.50 times, at this moment, adjust the tension force of length, clip interval and the clip of tenter frame apparatus, the maximal value that makes the angle of orientation that the fabric width direction forms is that 45.3 °, minimum value are 44.7 °, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is 45 ± 0.3 °, angle of orientation variable cycle is 140m, the minimum amplitude in this cycle is 0.3 °, obtains cyclic olefin polymer film 202.
(the manufacturing of cellulose ester membrane 203: comparative example)
Identical with cyclic olefin polymer film 202, use the tenter frame apparatus identical with the stenter portion 8 of Fig. 7, fabric width direction 45 degree directions are stretched, at this moment, adjust the tension force of length, clip interval and the clip of tenter frame apparatus, the maximal value that makes the angle of orientation that the fabric width direction forms is that 45.3 °, minimum value are 44.7 °, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is 45 ± 1.5 °, angle of orientation variable cycle is 1.2m, the minimum amplitude in this cycle is 1.2 °, obtains cyclic olefin polymer film 203.
The cyclo-olefin-polymer films 203 that obtains is shown in Fig. 6 in the angle of orientation change of length direction.
Will as the angle of orientation of details, Ro, Rt, fabric width direction and the length direction of the above-mentioned cellulose ester membrane of making 101～104, cyclic olefin polymer film 201～203, angle of orientation variable cycle, the minimum amplitude in this cycle, and the size of each film when being cut into 60 inches (1 inch expression 2.54cm in addition) wide-angle sizes in the angle of orientation change and be shown in following table 1.
Table 1
| Film No | The film kind | Draw direction | ??Ro ??(nm) | ??Rt ??(nm) | Slow axis orientation angle (°) | Leading phase shaft orientation angle (°) | Angle of orientation variable cycle (m) | The variable cycle minimum amplitude (°) | Angle of orientation variation in 60 inches wide (°) | Appendix | ||
| Maximal value | Minimum value | Maximal value | Minimum value | |||||||||
| ??104 | Cellulose esters | ??TD | ??45 | ??130 | ??0.4 | ??-0.4 | ??0.4 | ??-0.4 | ??115 | ??0.3 | ??0.3 | The present invention |
| ??102 | Cellulose esters | ??TD | ??45 | ??130 | ??0.7 | ??-0.7 | ??0.7 | ??-0.7 | ??320 | ??0.7 | ??0.3 | The present invention |
| ??103 | Cellulose esters | 45 degree directions | ??150 | ??85 | ??45+0.3 | ??45-0.3 | ??45+0.3 | ??45-0.3 | ??140 | ??0.3 | ??0.3 | The present invention |
| ??201 | Cyclic olefin polymer | ??TD | ??45 | ??127 | ??0.4 | ??-0.4 | ??0.4 | ??-0.4 | ??115 | ??0.4 | ??0.3 | The present invention |
| ??202 | Cyclic olefin polymer | 45 degree directions | ??150 | ??120 | ??45+0.3 | ??45-0.3 | ??45+0.3 | ??45-0.3 | ??140 | ??0.3 | ??0.3 | The present invention |
| ??104 | Cellulose esters | ??TD | ??45 | ??130 | ??1.4 | ??-1.4 | ??1.4 | ??-1.4 | ??120 | ??1.4 | ??0.6 | Comparative example |
| ??203 | Cyclic olefin polymer | 45 degree directions | ??150 | ??85 | ??45+0.3 | ??45-0.3 | ??45+0.3 | ??45-0.3 | ??1.2 | ??1.2 | ??0.6 | Comparative example |
Use the above-mentioned cellulose ester membrane of making 101,102,104, cyclic olefin polymer film 201, make polaroid and liquid crystal indicator according to following main points.
(manufacturing of polaroid P101, P102, P104, P201)
Use the reel sample of the above-mentioned cellulose ester membrane of making, cyclic olefin polymer film, carry out the alkali soap processing of following record, the manufacturing of polaroid.
| The alkali soap processing | |||
| In the saponifying process washing step and the operation washing step | 2M-NaOH water 10 quality %HCl water | ?50℃ ??30℃ ??30℃ ??30℃ | 90 |
Saponification is washed successively, neutralizes, is washed after handling, and carries out drying then under 80 ℃.
(manufacturing of polariscope)
The long size roller of thickness 120 μ m is batched shaped polyethylene alcohol film immersion containing iodine 1 mass parts.In aqueous solution 100 mass parts of boric acid 4 mass parts, stretch 6 times at direction of transfer under 50 ℃, make polarizing coating.
The identical KC8UX2M (being recited as TAC among the figure) of コ ニ カ ミ ノ Le オ プ ト (strain) manufacturing of saponification processing, cellulose ester membrane, the polymer of cyclic hydrocarbon film of on its reverse side, the aforementioned bases saponification being handled of carrying out of single face with above-mentioned polarizing coating, with fully saponified type polyvinyl alcohol (PVA) 5% aqueous solution as bonding agent, use reel-fibrous bundle-reel respectively, fitted, make the interior slow axis of the face that sees through axle and film of polariscope parallel, carry out drying, make polaroid P101, P102, P104, P201.
(manufacturing of liquid crystal indicator A, B, D, F)
Polaroid P101, the P102, P104, P201 and the system liquid crystal panel LL-T1620 of Sharp that obtain are made up, peel off the polaroid that is fitted in advance on this liquid crystal panel, forming configuration shown in Figure 8 on the two sides of liquid crystal cell constitutes, the axle that sees through of polaroid is formed in identical direction with the axle that sees through of the polaroid of fitting in advance, by bonding agent applying polaroid, make liquid crystal indicator.
Use cellulose ester membrane 103, the cyclo-olefin-polymer films 202,203 of above-mentioned manufacturing then, make polaroid and liquid crystal indicator according to following main points.
(manufacturing of polaroid P103, P202, P203)
Use the reel sample of the above-mentioned cellulose ester membrane of making 103, cyclo-olefin-polymer films 202,203 and TAC, identical with the manufacturing of above-mentioned polaroid, carry out the alkali soap processing, make polaroid, make polaroid P103, P202, P203.
(manufacturing of liquid crystal indicator C, E, G)
Make polaroid P103, the P202, P203 and the combination of following liquid crystal indicator that obtain, make a unanimity that sees through of polaroid, by bonding agent, the applying polaroid makes and forms configuration shown in Figure 9 on the single face of liquid crystal cell and constitute, and makes liquid crystal indicator C, E, G.
(manufacturing of TN type reflection-type liquid-crystal display device)
Preparation is provided with the glass substrate of ito transparent electrode, and the glass substrate of the aluminium reflection electrode that has formed micro concavo-convex is set.In the electrode side of two sheet glass substrates, form pi alignment films (SE-7992, daily output chemistry (strain) system) respectively, carry out friction treatment.By the barrier film of 3.4 μ m, make two plate base alignment films overlapping in opposite directions.The frictional direction that the direction of regulating substrate makes two alignment films is with 110 ℃ angular cross.In the gap of substrate, inject liquid crystal (MLC-6252, メ Le Network corporate system), form liquid crystal layer.Make 70 ° of torsion angles, Δ nd value TN type liquid crystal cell like this for 269nm.In glass substrate one side that is provided with ito transparent electrode, paste the polaroid of making.The reflection-type liquid-crystal display device of making is applied the square-wave voltage of 1kHz.With white demonstration 1.5V, the black 4.5V that shows, the visual evaluation can confirm no matter be white demonstration, black demonstration, all do not have colour difference, carry out neutral gray and show.
(evaluation of polaroid and liquid crystal indicator)
With the method for following demonstration, carry out the evaluation of polaroid and liquid crystal indicator.
(evaluation of polaroid)
The polaroid yield
The polaroid of making is fixed on fabric width direction position, and the interval with arbitrary interval, is punched each 20 pieces respectively with 16 inches sizes from 0.5m to 100m, at first, measure parallel transmitance and craspedodrome transmitance, utilizes following formula to calculate degree of polarization.Then, under 60 ℃, 90% condition, make each polaroid carry out 500 hours forced aging respectively after, measure parallel transmitance and craspedodrome transmitance once more, utilize following formula to calculate degree of polarization.Utilize following formula to try to achieve the degree of polarization variable quantity.
Degree of polarization P=((H0-H90))/(H0+H90))
1/2* 100
Degree of polarization variable quantity=P0-P500
H0: parallel transmitance
H90: craspedodrome transmitance
P0: the degree of polarization before the forced aging
P500: force the degree of polarization of deterioration after 500 hours
From the degree of polarization variable quantity that obtains, evaluate according to following benchmark, ◎, zero no problem in the practicality estimates resultant number as the polaroid yield.
◎: the degree of polarization rate of change is less than 10%, and is no problem fully in the practicality
Zero: degree of polarization rate of change 10%～25%, no problem in the practicality
*: the degree of polarization rate of change is 25% or 25% when above, and problem (light leak amount (permanance)) is arranged in the practicality
Make 2 polaroids making being equivalent to carry out the crossed nicols configuration on 60 inches the glass plate, use the spectrophotometer U3100 of (strain) Hitachi, measure the transmitance (T1) of 590nm.2 polaroids were handled 500 hours under 80 ℃ condition simultaneously, afterwards, same as described above carrying out measured transmitance (T2) when crossed nicols disposes, and the transmitance of investigating the thermal treatment front and back changes, measure the light leak amount according to following formula, utilize following metewand to estimate.
Light leak amount (%)=T2 (%)-T1 (%)
Although the light leak amount is 0～5%, practical no problem, but preferred 0～4%, more preferably 0～3%, preferred especially 0～1%.
◎: do not observe light leak fully
Zero: light leak is few, but practical no problem
*: light leak is many, can not use.
(evaluation of liquid crystal indicator)
Contrast is irregular
At first, the EZ-contrast with ELDIM society makes carries out the viewing angle characteristic evaluation of liquid crystal indicator, the light transmission capacity when measuring black demonstration and white the demonstration.The visual angle is estimated, and calculates contrast=(light transmission capacity when showing in vain)/(light transmission capacity during black the demonstration), estimates according to following benchmark.
The visual angle is estimated, and is index with the angle at the visual angle of expression contrast 10, estimates.
◎: do not have contrast irregular fully
Zero: contrast is irregular few, but use no problem
*: contrast is irregular many, can not use.
Under 40 ℃, 80% condition, above-mentioned display panels is carried out forced aging (long duration test), again to each display panels, with the irregular evaluation of above-mentioned degree of comparing equally.
Above-mentioned evaluation result is shown in table 2.
Table 2
| Polaroid No. | Use film No. | 16 inches yields (sheet number) | 60 inches light leaks | Liquid crystal indicator No. | The polaroid No. that uses | Contrast is irregular | The irregular situation occurred of long duration test contrast | Appendix |
| ??P101 | ??101 | ??20/20 | ??◎ | ??A | ??P101 | ??◎ | ??◎ | The present invention |
| ??P102 | ??102 | ??18/20 | ??○ | ??B | ??P102 | ??○ | ??○ | The present invention |
| ??P103 | ??103 | ??18/20 | ??◎ | ??C | ??P103 | ??○ | ??○ | The present invention |
| ??P201 | ??201 | ??18/20 | ??◎ | ??D | ??P201 | ??◎ | ??◎ | The present invention |
| ??P202 | ??202 | ??19/20 | ??◎ | ??E | ??P202 | ??○ | ??○ | The present invention |
| ??P104 | ??104 | ??5/20 | ??× | ??F | ??P104 | ??× | ??× | Comparative example |
| ??P203 | ??203 | ??3/20 | ??× | ??G | ??P203 | ??× | ??× | Comparative example |
As can be known from the above table, film of the present invention, the polaroid that uses this film and liquid crystal indicator have good polaroid yield and light leak, and have good contrast.
Comparative example
Create conditions down at the cellulose ester membrane 101 of embodiment 1, make with variable cycle synchronous, make the tension force of clip and the temperature in the stenter, the wind speed change, the angle of orientation deviation that slow axis and film web cross direction form in the face of film is ± 0.3 °, the maximal value of the angle of orientation that leading phase shaft and film length direction form in the face of film is less than+0.1 °, angle of orientation variable cycle is that the minimum amplitude of 115m and this variable cycle is less than 0.1 °, so the result who adjusts is, compare with manufacturing cellulose ester membrane 101, the frequency of breaking rises to more than 50 times suddenly, and the steady production of long yardstick film is caused very big obstacle.
Claims (15)
1. the manufacture method of a drum phase retardation film, to be the fabric width direction of slow axis and this film forms in the face in the effective width of drum film angle be ± 1 ° scope to this method, the angle that the length direction of leading phase shaft and this film forms in the face of this film is the phase retardation film manufacture method of ± 1 ° scope, it is characterized in that, make the interior leading phase shaft of face of aforementioned films and the angle that this film length direction forms, have cycle of 1.5m～500m in this film length direction, and minimum amplitude that should the cycle is set at 0.1 °～1 °.
2. the manufacture method of a drum phase retardation film, this method is that the fabric width direction of slow axis and this film forms in the face in the effective width of drum film angle is 45 ± 1 ° a scope, the angle that the length direction of leading phase shaft and this film forms in the face of this film is the phase retardation film manufacture method of 45 ± 1 ° scope, it is characterized in that, make the interior leading phase shaft of face of aforementioned films and the angle that this film length direction forms, have cycle of 1.5m～500 in this film length direction, and minimum amplitude that should the cycle is set at 0.1 °～1 °.
3. the manufacture method of drum phase retardation film as claimed in claim 1 or 2 is characterized in that, with reel-fibrous bundle-reel itself and drum polarizing coating is pasted mutually.
4. as the manufacture method of any one described drum phase retardation film of claim 1～3, it is characterized in that, on aforesaid roll tubular phase retardation film at least one direction in length direction or fabric width direction, carry out stretch processing in the scope of 1.05～2 times of stretching ratios.
5. as the manufacture method of any one described drum phase retardation film of claim 1～4, it is characterized in that, control the two ends, the left and right sides of continuous film, apply tension force in the fabric width direction, transmit this film simultaneously, utilize stretching device to stretch, utilize the left and right sides grasping device of aforementioned stretching device, about independently controlling diaphragm control length (from controlling the distance that begins to controlling end), stretch thus.
6. as the manufacture method of any one described drum phase retardation film of claim 1～5, it is characterized in that, change about crossing by at least one square tube of controlling the reference position fixed position of clip (set) (Network リ Star プ Network ロ one ザ one) or controlling end position (setting the open site of clip) on the left and right sides grasping device that makes stretching device, about independently controlling diaphragm about control length.
7. as the manufacture method of any one described drum phase retardation film of claim 1～6, it is characterized in that, control the two ends, the left and right sides of continuous film, and about change the mobile of the grasping device that is connected give horizontal tension independently with trackless guide rail left and right sides length, about change independently, thus about independently controlling diaphragm control length.
8. as the manufacture method of any one described drum phase retardation film of claim 1～7, it is characterized in that, in the grasping device of the left and right sides of aforementioned stretching device, control rate independently about this grasping device.
9. as the manufacture method of any one described drum phase retardation film of claim 1～8, it is characterized in that, batch the preceding film angle of orientation with on-line determination, based on this measurement result, utilize following at least a method to make, i.e. left and right sides grasping device by stretching device, with the method for controlling independent control about length of film, or about the method for left and right sides grasping device speed of independent control stretching device.
10. as the manufacture method of any one described drum phase retardation film of claim 1～9, it is characterized in that, online detection is in the position of controlling the starting position and controlling the left and right sides grasping device of end position, try to achieve at this and control the film phase differential that the position produces, based on this measurement result, utilize following at least a method to make, promptly the left and right sides grasping device by stretching device with film control length carry out about the method for independent control, or about the method for speed of left and right sides grasping device of independent control stretching device.
11. a phase retardation film, it utilizes in the claim 1～10 any one described method to make.
12. phase retardation film as claimed in claim 11 is characterized in that, is 25～300nm (Ro) by postponing (リ one デ one シ ヨ Application) in the face of following general formula (1) expression
Formula (1) Ro value=(nx-ny) * d
[in the formula, nx represents the refractive index of the maximum direction of refractive index in the face, ny represent with the rectangular direction of nx on face in refractive index, d represents the thickness (nm) of film].
13. phase retardation film as claimed in claim 12 is characterized in that, is-100～400nm by the delay (Rt) of the thickness direction of following general formula (2) expression
Formula (2) Rt value=((nx+ny)/2-nz) * d
[in the formula, nx represents the refractive index of the maximum direction of index of refraction in the face, ny represent with the rectangular direction of nx on face in refractive index, nz represents the refractive index of film thickness direction, the thickness (nm) that d represents film].
14。A kind of polaroid is characterized in that, it has any one described phase retardation film of claim 11～13.
15. a display device is characterized in that, it has the phase retardation film of claim 11～13 described in any one.
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