CN100590458C - Optical resin film and polarizing film and liquid crystal display device using the same - Google Patents
Optical resin film and polarizing film and liquid crystal display device using the same Download PDFInfo
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- CN100590458C CN100590458C CN200610115043A CN200610115043A CN100590458C CN 100590458 C CN100590458 C CN 100590458C CN 200610115043 A CN200610115043 A CN 200610115043A CN 200610115043 A CN200610115043 A CN 200610115043A CN 100590458 C CN100590458 C CN 100590458C
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Abstract
An optical resin film, which has Re (lambda) and Rth (lambda) satisfying retardation requirements (A) to (D), and has an in-plane width direction retardation (Re) variation coefficient of 5% or less and a thickness direction retardation (Rth) variation coefficient of 10% or less: (A) 0.1<Re (450)/Re (550)<0.95 (B) 1.03<Re (650)/Re (550)<1.93 (C) 0.4<(Re/Rth (450))/(Re/Rth (550)))<0.95 (D) 1.05<(Re/Rth (650)/(Re/Rth (550))<1.9, and a polarizing plate and a liquid crystal display device using the optical resin film.
Description
Technical field
The Polarizer and the liquid crystal indicator that the present invention relates to the optical resin film and comprise this optical resin film.
Background technology
Since liquid crystal indicator can be advantageously with the low power consumption low pressure operation and can obtain little size and thickness, so they have been widely used in the monitor of personal computer and mobile phone, televisor etc.According to the arrangement of liquid crystal molecule in liquid crystal cell, the liquid crystal indicator of various modes has been proposed.Till now, wherein liquid crystal molecule has become main flow to upper base with the TN patterns of about 90 degree aligned twisted from the bottom matrix of liquid crystal cell.
Liquid crystal indicator generally includes liquid crystal cell, optical compensating gage and polarizer.Optical compensating gage is used to eliminate undesirable image colour developing or increases field-of-view angle.As such optical compensating gage, used the stretching birefringent film here or be coated with the hyaline membrane of liquid crystal.For example, disclose a kind of comprising by discotic mesogenic being coated on the tri acetyl cellulose membrane optical compensating gage directed then and that fixedly coating layer obtained among the JP-A-62-210423, be applied to TN mode liquid crystal element be used for the broadening one's vision technology of angle.Yet, has strict requirement for the dependence of field-of-view angle at the liquid crystal indicator of the widescreen TV that is used for to watch from various angles.Even can not satisfy these requirements by top mentioned method.For this purpose, to being different from the TN pattern, comprise that the liquid crystal indicator of IPS (face internal conversion) pattern, OCB (optical compensation curved) pattern, VA (homeotropic alignment) pattern is studied.Particularly, the VA pattern has been designated as the liquid crystal indicator that is used for the TV purposes, and this is because it has provided high-contrast image and can be with high relatively throughput rate production.
Although the VA mode LCD can reach almost complete black the demonstration in the normal direction along panel, when from vergence direction observation panel the time, light leak has taken place disadvantageously, caused that field-of-view angle reduces.In order to address this problem, proposed to provide at least one gap between liquid crystal layer and Polarizer retardation plate to eliminate light leak (being disclosed in JP-A-62-210423) with refraction ansiotropy nx=ny＞nz.Proposed also to be used in combination and had the positive refraction anisotropy that ((second retardation plate of nx=ny＞nz) is eliminated light leak (being disclosed in Jap.P. 3,027,805) to first retardation plate of nx＞ny=nz) with having the negative refraction anisotropy.Also further proposed to use optics biaxial retardant plates to improve the field-of-view angle performance (being disclosed in Jap.P. No.3,330,574) of VA mode LCD with refraction ansiotropy nx＞ny＞nz.Mark nx, ny and nz represent the refractive index of above mentioned retardation plate on X-axis, Y-axis and Z-direction respectively.Above mentioned X-direction be the longitudinal direction of above mentioned retardation plate direction in face show largest refractive index along longitudinal direction.Above mentioned Y direction be perpendicular to the longitudinal direction of above mentioned X-direction in the plate mentioned in the above.Above mentioned Z-direction show thickness direction perpendicular to the mentioned Y direction in top mentioned X-direction and front.
Yet these methods only can be eliminated at particular range of wavelengths () light leak for example, near the green light 550nm, and do not consider the light leak of other wavelength coverage (for example near the blue light the 450nm, near 650nm ruddiness).Correspondingly, these methods have stayed some and have wished the so-called aberration problem of solution, that is to say, in the black process that shows, have manifested blue or red color in the time of oblique view.
Summary of the invention
The present invention finishes in these cases.An object of the present invention is to provide the optical resin film and Polarizer that comprises it and the liquid crystal indicator that in wide scope, show high contrast ratio.
These targets are finished by following structure.
(1) a kind of optical resin film, it has Re (λ) and the Rth (λ) that satisfy to postpone requires (A)-(D), and has 5% or delay (Re) variation factor of face insied width direction still less and 10% or thickness direction retardation still less (Rth) variation factor:
(A)0.1＜Re(450)/Re(550)＜0.95
(B)1.03＜Re(650)/Re(550)＜1.93
(C)0.4＜(Re/Rth(450))/(Re/Rth(550)))＜0.95
(D)1.05＜(Re/Rth(650)/(Re/Rth(550))＜1.9
Wherein, Re (λ) expression is the light of λ nm for wavelength, length of delay in the face of this optical resin film;
Rth (λ) expression is the light of λ nm for wavelength, and this optical resin film is at the length of delay of thickness direction; And
Re/Rth (λ) expression is the light of λ nm for wavelength, the ratio (unit: nm) of the length of delay in the face of this optical resin film on length of delay and the thickness direction.
(2) according to the optical resin film described in top (1), it comprises cellulose acylate film.
(3) according to each described optical resin film in top (1) or (2), it comprises and is selected from by plastifier, ultraviolet light absorber, peels off at least a in the group that promoter, dyestuff and delustring material form.
(4) according to each described optical resin film in top (1)-(3), it comprises at least a delay developping agent that comprises bar-shaped compound or discotic compound.
(5) a kind of Polarizer, it comprises:
Polarizer with polyvinyl alcohol (PVA); With
At least two diaphragms that on these polarizer both sides, provide,
In wherein said at least two diaphragms at least one is each described optical resin film in top (1)-(4).
(6) Polarizer described in top (5), it further comprises and is provided in these two diaphragms lip-deep at least one layer that is selected from the group that is made of hard conating, antiglare layer and anti-reflection layer of film at least.
(7) as top (5) or (6) described Polarizer, it further comprises and is provided in the optical anisotropic layer at least one film in these at least two diaphragms.
(8) a kind of liquid crystal indicator that comprises the Polarizer of describing in one of superincumbent (5)-(7).
Description of drawings
Fig. 1 is the synoptic diagram of example of having described the VA mode LCD structure of correlation technique;
Fig. 2 is the synoptic diagram of another example of having described the VA mode LCD structure of correlation technique;
Fig. 3 is a synoptic diagram of having described the example of liquid crystal indicator structure of the present invention;
Fig. 4 is a synoptic diagram of having described an example that is used in optical compensation films of the present invention;
Fig. 5 is the synoptic diagram that is used to explain the poincare sphere that the degree of polarization of the incident light on liquid crystal indicator of the present invention changes;
Fig. 6 is the synoptic diagram that is used to explain the poincare sphere that the degree of polarization of the light on the example of the liquid crystal indicator that is incident on correlation technique changes;
Fig. 7 be graphic representation the figure of cross section structure of an example of Polarizer of the present invention described;
Fig. 8 be graphic representation the figure of cross section structure of another example of Polarizer of the present invention described;
Fig. 9 is the figure that has described an example of liquid crystal indicator structure of the present invention;
Figure 10 is the figure that has described an example of liquid crystal indicator structure of the present invention;
Figure 11 is the figure that has described the relation between clamping steps A of the present invention, cross directional stretch step B and the transverse relaxation step C; With
Figure 12 is a chart of having described the embodiment of stretching step B.
Embodiment
Effect of the present invention will be described in conjunction with the accompanying drawings.Fig. 1 is the diagram that has shown the structure of common VA mode LCD.The VA mode LCD comprises the liquid crystal cell 3 that has when not applying voltage, promptly causes the liquid crystal layer that liquid crystal molecule is arranged perpendicular to matrix surface in black the demonstration, and with aims between the liquid crystal cell between them 3 arrange and their transmission shaft (shown in the striped of Fig. 1) by the Polarizer 1 and 2 of mutual vertical placement.In Fig. 1, light is in the 1 side incident of liquid crystal indicator Polarizer.When in Polarizer 1 normal to a surface direction, be when light that the z direction of principal axis is propagated is incident on the liquid crystal indicator, the light beam that Polarizer 1 is crossed in transmission by liquid crystal cell 3, is stopped by Polarizer 2 in by linear polarisation then fully.The result is to show the image with high-contrast.
Yet as shown in Figure 2, the oblique incidence of light is expressively and unlike normal incidence.Not the axial vergence direction of z, promptly favouring on the direction (so-called OFF-AXIS) of the polarization direction of Polarizer 1 and 2, be incident on the influence that light on the liquid crystal indicator is subjected to delay, in the time of the liquid crystal layer of the homeotropic alignment of its transflective liquid crystal element 3, demonstrated the variation of degree of polarization.In addition, the surperficial transmission shaft of Polarizer 1 and Polarizer 2 has departed from verticality.Owing to these two reasons, can not be stopped fully by Polarizer 2 with the light of OFF AXIS vergence direction incident, thereby in black the demonstration, cause light leak and reduced contrast.
Polar angle and position angle will be by following qualifications.Polar angle be depart from film Surface Vertical direction, be the pitch angle of the z axle among Fig. 1 and 2.For example, the polar angle that has 0 ° perpendicular to the direction on film surface.The direction of the line that turns clockwise from the forward of x axle is represented at the position angle.For example, the forward of x axle has 0 ° position angle.The forward of y axle has 90 ° azimuth direction.Above the vergence direction of mentioned OFFAXIS comprise that mainly polar angle is not that 0 ° and position angle are those of 45 °, 135 °, 225 ° or 315 °.
Fig. 3 has described the diagram of the example of the structure that is used to explain effect of the present invention.Except providing between liquid crystal cell 3 and the Polarizer 1 the optical resin film (being also referred to as " optical compensation films " hereinafter) 4, the structure of Fig. 3 is identical with the structure of Fig. 1.As previously mentioned, optical compensation films 4 satisfies relation of plane down:
(A)0.1＜Re(450)/Re(550)＜0.95
(B)1.03＜Re(650)/Re(550)＜1.93
(C)0.4＜(Re/Rth(450))/(Re/Rth(550)))＜0.95
(D)1.05＜(Re/Rth(650)/(Re/Rth(550))＜1.9
According to the present invention, use optical compensation films with optical property described above, make it might optically compensate R, G and B by the slow axis oblique incidence, and with the delay of wavelength variations.The result is, compares with the liquid crystal indicator of correlation technique, and the field-of-view angle contrast in black the demonstration can greatly be improved, and the colour developing on the direction of observation is greatly eliminated in black the demonstration.In instructions, the wavelength of R, G and B is respectively 650nm, 550nm and 450nm.The wavelength of R, G and B might not be by these value representatives.Yet these wavelength value are considered to be fit to be used for limiting the optical property that can bring into play effect of the present invention.
In the present invention, particularly pointed out the ratio R e/Rth of Re and Rth.This be because Re/Rth value determined in the twin shaft birefringent medium light that transmits with vergence direction along two in polarizing axis.Fig. 4 has described when only oblique incidence is on optical compensation films used in the present invention, the example of the result of calculation of the direction of an axle and the relation between the Re/Rth in formed these two inherent polarizing axis.In this calculated, the direction of suppose the light propagation was 34 ° of 45 ° at position angle and polar angles.Can shown result find out from Fig. 4 that in case Re/Rth is determined, an axle in the then inherent polarizing axis just can be determined.When incident light by optical compensation films the time, how incident light changes on degree of polarization mainly is to determine by the orientation of slow axis in the face of optical compensation films and the delay of optical compensation films.In the present invention, define the relation of Re/Rth for R, G and B wavelength, make in the face slow axis and postpone optimization, for R, G and B wavelength, this is mainly to determine the factor that degree of polarization changes.The result is, even have two kinds of factors, be that the inclination of liquid crystal layer postpones the skew for the surperficial transmission shaft of the influence of oblique incidence light and Polarizer 1 and 2, also allows by an optical compensation films full remuneration, and this makes the reduction that might eliminate contrast.This means when the time, can realize compensating substantially completely in whole visible region with R, the G of the whole visible-range of representative and parameter that B determines film.
When not applying voltage, that is, in black the demonstration, the VA mode LCD makes its liquid crystal molecule homeotropic alignment.Correspondingly, slow axis is perpendicular or parallel in the face of preferred optical compensation films 4 is provided with in Polarizer 1 or Polarizer 2, makes in black the demonstration, can not be subjected to the influence of the delay of optical compensation films 4 along the polarisation of the incident light of normal direction.Can also between Polarizer 2 and liquid crystal cell 3, further provide optical compensation films.In this case, slow axis is perpendicular or parallel in the face of also preferred this optical compensation films is provided with in Polarizer 1 or Polarizer 2.
Fig. 5 has described the diagram of the compensatory michanism of the structure that uses poincare sphere that Fig. 3 has been described.In this diagram, the transmission of light is 34 ° of 45 ° and polar angles at the position angle.In Fig. 5, such one axle that extends perpendicular to the direction of paper that the S2 axle is in the figure to be seen.Fig. 5 is the figure that observes poincare sphere from the forward of S2 axle.Drawing demonstration because Fig. 5 is a two dimension, is to show by the straight arrows among the figure because degree of polarization changes the displacement of the point that is caused.In fact, when the change of light, be by on poincare sphere, representing round the rotation of the specific axis of determining according to each optical characteristics with specific angle by liquid crystal layer or the caused degree of polarization of optical compensation films.
The polarisation of the incident light by Polarizer 1 among Fig. 3 is corresponding to the point (i) among Fig. 5.The polarisation of the light that is stopped by the absorption axes of Polarizer 2 in Fig. 3 corresponding to the point among Fig. 5 (ii).In the VA of correlation technique mode LCD, the OFF AXIS light leak on the vergence direction is to be caused by point (i) and skew (ii).Optical compensation films is used to the polarisation of incident light is changed to a little (ii) from point (i) usually, and this comprises the change of the degree of polarization of liquid crystal layer.The liquid crystal layer of liquid crystal cell 3 demonstrates the positive refraction anisotropy and is homeotropic alignment.Correspondingly, when the change of light by the degree of polarization of the caused incident light of liquid crystal layer is that the arrow that extends downwards in by Fig. 5 shows, and be to represent by rotation around the S1 axle.Correspondingly, can be stopped that among R, G and the B each, the starting point of rotation must be positioned to make a little and (ii) rotate on the formed line around the S1 axle by Polarizer 2 fully in order to make visible light by liquid crystal layer.Moreover, owing to rotation angle is directly proportional with the value Δ n ' d '/λ that removes effective delay Δ n ' d ' of the liquid crystal layer on the vergence direction with wavelength, therefore inequality in the rotation angle of each wavelength coverage R, G and B.Correspondingly,, be necessary, the polarisation of R, G before rotation and B all be positioned at by making a little (ii) rotate on the formed line round the S1 axle according to each rotation angle shown in Figure 5 for all polarisations that make R, G and B after rotation can reach a little (ii).In the present invention, for make by optical compensation films 4 and the polarisation of R, the G by liquid crystal cell 3 and B light can be as mentioned above like that, provide the Re/Rth that makes R, G and B to satisfy optical compensation films that predetermined relation arranges to realize optical compensation.
On the other hand, Fig. 6 has shown an example of correlation technique structure equally.Shown example has related to and has used the optical compensation films that has constant Re/Rth for wavelength in Fig. 6.In this case, even when adjusting the optical property of optical compensation films for G light and make rotation starting point by liquid crystal layer be located to make on the formed line that a little (ii) rotates around the S1 axle, the rotation starting point of R and B light can not be arranged on the identical line.Correspondingly, R and the B light by liquid crystal layer can not change according to some polarisation (ii), thereby can not be stopped fully by the absorption axes of this Polarizer.The result is the light leak of R light and B light to have taken place, thereby caused the aberration in the black demonstration.Even when having used for R and the optimized optical compensation films of B light, also same trouble can take place.
The invention is characterized in, provide have the light of normal direction incident with vergence direction, for example be the film of the different optical property of 60 ° the delay wavelength dispersion of light of direction incident at polar angle, and the positive purposes of such film in optical compensation.Scope of the present invention is not limited to the liquid crystal layer of this display mode.The present invention can be applied to having any display mode for example on the liquid crystal indicator of VA, IPS, ECB, TN and ocb mode.
Hereinafter, the optical characteristics, starting material, production method etc. with reference to them further describes optical resin film of the present invention (optical compensation films).
Under the situation of numeric representation physical property value, eigenwert etc., employed in this article term " from (numerical value 1) to (numerical value 2) " means that expression " is not less than (numerical value 1) to being not more than (numerical value 2) ".In addition, employed in this article term " (methyl) acrylate " means expression " in acrylate and the methacrylate at least any one ", and this is suitable for " (methyl) acrylic acid " etc. equally.
[optical compensation films]
Optical resin film of the present invention helps to enlarge the field-of-view angle contrast of liquid crystal indicator, especially VA mode LCD, and helps to eliminate the aberration that these liquid crystal indicators depend on field-of-view angle.Optical compensation of the present invention can be set between the Polarizer of observer's side and the liquid crystal cell and overleaf between the Polarizer of side and the liquid crystal cell in any position or two positions in.For example, this optical compensation films can be used as independently combination of elements in liquid crystal indicator inside.Alternatively, optical characteristics can be offered the diaphragm that is used to protect polarizer in the optical compensation films, make that this optical compensation films can also be as the hyaline membrane as the Polarizer element that is attached in the liquid crystal indicator inside.
As mentioned above such, optical compensation films of the present invention satisfies relation of plane down:
(A)0.1＜Re(450)/Re(550)＜0.95；
(B)1.03＜Re(650)/Re(550)＜1.93；
(C) 0.4＜(Re/Rth (450))/(Re/Rth (550)))＜0.95; And
(D) 1.05＜(Re/Rth (650)/(Re/Rth (550))＜1.9, more preferably
(A)0.3＜Re(450)/Re(550)＜0.9
(B)1.05＜Re(650)/Re(550)＜1.8
(C)0.6＜(Re/Rth(450))/(Re/Rth(550)))＜0.8
(D)1.2＜(Re/Rth(650))/(Re/Rth(550))＜1.7
R, G and the B Re/Rth in each preferably drops in the scope of 0.1-0.8.
Preferably, pre-determine delay (Rth) on the whole optical compensation films thickness direction to eliminate the delay of this liquid crystal layer.Correspondingly, the preferable range of the delay (Rth) on the whole optical compensation films thickness direction changes along with the embodiment of various liquid crystal display layers.For example, (for example be used for VA mode liquid crystal element at optical compensation films of the present invention, the product of Δ nd is the VA mode liquid crystal element of 0.2 μ m-1.0 μ m, wherein d is that the thickness (μ m) and the Δ n of liquid crystal cell are the refraction ansiotropies of liquid crystal cell) optical compensation in, delay (Rth) on the whole optical compensation films thickness direction is preferably 70nm-400nm, 100nm-400nm more preferably, and be more preferably 100nm-300nm.Re length of delay for optical compensation films does not have concrete restriction, but it typically is 20nm-150nm, 20-70nm more preferably, and be more preferably 30-70nm.In addition,, it typically is 110 μ m or still less, be preferably 40 μ m-110 μ m, more preferably 60 μ m-110 μ m, more preferably 80 μ m-110 μ m though the thickness of optical compensation films is not had concrete restriction.
This optical compensation films has three mean refractive index nx, ny and nz respectively at orthogonal x, y and z direction of principal axis.These three refractive index characteristics that value is an optical compensation films.Rth and Re determine by the thickness d 1 of these values and film.Correspondingly, by selecting starting material, these raw-material additions, working condition etc. suitably, and in the scope of hope, adjust these factors, can prepare the optical compensation films that satisfies above-mentioned optics requirement.Owing to nx, ny and nz along with wavelength changes, so Rth and Re also change along with wavelength.By utilizing these characteristics, can prepare above mentioned optical compensation films.
In the present invention, the material for optical compensation films is not specifically limited.For example, this optical compensation films can be the birefringent polymer film that stretches or pass through the fixedly formed optical anisotropic layer of liquid-crystal compounds of specific arrangement.In addition, this optical compensation films is not limited to single layer structure and can has by a plurality of superimposed layer structures of forming at layer over each other.In the technical scheme of layer structure, the material of each layer can be different.For example, the laminar product that can use polymer film to constitute with the optical anisotropic layer that makes by liquid-crystal compounds.
Using liquid-crystal compounds to prepare under the situation of optical compensation films described above, because this liquid-crystal compounds has different embodiments of arranging, so the prepared anisotropic band of liquid-crystal compounds by fixing specific arrangement shows the optical property of hope in the laminated thing form use with individual layer or a plurality of layers.Specifically, above-mentioned optical compensation films can be to have stilt and the form of one or more optical anisotropic layers of forming on this stilt.The delay of the optical compensation films of this form can be regulated by the optical anisotropy of optical anisotropic layer as a whole.Liquid-crystal compounds can be divided into rod shaped liquid crystal compound and disc liquid-crystal compounds according to the shape of molecule.Each of these liquid-crystal compoundss all has degraded mould assembly or polymer-type.Any can use in the liquid-crystal compounds of these types.Using liquid-crystal compounds to prepare under the situation of optical compensation films recited above, preferably use rod shaped liquid crystal compound or disc liquid-crystal compounds.More preferably, use the disc liquid-crystal compounds that has the rod shaped liquid crystal compound of polymerizable groups or have polymerizable groups.
Optical compensation films can be made by polymer film.This polymer film can be the polymer film that stretches.As the material of this polymer film, use synthetic polymer (for example, polycarbonate, polysulfones, polyethersulfone, polyacrylate, polymethacrylate, norbornene resin, triacetyl cellulose) usually.By the bar-shaped compound (aromatic compounds that promptly has two aromatic rings) with aromatic ring being attached to the acylated cellulose basement membrane that the composition film forming in the acylated cellulose obtained also is preferred.The kind by regulating aromatic compounds suitably and the stretching condition of addition and film can prepare the polymer film of the optical property with hope.
(postponing to distribute)
In the present invention, the variation factor that postpones (Re) in the athwartship plane of optical compensation films preferably 5% or still less, more preferably 3% or still less, further preferred 2% or still less.The variation factor of the delay on the optical compensation film thickness direction (Rth) is preferably 10% or still less, and more preferably 8% or still less, further preferred 5% or still less.
Above-mentioned delay distribution value be by on the film that is obtained with the variation factor of the measured length of delay in the lateral separation of 1cm.
(being used to measure the method for delay)
Use the automatic birefringence instrument of KOBRA 21ADH type (by Ouji ScientificInstruments Co., Ltd. produces), in the atmosphere of 25 ℃ and 60%RH, under the wavelength of 590nm, measure the three-dimensional birefraction of film sample with the lateral separation of 1cm.Make the Re and the Rth of such mensuration calculate to determine variation factor (CV) then through following equation.
Variation factor (CV)=standard deviation/average retardation * 100
(wavelength dispersion performance)
Use the automatic birefringence instrument of KOBRA 21ADH type (by Ouji ScientificInstruments Co., Ltd. produces), in the atmosphere of 25 ℃ and 60%RH, under the wavelength of 450nm, 550nm and 650nm, measure the three-dimensional birefraction of this film sample.The length of delay of Huo Deing is used as Re (450), Re (550) and Re (650) respectively like this.
[production method]
The production of film of the present invention is preferably undertaken by following production method 1 or production method 2.
The production method that comprises production method 1 and production method 2 also is preferred.
To further describe hereinafter and preferably be used in production method 1 of the present invention and 2.
(production method 1)
According to the present invention, in order to prepare the film that has little horizontal delay rate of change according to of the present invention, the drying condition in the controlling diaphragm stretch processing is very important.In drawing process, use stenter usually.
In production method 1, stenter normally is made of at the step C of the step B of the steps A of laterally clamping film, cross directional stretch film and transverse relaxation film order.
Preferably, suppose at the average rate of drying of clamping step and stretching step it is that A%/second and the average rate of drying in relaxation step are B%/second,, can realize having the film that little delay distributes when film is when being the 1.9-4.2 drying with A/B.
Employed here term " rate of drying " means and is illustrated in the solvent in the film in the above-mentioned steps, that is, and and the % reduction (quality %) of residual solvent in the time per unit.(
In this instructions, mass ratio equals weight ratio).With further reference to measuring method, in measuring the step of average rate of drying, the film sample that is dried is with the interval of the 5m sample in the arbitrfary point.Then in the amount of each point measurement residual solvent.This measurement is carried out on a lot of points.Determined the minimizing percentage of per minute residual solvent amount according to travelling speed (m/min).Average then these measured values are determined average rate of drying.
In the present invention, the average rate of drying of clamping steps A and stretching step B is A%/second and average rate of drying in relaxation step C is that ratio A/B of B%/second is preferably 1.9-4.2, more preferably 2.4-4.1.Exchange the equal rate of drying of leveling so that the mode that A/B drops in the top restricted portion is not specifically limited.Yet, be the most effective at each step adjustment baking temperature and dry air flow rates.In keep dry temperature and dry air flow rates of the horizontal direction of film also is very important.
(production method 2)
As the result of broad research, the present inventor finds to adopt the production method of the collapse step of the stretching step that comprises stretched film and shrink film, might obtain to have the blooming of the optical physics performance of above-mentioned hope.
In the present invention, the preferred especially stretching step of using the carriage direction stretched film that is included in film and by the method for the production blooming of the collapse step of shrink film when laterally clamping perhaps is included in the stretching step of horizontal direction stretched film and the method that is used to produce blooming in the collapse step of the carriage direction shrink film of film.
[can be applied to the polymkeric substance in the film of the present invention]
As being applied to polymkeric substance in the film of the present invention, can use the acylated cellulose of for example describing in the back.Yet the adaptable here polymkeric substance that is included in the film of the present invention is not limited to acylated cellulose.The present invention can use all polymkeric substance that can be used as blooming.Can expect and obtain the effect identical with acylated cellulose.
As the polymkeric substance that can be used as the optical resin film, the fluoropolymer resin that can use Copolycarbonate for example or have the cycloolefin structure.When using such polymkeric substance, can obtain to have the film of good anti-environmental change.
The example that can be applied to Copolycarbonate herein comprises and comprising by the repetitive of following formula (Z) expression with by the Copolycarbonate of the repetitive of following formula (B) expression, wherein accounted for the 30-80mol% of repetitive total amount by the repetitive of following formula (Z) expression.
In formula (Z), R
1-R
8Represent hydrogen atom, halogen atom or C independently of one another
1-C
6Alkyl.C
1-C
6The example of alkyl comprises for example methyl, ethyl, isopropyl and cyclohexyl and aryl phenyl for example of alkyl.Preferably hydrogen atom and methyl in these groups.
In formula (Z), X represents the group by following formula (X) expression.R
9And R
10Represent hydrogen atom, halogen atom or C independently of one another
1-C
3Alkyl.Halogen atom and C
1-C
3The example of alkyl comprises as top listed identical halogen atom and alkyl.
In formula (B), R
11-R
18Represent hydrogen atom, halogen atom or C independently of one another
11-C
22Alkyl.C
1-C
22The example of alkyl comprises C
1-C
9Alkyl is for example phenyl, xenyl and triphenyl of methyl, ethyl, isopropyl and cyclohexyl and aryl for example.Preferably hydrogen atom and methyl in these groups.
In formula (B), Y represents to be selected from the group in the group that is made of following group, wherein R
19-R
21, R
23And R
24Represent that independently of one another at least one is selected from by hydrogen atom, halogen atom and C
1-C
22Group in the group that alkyl is formed.The example of alkyl comprises and above-described identical group.R
22And R
25Represent C independently of one another
1-C
20Alkyl.The example of this alkyl comprises methyl, ethylidene, propylidene, butylidene, cyclohexylidene, phenylene, naphthylene and inferior terphenyl.Ar
1-Ar
3Example comprise C
6-C
10Aryl is phenyl and naphthyl for example.
As above-mentioned Copolycarbonate, preferred here the use comprises that 30-60mol% is by the repetitive of following formula (C) expression and the 40-70mol% Copolycarbonate by the repetitive of following formula (D) expression.
More preferably, use and to comprise that 45-55mol% is by the repetitive of formula (C) expression and the 45-55mol% Copolycarbonate by the repetitive of formula (D) expression.
In formula (C), R
26-R
27Represent hydrogen atom or methyl independently of one another, from the viewpoint of operating performance, preferable methyl.
In formula (D), R
28-R
29Represent hydrogen atom or methyl independently of one another, from the viewpoint of economy, film properties etc., preferred hydrogen atom.
As blooming of the present invention, the preferred film that comprises top mentioned Copolycarbonate that uses with fluorene skeleton.Copolycarbonate with fluorene skeleton preferably have the different component ratio by the repetitive of formula (Z) expression with by the potpourri of the Copolycarbonate of the repetitive of formula (B) expression.Be preferably the 30-80mol% of whole Copolycarbonate by the percentage composition of the repetitive of formula (Z) expression, more preferably 35-75mol%, further preferred 40-70mol%.
Multipolymer recited above can be two or more by formula (Z) expression repetitive and the combination of two or more repetitives by formula (B) expression.
On the whole polycarbonate body that constitutes blooming, above-mentioned mol ratio can for example nuclear magnetic resonance (NMR) spectrometer be definite by using.
Above-mentioned Copolycarbonate can be by any known method production.This polycarbonate preferably produces dihydroxy compounds and phosgene polycondensation method, melt polycondensation method etc. by comprising.
The intrinsic viscosity of above-mentioned Copolycarbonate is preferably 0.3-2.0dl/g.When the intrinsic viscosity of above-mentioned Copolycarbonate in below 0.3, formed Copolycarbonate become too crisp in case its physical strength that can not keep it from but disadvantageous.On the contrary, when the intrinsic viscosity of above-mentioned Copolycarbonate surpassed 2.0, formed solution had too high viscosity, had caused to produce the problem of film-pressing line or be difficult to when polymerization finishes in the process of solution film-forming to purify.
Blooming of the present invention can be the composition (admixture) of above-mentioned Copolycarbonate and other polymer compound.In this case, it is preferably substantially the same that this polymer compound preferably can refractive indexes compatible with above-mentioned Copolycarbonate or these polymkeric substance, and this is because blooming of the present invention need be optically transparent.The instantiation of other polymkeric substance comprises poly-(styrene-be total to-maleic anhydride).About the ratio of components of Copolycarbonate and polymer compound, the ratio of components of this Copolycarbonate is 30-80 quality %, and preferably 40-80 quality %, and the ratio of components of polymer compound is 20-70 quality %, is preferably 20-60 quality %.Under the situation of admixture, two or more repetitives of Copolycarbonate also can be in conjunction with providing.The admixture that this admixture is preferably compatible.Even the composition of this admixture each other can not be compatible fully, the refractive index of these compositions can combine the light scattering of constituents for suppressing to component, and this makes might improve transparency.This admixture can comprise two or more materials of combination.Multiple Copolycarbonate and the also combination each other of other polymer compound.
The matter average molecular weight of polycarbonate is 1,000-1, and 000,000, preferred 5,000-500,000.Each matter average molecular weight of other polymer compound is 500-100,000, be preferably 1,000-50,000.
Example with polymer resin (being also referred to as " cyclic polyolefin hydrocarbon system resin " or " cyclic polyolefin " hereinafter) of cycloolefin structure comprises (1) norbornene resin, (2) polymkeric substance of monocycle shape alkene, (3) polymkeric substance of cyclic conjugated diene, the hydride of (4) alicyclic vinyl cyclic hydrocarbon polymer, and fluoropolymer resin (1)-(4).The example that preferably is used in polymkeric substance of the present invention comprises and contains at least one addition (be total to) polymkeric substance ring-type polyolefin by the repetitive of following formula (b) expression, and optional further comprise at least a repetitive of representing by formula (a) addition (being total to) polymkeric substance ring-type polyolefin.In addition, can advantageously use addition (being total to) polymkeric substance (comprising open loop (being total to) polymkeric substance) that contains at least a repetitive by formula (c) expression.In addition, can advantageously use and contain at least a repetitive and optional addition (being total to) the polymkeric substance ring-type polyolefin that further comprises at least a repetitive by formula (a) expression by formula (c) expression.
Formula (a)
Formula (b)
Formula (c)
In formula (a)-(c), m represents the integer of 0-4.R
1-R
6Represent hydrogen atom or C separately
1-C
10Alkyl.X
1-X
3And Y
1-Y
3Represent hydrogen atom, C separately
1-C
10The C that alkyl, halogen atom, halogen replace
1-C
10Alkyl, by X
1And Y
1, X
2And Y
2Or X
3And Y
3Form-(CH
2)
nCOOR
11,-(CH
2)
nOCOR
12,-(CH
2)
nNCO ,-(CH
2)
nNO
2,-(CH
2)
nCN ,-(CH
2)
nCONR
13R
14,-(CH
2)
nCONR
13R
14,-(CH
2)
nOZ ,-(CH
2)
nW or-(CO)
2O or-(CO)
2NR
15R
11, R
12, R
13, R
14And R
15Represent hydrogen atom or C separately
1-C
20Alkyl.Z represents alkyl or halo alkyl.W represents SiR
16 PD
3-P(wherein, R
16Expression unit C
1-C
10Alkyl; D represent halogen atom ,-OCOR
16Or-OR
16And p represents the integer of 0-3).Subscript n is represented the integer of 0-10.
In conjunction with functional group with high polarity very as substituent X
1-X
3And Y
1-Y
3, might increase the delay (Rth) of optical film thickness direction, and thereby improve the developability that postpones (Re) in the face of blooming.When stretching has the film of very big Re developability in film forming procedure, can improve the Re value of film.
Norborene is that addition (being total to) polymkeric substance is disclosed among JP-A-10-7732, JP-T-2002-504184, US2004229157A1, the WO2004/070463A1 etc.Norborene is that addition (being total to) polymkeric substance is to be that addition (being total to) polymerization of polynary ring unsaturated polymer obtains by norborene.If necessary, can make norborene is polynary ring unsaturated compound and conjugated diolefine for example ethene, propylene, butylene, butadiene and isoprene, non-conjugated diene for example ethylidene norbornene or linear diolefin compound for example vinyl cyanide, acrylic acid, methacrylic acid, maleic anhydride, acrylate, methacrylate, maleimide, vinyl acetate and vinyl chloride through addition polymerization.This norborene is that addition (being total to) polymkeric substance can be buied from Mitsubishi Chemical Corporation with trade name APL.APL can buy from the market with the various grades with different glass transition temperature (Tg), for example, and APL8008T (Tg:70 ℃), APL6013T (Tg:125 ℃), APL6015T (Tg:145 ℃).The norborene of granulation is that addition (being total to) polymkeric substance can be with trade name TOPAS8007,6013,6015 etc. from Polyplastics Co., and Ltd. buys.In addition, Appear3000 can buy from Ferrania Company.
Bornylene based polymer hydride is as disclosed among JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, JP-A-2003-159767 and the JP-A-2004-309979, by with polynary ring unsaturated compound process addition polymerization or ring-opening metathesis polymerization, next prepare by hydrogenation.In will being used in bornylene based polymer of the present invention, R
5And R
6Be preferably separately hydrogen atom or-CH
3X
3And Y
3Be preferably separately hydrogen atom, Cl or-COOCH
3Other substituting group is selected suitably.This norbornene resin can be buied or buy from ZEON CORPORATION with trade name ZeonorZF14, ZF16, Zeonex 250 or Zeonex 280 from JSRCorporation with trade name Arton G or Arton F.These products can be used among the present invention.
Hereinafter; to mainly consult and use under the situation of acylated cellulose; the production method of the starting material of optical resin film of the present invention, optical resin film of the present invention, the Polarizer that comprises this optical resin film and liquid crystal indicator etc. are described, but the present invention is not limited to acylated cellulose.
(acylated cellulose)
To describe hereinafter and be fit to be used in acylated cellulose of the present invention.
β-1, the cellulose that the glucose unit of 4-bonding constitutes has the free hydroxyl group at 2-, 3-and 6-position.Acylated cellulose is by using some or all polymkeric substance that obtain in these hydroxyls of carboxyl groups esterification with two or more carbon atoms.The degree of substitution of acyl group means in cellulosic 2-, 3-and 6-position on each position, the percentage of esterified hydroxy groups (100% esterification means that degree of substitution is 1).
Total degree of substitution, that is, DS2+DS3+DS6 is preferably 2.00-3.00, and more preferably 2.20-2.90 is preferably 2.40-2.82 especially.In addition, DS6/ (DS2+DS3+DS6) is preferably 0.315 or more, and preferred especially 0.32 or more, most preferably 0.325 or more.
DS2 is by the degree of acyl substituted (being called as " 2-position degree of substitution " hereinafter once in a while) at the locational hydroxyl of the 2-of glucose unit; DS3 be at the locational hydroxyl of the 3-of glucose unit by the degree of acyl substituted (being called as " 3-position degree of substitution " hereinafter once in a while), and DS6 is by the degree of acyl substituted (being called as " 6-position degree of substitution " hereinafter once in a while) at the locational hydroxyl of the 6-of glucose unit.
The quantity that is attached to the acyl group in the acylated cellulose of the present invention can only be a kind or two or more.When using two or more acyl groups, in the acyl group one acetyl group preferably.Suppose that the hydroxyl in 2-, 3-and 6-position is A by the degree of substitution sum that acetyl group replaces; the degree of substitution degree sum that hydroxyl in 2-, 3-and 6-position is replaced by propiono is that B and the hydroxyl in 2-, 3-and 6-position are C by the degree of substitution sum that bytyry replaces; then A is preferably 1.60-2.0; 1.7-1.9 more preferably; (B+C) and be preferably 0.60-0.80, more preferably 0.65-0.75.
For the measurement of the degree of substitution that is replaced by acetyl group, propiono and/or bytyry, can use ASTM:D-817-96 (be used to test cellulose acetate etc. method).Then these measured values are calculated.
For determining of the amount of unsubstituted hydroxyl on 2-, the 3-of acylated cellulose and 6-position, stay unsubstituted hydroxyl in the acylated cellulose with acyl substituted.Then the acylated cellulose that is replaced is like this carried out
13C-NMR.For the details of measuring method, can be with reference to Teduka et al, " Carbohydr.Res. ", 273 (1995), pp.83-91.
(method of synthetic acylated cellulose)
The ultimate principle of synthetic acylated cellulose is described in Migita et al, " Mokuzai Kagaku (Wood Chemistry) ", pp.180-190, Kyoritsu Shuppan, 1968.Typical synthetic method is included in the liquid phase acetylation under carboxylic acid anhydrides-acetate-sulfuric acid catalyst existence.
In order to obtain above-mentioned acylated cellulose; to cellulosic material for example velveteen and wood pulp carry out an amount of acetate pre-service, that puts into cooling in advance then is synthesized complete acylated cellulose (almost is 3.00 at 2-, 3-and the locational total degree of substitution of 6-) by the potpourri of carboxylic acidization through esterification.Above-mentioned potpourri by carboxylation generally includes acetate as solvent, carboxylic acid anhydrides as esterifying reagent and sulfuric acid as catalyzer.Carboxylic acid anhydrides normally surpasses with the summation of the cellulosic amount of carboxylic acid anhydrides reaction and the water capacity in this system with stoichiometry and uses.For hydrolysis stay in this system the excess carboxylic acid acid anhydride and in and the partial esterification catalyzer, after esterification finishes, then add neutralization reagent (for example, the oxide of carbonate, acetate or calcium, magnesium, iron, aluminium or zinc) aqueous solution.Next; in the presence of a small amount of acylation reaction catalyst (common remaining sulfuric acid); the complete acylated cellulose that obtains like this remained under 50-90 ℃ the temperature, make its experience cause that it is converted to the saponification slaking of the acylated cellulose of the acyl substituted degree with hope and the degree of polymerization.When obtaining the acylated cellulose of such hope; the catalyzer that is retained in this system is neutralized fully or this acylated cellobiose cellulose solution put into water or dilute sulfuric acid and do not need to be neutralized (alternatively with above mentioned neutralization reagent; water or dilute sulfuric acid are put into this acylated cellobiose cellulose solution) separate this acylated cellulose, this acylated cellulose process flushing and stabilization or other are processed obtained above-mentioned specific acylated cellulose.
In above-mentioned cellulose acylate film, constitute that the component of polymer of this film preferably makes by above-mentioned specific acylated cellulose basically.Employed here " basically " means the component of polymer of expression 55% or more (preferred 70% or more, more preferably 80% or more).
Preferred above-mentioned acylated cellulose uses with particle form.Employed 90 quality % or more particles preferably have the particle diameter of 0.5-5mm.In addition, employed 50 quality % or more particles preferably have the particle diameter of 1-4mm.The particle acylated cellulose preferably approaches spherical form.
The acylated cellulose that preferably is used among the present invention is preferably 200-700 according to the degree of polymerization that viscometric degree of polymerization calculates, more preferably 250-550, further preferred 250-400, preferred especially 250-350.Average degree of polymerization can be measured (Kazuo Uda by the intrinsic viscosity method that is proposed by Uda et al, Hideo Saito, " Seni Gakkaishi (JOURNAL OF THESOCIETY OF FIBER SCIENCE AND TECHNOLOGY; JAPAN) ", No.1, Vol.18, pp.105-120,1962).For more details, can be referring to JP-A-9-95538.
When low molecular composition was removed, formed acylated cellulose had the mean molecular weight (degree of polymerization) that is enhanced.Yet the viscosity of this acylated cellulose is lower than the viscosity of common acylate.Like this, as above-mentioned acylated cellulose, those that do not have a low molecular composition are suitable.Acylated cellulose with low content low molecular composition can obtain by remove low molecular composition from the acylated cellulose that synthesizes by conventional method.Removing of low molecular composition can usually be carried out by clean this acylated cellobiose with appropriate organic solvent.In order to produce the acylated cellulose of low molecular composition with low content, be preferably based on the acylated cellulose of 100 mass parts, the amount of the sulfuric acid catalyst in the acylation reaction is adjusted in the scope of 0.5-25 mass parts.Above the amount of sulfuric acid catalyst drops in the restricted portion time, the acylated cellulose of (molecular weight distribution uniformly) of catering to the need can synthetic molecular weight distributes.When in the production that is used in acylated cellulose the time, this acylated cellulose preferably has 2 quality % or lower, more preferably 1 quality % or lower, particularly 0.7 quality % or lower water cut.Acylated cellulose contains the water cut of water and the known 2.5-5 of having quality % usually.In order to provide water cut to drop on acylated cellulose in the scope of the invention, need dry this acylated cellulose.Do not limit drying means is concrete, as long as can reach the water cut of hope.
For as the cotton of the parent material of above-mentioned acylated cellulose and the details of its synthetic method, can be with reference to Kokai Giho No.2001-1745, March 15 calendar year 2001, JanpanInstitute of Invention and Innovation, pp.7-12.
Can be according to cellulose acylate film of the present invention by obtaining with above-mentioned acylated cellulose and the optional solution film forming of adjuvant in organic solvent.
(adjuvant)
The example that can be incorporated into the adjuvant in this resin solution above-mentioned acylated cellobiose cellulose solution for example of the present invention comprises that plastifier, ultraviolet light absorber, wear inhibitor, delay (optical anisotropy) development agent, delay (optical anisotropy) reduce agent, particulate material, peel off promoter and infrared absorbent.In the present invention, the preferred use postpones developping agent.In addition, preferably use plastifier, ultraviolet light absorber, peel off at least a in promoter, dyestuff and the matting agent.
These adjuvants can be that solid matter or oil are the form of material.In other words, not restriction particularly of the fusing point of these adjuvants or boiling point.For example, fusing point is that 20 ℃ or lower and 20 ℃ or higher ultraviolet light absorber can mix each other and use or use with potpourri with plastifier.For details, can be with reference to JP-A-2001-151901.
As ultraviolet light absorber, can use the ultraviolet light absorber of any kind of according to purpose.The example that can be applied to the ultraviolet light absorber of this paper comprises that salicylic acid is that absorbing agent, benzophenone series absorbing agent, benzotriazole are that absorbing agent, benzoic ether are that absorbing agent, cyanoacrylate are that absorbing agent and nickel complex salt are absorbing agent.In these ultraviolet light absorbers, preferably benzophenone series absorbing agent, benzotriazole are that absorbing agent and salicylate are absorbing agent.The example of benzophenone series ultraviolet light absorber comprises 2,4-dihydroxy benaophenonel, 2-hydroxyl-4-acetoxyl group benzophenone, 2-hydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxy-4-methoxy benzophenone, 2,2 '-dihydroxy-4,4 '-methoxy benzophenone, Octabenzone, 2-hydroxyl-4-dodecyloxy benzophenone and 2-hydroxyl-4-(2-hydroxy-3-methyl propenyloxy group) propoxyl group benzophenone.Benzotriazole be the example of ultraviolet light absorber comprise 2 (2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2 (2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2 (2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole, 2 (2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole and 2 (2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole.Salicylate is that the example of absorbing agent comprises phenyl salicytate, p-octylphenyl salicylate and p-t-butylphenyl salicylate.In these ultraviolet light absorbers as an example, particularly preferably be 2-hydroxyl-4-methoxy benzophenone, 2,2-dihydroxy-44 '-methoxy benzophenone, 2 (2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2 (2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2 (2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole and 2 (2 '-hydroxyl-3 ', 5 '-two 2-methyl-2-phenylpropane bases)-the 5-chlorobenzotriazole.
The preferred multiple ultraviolet light absorber with different absorbing wavelength that uses to obtain the high-barrier effect in wide wavelength coverage.As the ultraviolet light absorber that is used for liquid crystal, from the viewpoint that prevents that liquid crystal from degenerating, the preferred ultraviolet light absorber that has excellent absorption for the ultraviolet ray of 370nm or lower wavelength that uses is perhaps for the almost non-absorbent ultraviolet light absorber of visible light of 400nm or higher wavelength.Benzotriazole based compound most preferably in these ultraviolet light absorbers, this is because they seldom cause the unnecessary dyeing of cellulose esters.
As this ultraviolet light absorber, can also use the compound that is disclosed among JP-A-60-235852, JP-A-3-199201, JP-A-5-1907073, JP-A-5-194789, JP-A-5-271471, JP-A-6-107854, JP-A-6-118233, JP-A-6-148430, JP-A-7-11056, JP-A-7-11055, JP-A-7-11056, JP-A-8-29619, JP-A-8-239509 and the JP-A-2000-204173 here.
Based on acylated cellulose, the amount of the ultraviolet light absorber of institute's combination is preferably 0.001-5 quality %, more preferably 0.01-1 quality %.When the amount of the ultraviolet light absorber of institute's combination drops on below the 0.001 quality %, then can not give full play to the desirable effect of these ultraviolet light absorbers.On the contrary, when will in conjunction with the amount of ultraviolet light absorber surpass 5 quality %, then this ultraviolet light absorber may ooze out from the surface of film.
In addition, this ultraviolet light absorber can add in the acylated cellulose dissolving, perhaps can join by dissolving in the prepared dope.Especially preferably use static mixer, ultraviolet light absorber is joined in the dope of preparing mobile mold, this is because can easily adjust spectral absorption characteristics.
Above-mentioned destruction inhibitor can be used for preventing the destruction of triacetyl cellulose etc.The example of destruction inhibitor comprises that for example butylamine, hindered amine compound (JP-A-8-325537), guanidine compound (JP-A-5-271471), benzotriazole are ultraviolet light absorber (JP-A-6-235819) and benzo benzophenone series ultraviolet light absorber (JP-A-6-118233) to compound.
As plastifier, here preferred use is phosphate or carboxylate.More preferably above-mentioned plastifier is selected from following group: triphenyl phosphate (TPP); tricresyl phosphate (TCP); phosphate toluene diphenyl ester; octyl diphenyl phosphate; phosphoric acid xenyl diphenyl ester (BDP); trioctyl phosphate; tributyl phosphate; dimethyl phosphate (DMP); diethyl phthalate (DEP); dibutyl phthalate (DBP); dioctyl phthalate (DOP); diphenyl phthalate (DPP); di (2-ethylhexyl) phthalate (DEHP); O-acetyl triethyl citrate (OACTE); O-tributyl 2-acetylcitrate (OACTB); citric acid acetyl triethyl; citric acid acetyl tributyl; butyl oleate; methyl acetylated castor oil carboxylic ester; dibutyl sebacate; glycerol triacetate; glycerin tributyrate; butyl phthalyl ethyl hexanol acid esters; ethyl phthalyl ethyl hexanol acid esters; methyl phthalyl ethyl hexanol acid esters; with butyl phthalyl butyl alcohol acid esters.In addition, above-mentioned plastifier is preferably selected from (two) pentaerythritol ester, glyceride and double glyceride.
The example of peeling off promoter comprises ETHYL CTTRATE.For the details of infrared absorbent, can be with reference to JP-A-2001-194522.
In addition, in the present invention, can add dyestuff and regulate colourity.Based on the quality of acylated cellulose, the content of dyestuff is preferably 10ppm-1,000ppm, more preferably 50ppm-500ppm.Combination of dyes transmits its light that might reduce acylated cellulose and improves yellowish color and luster.These compounds can add or add with solvent in the solution of preparation acylated cellulose or add individually in the process for preparing the acylated cellobiose cellulose solution or afterwards with acylated cellulose.Alternatively, these compounds can join with in the UVA solution that adds in the line.
Be used in dyestuff of the present invention preferably by following formula (I) or (II) expression compound.
Formula (I)
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Represent hydrogen atom, hydroxyl, aliphatic group, aryl, heterocyclic radical, halogen atom, cyano group, nitro, COR independently of one another
9, COOR
9, NR
9R
10, NR
10COR
11, NR
10SO
2R
11, CONR
9R
10, SO
2NR
9R
10, COR
11, SO
2R
11, OCOR
11, NR
9CONR
10R
11, CONHSO
2R
11Or SO
2NHCOR
11(wherein, R
9And R
10Represent hydrogen atom, aliphatic group, aryl or heterocyclic radical independently of one another; R11 represents aliphatic group, aryl or heterocyclic radical; R
9And R
10Can be interconnected to form 5-or 6-unit ring); And R
1And R
2Or R
2And R
3Can be interconnected to form ring.
Formula (II)
Wherein, R
21, R
23And R
24Represent hydrogen atom, hydroxyl, nitro, cyano group, aliphatic group, aryl, COR independently of one another
29, COOR
29, NR
29R
30, NR
30COR
31Perhaps NR
30SO
2R
31(wherein, R
29And R
30Have separately with formula (I) in R
9And R
10Identical implication; And R
31Have with (I) in R
11Identical implication).R
22Expression aliphatic group or aryl, condition is R
21, R
22, R
23And R
24In one or more are groups except hydrogen atom.
To further describe each group of constitutional formula (I) hereinafter.By R
1-R
11The aliphatic group of expression is represented C
1-C
20Alkyl (for example, methyl, ethyl, normal-butyl, isopropyl, 2-ethylhexyl, positive decyl, n-octadecane base), C
1-C
20Naphthenic base (for example, cyclopentyl, cyclohexyl) or allyl.Aliphatic group can have substituting group [for example, halogen atom (for example, F, Cl, Br, I), hydroxyl, cyano group, nitro, carboxylic acid group, C
6-C
10Aryl (for example, phenyl, naphthyl), C
0-C
20Amino (for example, NH
2, NHCH
3, N (C
2H
5)
2, N (C
4H
9)
2, N (C
8H
17)
2, anilino-, 4-methoxybenzene amido), C
1-C
20Amide group (for example, acetamido, hexanoyl amido, benzamido, stearamide base), C
1-C
20Carbamyl (for example, unsubstituted carbamyl, methylamino formoxyl, ethylamino formoxyl, octyl group carbamyl, cetyl methyl formoxyl), C
2-C
20Ester group (for example methoxycarbonyl group, carbethoxyl group, carbobenzoxy, positive butoxy carbonyl, dodecane oxygen carbonyl), C
1-C
20Alkoxy (for example, methoxyl, ethoxy, butoxy, isopropoxy, benzyloxy, phenoxy group, octadecane oxygen base), C
1-C
20Sulfoamido (for example, Methanesulfomide, ethyl sulfonamide, fourth sulfonamide, benzsulfamide, hot sulfonamide), C
0-C
20Sulfamoyl (for example, unsubstituted sulfamoyl, methyl sulfamoyl, butyl sulfamoyl, decyl sulfamoyl), 5-or 6-unit heterocycle (for example, pyridine radicals, pyrazolyl, morpholino base, piperidino, pyrrolinyl, benzoxazolyl)].
By R
1-R
11The aryl of expression represents to have substituting group [for example, those that are exemplified as the aliphatic group substituting group and C
1-C
20Alkyl (for example, methyl, ethyl, butyl, the tert-butyl group, octyl group)] C
6-C
10Aryl (for example, phenyl, naphthyl).
By R
1-R
11The heterocyclic radical of expression represents (for example can have substituting group, exemplify the substituent group that can have for above-mentioned aryl) 5-or 6-unit heterocycle (for example, pyridine, piperidines, morpholine, pyrrolidine, pyrazoles, pyrazolidine, pyrazoline, pyrazolone, benzoxazole).
By R
9Be connected to R
10The example of formed 5-or 6-unit ring comprises morpholine ring, piperidine ring and pyrrolidine ring.By R
1With R
2Or R
2With R
3The ring that is connected to form is 5-or 6-unit's ring (for example, phenyl ring, phthalimide ring) preferably.
Hereinafter will further describe the various groups in the formula (II).By R
21-R
24The expression aliphatic group have separately with formula (I) in R
1-R
11The identical implication of aliphatic group of expression.By R
21-R
24The expression aryl have separately with formula (I) in R
1-R
11The identical implication of aliphatic group of expression.
These adjuvants can add in any time in the preparation dope process.The step that adds these adjuvants can be carried out at the final step in the process of this dope of preparation.In addition, for the not concrete restriction of addition of these materials, as long as can show their function.At cellulose acylate film is that the kind of the adjuvant in each layer can be different with addition under the situation about forming with multilayer form.It is disclosed like that for example to be disclosed in JP-A-2001-151902, and these technology are known up to now.Preferred kind and addition by suitably selecting these adjuvants; will be by cupping machine (Vibron:DVA-225; produce by ITKeisoku K.K.) glass transition temperature Tg of the cellulose acylate film that constitutes by acylated cellulose of measurement; pre-determine at 70 ℃-150 ℃, more preferably in 80 ℃-135 ℃ the scope.In other words, from the processing applicability viewpoint of the assembling of the processing of Polarizer and liquid crystal indicator for example, preferably drop in the top restricted portion according to the glass transition temperature T g of cellulose acylate film of the present invention.
As these adjuvants, preferred use is disclosed in Kokai GihoNo.2001-1745, March 15 calendar year 2001, pp.16 and back, those of Japan Institute ofInvention and Innovation in detail.
(delay developping agent)
In the present invention, the preferred delay developping agent that uses is realized the length of delay of wishing.
Contain the component of polymer of acylated cellulose etc. based on 100 mass parts, postpone developping agent and be to add, Rth is improved every μ m film thickness 0.11 or more, more preferably 0.2 or more, more preferably 0.3 or more with the amount of 1 mass parts.
Being used in delay developping agent of the present invention can be by development agent bar-shaped or that discotic compound makes.
As above-mentioned bar-shaped or discotic compound, can use compound with at least two aromatic rings.
Contain the component of polymer of acylated cellulose based on 100 mass parts, will in conjunction with the amount of the delay developping agent that makes by bar-shaped compound be preferably the 0.1-30 mass parts, more preferably 0.5-20 mass parts.
Contain the component of polymer of acylated cellulose based on 100 mass parts, plate-like postpones developping agent preferably with the 0.05-30 mass parts, and more preferably the 0.1-20 mass parts is more preferably the 0.2-15 mass parts, and most preferably the amount of 0.5-10 mass parts is used.
Discotic compound postpones to be better than bar-shaped compound on the extensibility at Rth, therefore is preferred the use under the situation that the very large Rth of needs postpones.
Two or more postpone developping agent and can be used in combination.
The above-mentioned delay developping agent that is made by bar-shaped compound or discotic compound preferably has maximum absorption and does not almost absorb at visible-range at 250-400 wavelength place so.
To further describe this discotic compound hereinafter.As discotic compound, can use compound here with at least two aromatic rings.
Employed in this article " aromatic ring " means also comprise heteroaromatic group except aromatic hydrocarbon ring.
Aromatic hydrocarbon ring is 6-unit's ring (that is phenyl ring) especially preferably.
Heteroaromatic group is the unsaturated heterocycle group normally.Heteroaromatic group is 5-unit ring preferably, 6-unit ring or 7-unit ring, more preferably 5-unit ring or 6-unit ring.Aromatic heterocyclic has maximum two keys usually.As heteroatoms, preferably use nitrogen-atoms, oxygen atom and sulphur atom, particularly nitrogen-atoms here.The example of virtue heterocycle comprises 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, the 5-triazine ring.
The preferred examples of aromatic ring comprises 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-triazines ring.In these aromatic rings, particularly preferably be the 1,3,5-triazines ring.Quite at length, as discotic compound, the preferred here discotic compound that is disclosed among the JP-A-2001-166144 that uses.
The quantity that is included in the aromatic ring in the above-mentioned discotic compound is preferably 2-20, and more preferably 2-12 is more preferably 2-8, most preferably 2-6.
About the connection of two aromatic rings, (a) they can form condensed ring, and (b) they can directly interconnect by singly-bound, or (c) they can change connection (because aromatic ring can not form the spiral shell key) mutually by linking group.Can set up any connection in (a)-(d).
The preferred examples of condensed ring (a) (being formed by the polycondensation of two or more aromatic rings) comprises the indenes ring, naphthalene nucleus, the azlene ring, the fluorenes ring, phenanthrene ring (phenathrene), anthracene nucleus, the acenaphthenylene ring, inferior cyclohexyl biphenyl, the naphtho-naphthalene nucleus, the pyrene ring, indole ring, the iso-indoles ring, the coumarone ring, the benzothiophene ring, the benzotriazole ring, purine ring, the indazole ring, the chromene ring, the quinoline ring, the isoquinoline ring, the quinolidine ring, the quinazoline ring, the cinnolines ring, quinoxaline ring, the phthaladine ring, the puteridine ring, the carbazole ring, the acridine ring, the phenathridine ring, the oxa-anthracene nucleus, the azophenlyene ring, the phenothiazine ring, phenoxathine ring phenoxazine ring, with the thianthrene ring.In these condensed ring, preferably naphthalene nucleus, azlene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring.
Singly-bound (b) is the key between the carbon atom of two aromatic rings preferably.Two or more aromatic rings can connect by two or more singly-bounds and form two fat hydrocarbon ring or non-aromaticity heterocycles between the aromatic ring.
Linking group (c) also preferably is connected on the carbon atom of two aromatic rings.This linking group preferably alkylidene, alkenylene, alkynylene ,-CO-,-O-,-NH-,-S-or their combination.To provide below in conjunction with comprise these groups the example of connection base.Putting in order of composition in following linking group can be reversed.
c1：-CO-O-
c2：-CO-NH-
C3:-alkylidene-O-
c4：-NH-CO-NH-
c5：-NH-CO-O-
c6：-O-CO-O-
C7:-O-alkylidene-O-
The c8:-CO-alkenylene-
C9:-CO-alkenylene-NH-
C10:-CO-alkenylene-O-
C11: alkylidene-CO-O-alkylidene-O-CO-alkylidene-
C12:-O-alkylidene-CO-O-alkylidene-O-CO-alkylidene-O-
C13:-O-CO-alkylidene-CO-O-
The c14:-NH-CO-alkenylene-
The c15:-O-CO-alkenylene-
Aromatic ring and linking group can have substituting group.
Substituent example comprises halogen atom (F; Cl; Br; I); hydroxyl; carboxyl; cyano group; amino; sulfo group; carbamyl; sulfamoyl; urea groups; alkyl; alkenyl; alkynyl; aliphatic acyl; the aliphatic series acyloxy; alkoxy; alkoxy carbonyl group; alkoxycarbonyl amido; alkylthio group; alkyl sulphonyl; the aliphatic series amide group; the aliphatic series sulfoamido; the amino that aliphatic series replaces; the carbamyl that aliphatic series replaces; the sulfamoyl that aliphatic series replaces; the urea groups that aliphatic series replaces; with non-aromaticity heterocyclic group.
The quantity of the carbon atom in the alkyl is preferably 1-8.Chain-like alkyl is better than cyclic alkyl.Straight chained alkyl is particularly preferred.This alkyl further preferably has substituting group (for example, the amino of hydroxyl, carboxyl, alkoxy, alkyl replacement).The example of alkyl (alkyl that comprises replacement) comprises methyl, ethyl, normal-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxy ethyl and 2-diethylamino ethyl.
The quantity of the carbon atom in the thiazolinyl is preferably 2-8.The chain alkynyl is better than the ring-type thiazolinyl.Straight-chain alkenyl is particularly preferred.Thiazolinyl can further have substituting group.The example of thiazolinyl comprises vinyl, allyl and 1-hexenyl.
The quantity of the carbon atom in the alkynyl is preferably 2-8.The chain alkynyl is preferable over the ring-type alkynyl.Straight-chain alkynyl is particularly preferred.Alkynyl can further have substituting group.The example of alkynyl comprises ethinyl, 1-butynyl and 1-hexin base.
Carbon number in the aliphatic acyl is preferably 1-10.The example of aliphatic acyl comprises acetyl group, propiono and bytyry.
Carbon number in the aliphatic series acyloxy is preferably 1-10.The example of aliphatic series acyloxy comprises acetoxyl group.
Carbon number in the alkoxy is preferably 1-8.Alkoxy can further have substituting group
(for example alkoxy).The example of alkoxy (alkoxy that comprises replacement) comprises methoxyl, ethoxy, butoxy and methoxy ethoxy.
Carbon number in the alkoxy carbonyl group is preferably 2-10.The example of alkoxy carbonyl group comprises methoxycarbonyl group and carbethoxyl group.
The quantity of the carbon atom in the alkoxycarbonyl amido is preferably 2-10, and the example of alkoxycarbonyl amido comprises the amino and carbethoxyl group amino of methoxycarbonyl group.
Carbon number in the alkylthio group is preferably 1-12.The example of alkylthio group comprises methyl mercapto, ethylmercapto group and hot sulfenyl.
Carbon number in the alkyl sulphonyl is preferably 1-8.The example of alkyl sulphonyl comprises mesyl and ethylsulfonyl.
Carbon number in the aliphatic series amide group is preferably 1-10.The example bag acetamido of aliphatic series amide group.
Carbon number in the aliphatic series sulfoamido is preferably 1-8.Example armored sulfoamido, fourth sulfoamido and the positive hot sulfoamido of aliphatic series sulfoamido.
Carbon number in the amino that aliphatic series replaces is preferably 1-10.The example of the amino that aliphatic series replaces comprises dimethylamino, diethylamino and 2-carboxy ethyl amino.
Carbon number in the carbamyl that aliphatic series replaces is preferably 2-10.The example of the carbamyl that aliphatic series replaces comprises methylamino formoxyl and diethylamino formoxyl.
Carbon number in the sulfamoyl that aliphatic series replaces is preferably 1-8.The example of the sulfamoyl that aliphatic series replaces comprises methyl sulfamoyl and diethyl amino sulfonyl.
The carbon number of the urea groups that aliphatic series replaces is preferably 2-10.The urea groups that aliphatic series replaces example comprise the methyl urea groups.
The example of non-aromaticity heterocyclic group comprises piperidyl and morpholinyl.
The molecular weight of the delay developping agent that is made by discotic compound is preferably 300-800.
In the present invention, except discotic compound recited above, can preferably use bar-shaped compound with linearity molecular structure.Employed in this article " linearity molecular structure " means that the stable molecular structure of the thermodynamics of bar-shaped compound is linear.The stable structure of thermodynamics can be by crystalline texture analysis or Molecular Orbital Calculation.For example, can use Molecular Orbital Calculation software (for example, WinMOPAC2000, by Fujitsu Co., Ltd. produces) to implement Molecular Orbital Calculation, make it might determine to make the minimized molecular structure of formation heat of compound.Employed here term " linearity molecular structure " means that also the most stable thermodynamics molecular structure of such calculating has formed main chain with 140 degree or bigger angle.
This bar-shaped compound preferably has the compound of at least two aromatic rings.As bar-shaped compound with at least two aromatic rings, the preferred compound that following formula (1) expression is arranged that uses:
Ar
1-L
1-Ar
2 (1)
Wherein, Ar
1And Ar
2Represent aromatic ring separately.
The example that can be used in this aromatic ring comprises aryl (aromatic hydrocarbyl), the aryl that replaces and the aromatic heterocyclic group that replaces.
The aryl of aryl and replacement is better than the aromatic heterocyclic group of aromatic heterocyclic group and replacement.Heterocyclic radical in aromatic heterocyclic group is normally undersaturated.This aromatic heterocyclic group is 5-unit ring, 6-unit ring or 7-unit ring preferably, more preferably 5-unit ring or 6-unit ring.Aromatic heterocyclic group has maximum two keys usually.This heteroatoms is nitrogen-atoms, oxygen atom or sulphur atom preferably, more preferably nitrogen-atoms or sulphur atom.
The preferred embodiment of aromatic ring comprises phenyl ring, furan nucleus, thiphene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring and pyrazine ring in the aryl.In these aromatic rings, particularly preferably be phenyl ring.
Substituent example on the aromatic heterocyclic group of aryl that replaces and replacement comprises that halogen atom (for example; F; Cl; Br; I); hydroxyl; carboxyl; cyano group; amino; alkyl amino (for example; methylamino; ethylamino; fourth amino; dimethylamino); nitro; sulfo group; carbamyl; alkyl-carbamoyl (for example; N-methylamino formoxyl; N-ethylamino formoxyl; N; the N-formyl-dimethylamino); alkylsulfamoyl group (for example; N-methyl sulfamoyl; N-ethyl sulfamoyl; N; N-dimethylamino sulfonyl); urea groups; the alkyl urea groups (for example; N-methyl urea groups; N; N-dimethyl urea groups; N; N; N '-trimethyl urea groups); alkyl (for example; methyl; ethyl; propyl group; butyl; amyl group; heptyl; octyl group; isopropyl; the s-butyl; the t-amyl group; cyclohexyl; cyclopentyl); alkenyl (for example; vinyl; allyl; hexenyl); alkynyl (for example; ethinyl; butynyl); acyl group (for example; formoxyl; acetyl group; bytyry; caproyl; lauroyl); acyloxy (for example; acetoxyl group; butyryl acyloxy; hexylyloxy; the bay acyloxy); alkoxy (for example; methoxyl; ethoxy; propoxyl group; butoxy; amoxy; heptan the oxygen base; octyloxy); aryloxy group (for example; phenoxy group); alkoxy carbonyl group (for example; methoxycarbonyl group; carbethoxyl group; the third oxygen carbonyl; butoxy carbonyl; penta oxygen carbonyl; heptan the oxygen carbonyl); aryloxy carbonyl (for example; carbobenzoxy); alkoxycarbonyl amido (butoxy carbonyl amino; own oxygen carbonylamino); alkylthio group (for example; methyl mercapto; ethylmercapto group; the rosickyite base; butylthio; penta sulfenyl; heptan sulfenyl; hot sulfenyl); arylthio (for example; thiophenyl); alkyl sulphonyl (for example; methyl sulphonyl; ethylsulfonyl; the sulfonyl propyl base; the butyl sulfonyl; the amyl group sulfonyl; the heptyl sulfonyl; the octyl group sulfonyl); amide group (for example; acetamido; amide-based small; the hexanoyl amido; the lauroyl amido); with non-aromatic heterocyclic group (for example, morpholyl base; the pyradinyl yl).
Substituent example in the aryl that replaces and the aromatic heterocycle group of replacement comprises amino, acyl group, acyloxy, amide group, alkoxy carbonyl group, alkoxy, alkylthio group and the alkyl that halogen atom, cyano group, carboxyl, hydroxyl, amino, alkyl replace.
Moieties in alkyl amino, alkoxy carbonyl group, alkoxy and alkylthio group and alkyl group can further have substituting group.Substituent example on moieties and the alkyl group comprises halogen atom, hydroxyl, carboxyl, cyano group, amino, alkyl amino, nitro, sulfo group, carbamyl, alkyl-carbamoyl, sulfamoyl, alkylsulfamoyl group, urea groups, alkyl urea groups, alkenyl, alkynyl, acyl group, acyloxy, amide group, alkoxy, aryloxy group, alkoxy carbonyl group, aryloxy carbonyl, alkylthio group, arylthio, alkyl sulphonyl, amide group and non-aromatic heterocyclic group.Preferably halogen atom, hydroxyl, amino, alkyl amino, acyl group, acyloxy, acyl amino and alkoxy in the substituting group on moieties and alkyl group.
In formula (1), L1 represent to be selected from alkylidene, alkenylene, alkynylene ,-O-,-CO-and their combination.
Alkylidene can have ring texture.Cyclic alkylidene is cyclohexylidene preferably, and particularly 1, the 4-cyclohexylidene.As the alkylidene of chain, straight-chain alkyl-sub-is better than branched alkylidene.
Carbon number in the alkylidene is preferably 1-20, more preferably 1-15, further preferred 1-10, further preferred 1-8, most preferably 1-6.
This alkenylene and alkynylene preferably have chain structure rather than ring texture, are more preferably linear chain structure rather than branched structure.
Carbon number in this alkenylene and the alkynylene is preferably 2-10, more preferably 2-8, further preferred 2-6, further preferred 2-4, most preferably 2 (ethenylidene or ethynylenes).
Carbon number in the arlydene is preferably 6-20, more preferably 6-16, further preferred 6-12.
In the molecular structure of formula (1), by Ar
1And Ar
2And be preferably 140 degree or bigger between the formed angle of the L1 between them.
Bar-shaped compound can be synthetic by any method that is disclosed in the document.The example of these documents comprises " Mol.Cryst.Liq.Cryst ", vol.53, the 229th page, 1979, " Mol.Cryst.Liq.Cryst ", vol.89, the 93rd page, 1982, " Mol.Cryst.Liq.Cryst ", vol.145, the 11st page, 1987, " Mol.Cryst.Liq.Cryst ", vol.170, the 43rd page, 1989, " J.Am.Chem.Soc. " vol.113, the 1st, 349 page, 1991, " J.Am.Chem.Soc. " vol.118, the 5th, 346 page, 1996, " J.Am.Chem.Soc. " vol.92, the 1st, 582 page, 1970, " J.Am.Chem.Soc. " vol.40, the 420th page, 1975, " Tetrahedron ", vol.48, No.16, the 3rd, 437,1992.
In the present invention, more wish to use the bar-shaped compound of representing by following formula (A).To further describe compound hereinafter by formula (A) expression.
Formula (A)
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
9And R
10Represent hydrogen atom or substituting group independently of one another, prerequisite is R
1, R
2, R
3, R
4And R
5In represent one of at least electron donating group; And R
8Expression hydrogen atom, C
1-C
4Alkyl, C
2-C
6Alkynyl, C
6-C
12Aryl, C
1-C
12Alkoxy, C
6-C
12Aryloxy group, C
2-C
12Alkoxy carbonyl group, C
2-C
12Acyl amino, cyano group or halogen atom.
In formula (A), R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
9And R
10Represent hydrogen atom or substituting group independently of one another.As this substituting group, can use substituting group T described later.
R
1, R
2, R
3, R
4And R
5In represent one of at least electron donating group.Preferably, R
1, R
3And R
5In one of the expression electron donating group.More preferably, R
3It is electron donating group.
Employed in this article term " electron donating group " means that Hammett ' s σ ρ value is 0 or littler group.The preferred use is disclosed in " Chem.Rev. ", and the Hammett ' s σ ρ value in 91,165 (1991) is 0 or littler those.In these groups, what more wish is that Hammett ' s σ ρ value is those of-0.85 to 0.These examples of groups comprise alkyl, alkoxy, amino and hydroxyl.
As electron donating group, preferably use alkyl or alkoxy here, more preferably alkoxy (preferably have 1-12 carbon atom, more preferably have 1-8 carbon atom, further preferably have 1-6 carbon atom, especially preferably have 1-4 carbon atom).
R in formula (A)
1Preferably hydrogen atom or electron donating group are more preferably alkyl, alkoxy, amino or hydroxyl, further preferred C
1-C
4Alkyl or C
1-C
12Alkoxy, preferred especially alkoxy (preferably have 1-12 carbon atom, more preferably have 1-8 carbon atom, further preferably have 1-6 carbon atom, especially preferably have 1-4 carbon atom) most preferably is methoxyl.
R in formula (A)
2Preferably hydrogen atom, alkyl, alkoxy, amino or hydroxyl, more preferably hydrogen atom, alkyl or alkoxy, further preferred hydrogen atom, alkyl (preferred C
1-C
4Alkyl, more preferably methyl) or alkoxy (preferably have 1-12 carbon atom, more preferably have 1-8 carbon atom, further preferably have 1-6 carbon atom, especially preferably have 1-4 carbon atom), particularly hydrogen atom, methyl or methoxy.
R in formula (A)
3Preferably hydrogen atom or electron donating group, be more preferably hydrogen atom, alkyl, amino or hydroxyl, further preferred alkyl or alkoxy, preferred especially alkoxy (preferably has 1-12 carbon atom, more preferably have 1-8 carbon atom, further preferably have 1-6 carbon atom, especially preferably have 1-4 carbon atom), most preferably be positive propoxy, ethoxy or methoxyl.
R in formula (A)
4Preferably hydrogen atom or electron donating group are more preferably hydrogen atom, alkyl, alkoxy, amino or hydroxyl, further preferred hydrogen atom, C
1-C
4Alkyl or C
1-C
12 alkyl (preferably have 1-12 carbon atom, more preferably have 1-8 carbon atom, further preferably have 1-6 carbon atom, especially preferably have 1-4 carbon atom), preferred especially hydrogen atom, C
1-C
4Alkyl or C
1-C
4Alkoxy, most preferably hydrogen atom, methyl or methoxy.
R in formula (A)
5Preferably hydrogen atom, alkyl, alkoxy, amino or hydroxyl, more preferably hydrogen atom, alkyl or alkoxy, further preferred hydrogen atom, alkyl (preferred, C
1-C
4Alkyl, more preferably methyl) or alkoxy (preferably have 1-12 carbon atom, more preferably have 1-8 carbon atom, further preferably have 1-6 carbon atom, especially preferably have 1-4 carbon atom), preferred especially hydrogen atom, methyl or methoxy.
R in formula (A)
6, R
7, R
9And R
10Preferably hydrogen atom, C separately
1-C
12Alkyl, C
1-C
12Alkoxy or halogen atom, more preferably hydrogen atom or halogen atom, further preferred hydrogen atom.
R in formula (A)
8Represent hydrogen atom, C
1-C
4Alkyl, C
2-C
6Alkynyl, C
6-C
12Aryl, C
1-C
12Alkoxy, C
6-C
12Aryloxy group, C
2-C
12Alkoxy carbonyl group, C2-C12 acyloxy, amide group, cyano group or halogen atom.If possible, R
8Can have substituting group.As this substituting group, can use the substituting group T that describes later.
R in formula (A)
8C preferably
1-C
4Alkyl, C
2-C
6Alkynyl, C
6-C
12Aryl, C
1-C
12Alkoxy, C
2-C
12Aryloxy group, more preferably C
6-C
12Aryl, C
1-C
12Alkoxy, C
2-C
12Aryloxy group, and further preferred C
1-C
12Alkoxy (preferably have 1-12 carbon atom, more preferably have 1-8 carbon atom, further preferably have 1-6 carbon atom, especially preferably have 1-4 carbon atom), preferred especially methoxyl, ethoxy, positive propoxy, isopropoxy or n-butoxy.
Formula (A) is more preferably following formula (I-A).
Formula (I-A)
Wherein, R
11The expression alkyl; R
1, R
2, R
4, R
5, R
6, R
7, R
9And R
10Represent hydrogen atom or substituting group independently of one another; R
8Expression hydrogen atom, C
1-C
4Alkyl, C
2-C
6Alkynyl, C
6-C
12Aryl, C
1-C
12Alkoxy, C
6-C
12Aryloxy group, C
2-C
12Alkoxy carbonyl group, C
2-C
12Amide group, cyano group or halogen atom.
In formula (I-A), R
1, R
2, R
4, R
5, R
6, R
7, R
9And R
10Suc as formula (A) middle define identical, comprise their preferable range.
In formula (I-A), R
11Expression C
1-C
12Alkyl.By R
11The expression alkyl can be straight or branched or can further have substituting group.R
11C preferably
1-C
12Alkyl, more preferably C
1-C
8Alkyl, further preferred C
1-C
6Alkyl, preferred especially C
1-C
4Alkyl (for example, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group).
The formula (I-B) that formula (A) is more preferably following.
Formula (I-B)
Wherein, R
1, R
2, R
4, R
5, R
6, R
7, R
9And R
10Represent hydrogen atom or substituting group independently of one another; R
11Expression C
1-C
12Alkyl; And X represents C
1-C
4Alkyl, C
2-C
6Alkynyl, C
6-C
12Aryl, C
1-C
12Alkoxy, C
6-C
12Aryloxy group, C
2-C
12Alkoxy carbonyl group, C
2-C
12Amide group, cyano group or halogen atom.
In formula (I-B), R
1, R
2, R
4, R
5, R
6, R
7, R
9And R
10Suc as formula (A) middle define identical, comprise their preferable range.
In formula (I-B), R
11Identical as definition in formula (I-A) comprises their preferable range.
In formula (I-B), X represents C
1-C
4Alkyl, C
2-C
6Alkynyl, C
6-C
12Aryl, C
1-C
12Alkoxy, C
6-C
12Aryloxy group, C
2-C
12Alkoxy carbonyl group, C
2-C
12Amide group, cyano group or halogen atom.
Work as R
1, R
2, R
4And R
5Each is naturally hydrogen atom the time, X is preferably alkyl, alkynyl, aryl, alkoxy or aryloxy group, more preferably aryl, alkoxy or aryloxy group, more preferably alkoxy (preferably has 1-12 carbon atom, more preferably have 1-8 carbon atom, further preferably have 1-6 carbon atom, especially preferably have 1-4 carbon atom), preferred especially methoxyl, ethoxy, positive propoxy, isopropoxy or n-butoxy.
Work as R
1, R
2, R
4And R
5In at least one when being substituent, X is preferably alkynyl, aryl, alkoxy carbonyl group or cyano group, more preferably aryl (preferably having 6-12 carbon atom), cyano group, alkoxy carbonyl group (preferably having 2-12 carbon atom), more preferably aryl (preferred C
6-C
12Aryl, more preferably phenyl, to cyano-phenyl or p-methoxyphenyl), alkoxy carbonyl group (preferred C
2-C
12Alkoxy carbonyl group, more preferably C
2-C
6Alkoxy carbonyl group, further preferred C
2-C
4Alkoxy carbonyl group, preferred especially methoxycarbonyl group, carbethoxyl group or the positive third oxygen carbonyl), or cyano group, preferred especially phenyl, methoxycarbonyl group, carbethoxyl group, positive third oxygen carbonyl or the cyano group.
The formula (I-C) that formula (A) is more preferably following.
Formula (I-C)
Wherein, R
1, R
2, R
4, R
5, R
11With X identical suc as formula definition in (I-B), comprise their preferable range.
In these compounds, wish that more the compound by formula (A) expression is the compound of being represented by following formula (I-D).
Formula (I-D)
Wherein, R
2, R
4And R
5Suc as formula (I-C) middle define identical, comprise their preferable range; R
21 and R
22Represent C independently of one another
1-C
4Alkyl; And X
1Expression C
6-C
12Aryl, C
2-C
12Alkoxy carbonyl group or cyano group.
R
21Expression C
1-C
4Alkyl, preferred C
1-C
3Alkyl, more preferably ethyl or methyl.
R
22Expression C
1-C
4Alkyl, preferred C
1-C
3Alkyl, more preferably ethyl or methyl, further preferable methyl.
X
1Expression C
6-C
12Aryl, C
2-C
12Alkoxy carbonyl group or cyano group, preferred C
6-C
10Alkoxy carbonyl group or cyano group, more preferably phenyl, to cyano-phenyl, p-methoxyphenyl, methoxycarbonyl group, carbethoxyl group, positive third oxygen carbonyl or the cyano group, further preferred phenyl, methoxycarbonyl group, carbethoxyl group, the positive third oxygen carbonyl.
Formula (A) most preferably is following formula (I-E).
Formula (I-E)
Wherein, R
2, R
4And R
5Suc as formula (I-D) middle define identical, comprise their preferable range, prerequisite is R
2, R
4And R
5In any one is by-OR
13(wherein, R
13Be C
1-C
4Alkyl) Biao Shi group; And R
21, R
22And X
1Suc as formula (I-D) middle define identical, comprise their preferable range.
In formula (I-E), R
2, R
4And R
5Suc as formula (I-D) middle define identical, comprise their preferable range.Yet, R
2, R
4And R
5In any one is by-OR
13(wherein, R
13Be C
1-C
4Alkyl) Biao Shi group.Preferably, R
4Or R
5Be by-OR
13The group of expression.More preferably, R
4Be by-OR
13The group of expression.
R
13Expression C
1-C
4Alkyl, preferred C
1-C
3Alkyl, more preferably ethyl or methyl, further preferable methyl.
Hereinafter substituting group T above-mentioned will be described in further detail.
These substituting groups can further be replaced.
If present, two or multi-substituent can be identical or different mutually.If possible, they can mutually combine and form a ring.
To further describe compound hereinafter with reference to their instantiation, but the present invention is not limited to this by formula (A) expression.
The present invention by the compound of formula (A) expression can by the benzoic acid that replaces and amphyl any common esterification synthesize, as long as can form ester bond.The example of such esterification comprise the benzoic acid that will replace change into carboxylic acid halides as functional group next with the method for phenol condensation, and the method that comprises benzoic acid and phenol derivatives dehydrating condensation in the presence of condensation reagent or catalyzer of replacement.
Consider production technology, comprise that next the benzoic acid that will replace changes into carboxylic acid halides is preferred with the method for phenol condensation as functional group.
As reaction dissolvent, can use hydrocarbon system solvent (preferred toluene or dimethylbenzene), ether series solvent (preferred dimethyl ether, tetrahydrofuran, diox etc.), ketone series solvent, ester series solvent, acetonitrile, dimethyl formamide, dimethyl acetamide etc. here.These solvents can use separately or use with their two or more potpourri.As reaction dissolvent, preferred here toluene, acetonitrile, dimethyl formamide or dimethyl acetamide.
Temperature of reaction is preferably at 0 ℃-150 ℃, and more preferably 0 ℃-100 ℃, further preferred 0 ℃-90 ℃, preferred especially 20 ℃-90 ℃.
The present invention preferably carries out under the situation that does not have alkali.If used alkali, then this alkali can be organic base or inorganic base, and preferred organic base is pyridine and trialkylamine (preferred triethylamine, ethyl diisopropyl amine etc.) for example.
Two or more bar-shaped compounds that maximum absorption wavelength in the solution ultra-violet absorption spectrum (λ max) is shorter than 250nm can be used in combination.
[particle matting agent]
According to optical resin film of the present invention for example cellulose acylate film preferably have and be attached to its inner particulate material as matting agent.The example that can be applied to particulate material herein comprises silicon dioxide, titania, aluminium oxide, zirconia, lime carbonate, talcum, clay, calcined kaolin, calcining calcium silicate, afwillite, alumina silicate, magnesium silicate and calcium phosphate.This particulate material preferably contains silicon and reduces turbidity.Particularly, silicon dioxide is preferred.This particulate silica preferably has 20nm or littler primary average particle size, and 70g/ rises or bigger apparent specific gravity.The mean diameter of primary granule more preferably in the scope of 5-16nm to reduce turbidity.The apparent specific gravity of particulate silica is preferably and is not less than the 90-200g/ liter, and more preferably is not less than the 100-200g/ liter.Along with apparent specific gravity improves, the suspending liquid that might more easily prepare high concentration reduces turbidity and gathering.
If you are using, comprise the component of polymer of acylated cellulose based on 100 mass parts, the amount of above-mentioned particulate silica is preferably the 0.01-0.3 mass parts.
These particulates form the secondary that mean grain size is 0.1-3.0 μ m usually.These particles form with the aggregation of primary granule in film exists, and highly is the irregularity at 0.1-3.0 μ m thereby formed on the film surface.Secondary mean grain size is preferably and is not less than 0.2 μ m to being not more than 1.5 μ m, more preferably is not less than 0.4 μ m and is not less than 0.6 μ m to being not more than 1.1 μ m to being not more than 1.2 μ m, most preferably being.When secondary mean grain size surpassed 1.5 μ m, formed film showed the turbidity of rising.On the contrary, when secondary mean grain size drops on 0.2 μ m following the time, prevent that the effect of rolling sound (squeak) is lowered.
For the measurement of primary and secondary particle diameter, under scanning electron microscope, observe the particle in the film.External diameter of a circle by particle limits this particle diameter.200 particles that are positioned at distributed locations have been observed.The measured value equalization is determined mean grain size.
For silicon dioxide microparticle, can use the product that can buy on the market, for example, Aerosil R972, R972V, R974, R812,200,200V, 300, R202, OX50, TT600 (by Nippon Aerosil Co., Ltd. produces).The zirconia particulate can be buied from the market with AerosilR976 and R811 (by Nippon Aerosil Co., Ltd. produces).These products can be used among the present invention.
In these products, particularly preferably be Aerosil 200V and Aerosil R972, this is because they are primary average particle size is that 20nm or littler and apparent specific gravity are that 70g/ rises or bigger silicon dioxide microparticle, has brought into play the huge effect that reduces friction factor when the turbidity that keeps blooming is low.
In the present invention, the cellulose acylate film for the particle that obtains to contain little secondary mean grain size can propose several different methods and be used for preparing particle suspension liquid.For example, can use the microparticle suspending liquid that comprises in advance preparation particle in solvent, this particle suspension liquid and a small amount of acylated cellulose solution stirring of preparation are separately prepared solution, this solution is mixed with main acylated cellulose rich liquor solution.This preparation method is desirable, and this is because silica particle can be disperseed well and can be made it be difficult to reassociate.Except that this method, can use the plain ester of agitating solution and small amount of fibers and prepare solution, use decollator to make this solution and particulate material disperse to prepare particle solution incorporated therein, the solution that uses inline mixer to make then to combine particle mixes fully with rich liquor solution.The present invention is not limited to these methods.In the process with mixing such as solvent and dispersed silicon dioxide particulate, concentration of silicon dioxide is preferably 5-30 quality %, more preferably 10-25 quality %, most preferably 15-20 quality %.Along with suspension concentration raises, thereby the turbidity of solution reduces along with addition and has advantageously further reduced turbidity and gathering.The content of matting agent is preferably 0.01-1.0g/m in final acylated cellulose rich liquor solution
2, more preferably 0.03-0.3g/m
2, 0.08-0.16g/m most preferably
2
The preferred embodiment of lower alcohol solvent comprises methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol and butanols.Be not specifically limited for other solvent except that lower alcohol, but preferred use employed solvent in the process of preparation cellulose esters.
[solvent]
The above-mentioned organic solvent that has wherein dissolved as the acylated cellulose of the example of resin used in the present invention will be described hereinafter.
Employed in this article term " good solvent " means that expression can be under 25 ℃, with the solvent of every 100g dissolving 5g or more acylated cellulose.On the contrary, employed here term " poor solvent " means that expression can be less than the solvent of the acylated cellulose of 5g with every 100g dissolving under 25 ℃.
In the present invention, as this organic solvent, can use mainly the chlorine series solvent that constitutes by chlorine-based organic solvent or not chloride be the chlorine-free solvent of organic solvent.
(chlorine series solvent)
In order to prepare acylated cellobiose cellulose solution of the present invention,, preferably use chlorine-based organic solvent as main solvent.In the present invention, be not specifically limited as long as it can dissolve acylated cellulose and mobile mold forms film, thereby the purpose that has reached it just for the kind of chlorine-based organic solvent.This chlorine-based organic solvent is preferably methylene chloride or chloroform.Particularly, methylene chloride is preferred.This chlorine-based organic solvent can use with the potpourri with chlorine-based organic solvent other organic solvent in addition.In this case, methylene chloride is necessary to use with the amount of at least 50 quality % based on the total amount of organic solvent.Other organic solvent that can be used in combination with chlorine-based organic solvent will be described in the present invention below.At length, other organic solvent that can be applied to herein is preferably selected from the group of forming in by the ester with 3-12 carbon atom, ketone, ether, pure and mild hydrocarbon.This ester, ketone, ether can have ring texture.Have two or more esters, ketone and ether functional group (that is, and-O-,-CO-and-COO-) compound also can be used as solvent.The functional group that this solvent can have other for example alcohol is a hydroxyl.The quantity of the carbon atom in having the solvent of two or more functional groups (if you are using) can drop on in the compound institute restricted portion with any functional group in these functional groups.C
3-C
12The example of ester comprises ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate.C
3-C
12The example of ketone comprises acetone, methyl ethyl ketone, metacetone, diisobutyl ketone, cyclopentanone, cyclohexanone and methyl cyclohexanone.C
3-C
12The example of ether comprises Di Iso Propyl Ether, dimethoxymethane, dimethoxy-ethane, 1,4-diox, 1,3-dioxolanes, tetrahydrofuran, anisole and phenylethyl alcohol.Example with organic solvent of two or more functional groups comprises acetate 2-ethoxy ethyl ester, 2-methyl cellosolve and butoxy ethanol.
The alcohol that is used in combination with chlorine-based organic solvent can preferably be straight chain, side chain or ring-type.In these organic solvents, preferably saturated aliphatic hydrocrbon.Hydroxyl in the alcohol can be first to tertiary.The example that can be applied to the alcohol of this paper comprises methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, the tert-butyl alcohol, 1-amylalcohol, 2-methyl-2-butanols and cyclohexanol.As alcohol, can also use fluorine system alcohol here.The example of fluorine system alcohol comprises 2-fluoroethanol, 2,2,2 tfifluoroethyl alcohol and 2,2,3,3-tetrafluoro-1-propyl alcohol.In addition, this hydrocarbon can be straight chain, side chain or ring-type.Can use aromatic hydrocarbon or aliphatic hydrocarbon.Aliphatic hydrocarbon can be saturated or unsaturated.The example of hydrocarbon comprises cyclohexane, hexane, benzene, toluene and dimethylbenzene.
Can be applied to other organic solvent here and be preferably selected from by the prescription of chlorine-based organic solvent below the example that combines of other organic solvent comprises, but the present invention is not limited to this.
* methylene chloride/ethanol/butanols (80/10/5/5, mass parts)
* methylene chloride/acetone/methanol/propyl alcohol (80/10/5/5, mass parts)
* methylene chloride/butanols/cyclohexane (80/10/5/5, mass parts)
* methylene chloride/methyl ethyl ketone/methyl alcohol/butanols (80/10/5/5, mass parts)
* methylene chloride/acetone/methyl ethyl ketone/ethanol/isopropyl alcohol (75/8/5/5/7, mass parts)
* methylene chloride/cyclopentanone/methanol/isopropanol (80/7/5/8, mass parts)
* methylene chloride/methyl acetate/butanols (80/10/10, mass parts)
* methylene chloride/cyclohexanone/methyl alcohol/hexane (70/20/5/5, mass parts)
* methylene chloride/methyl ethyl ketone/acetone/methanol/ethanol (50/20/20/5/5, mass parts)
* methylene chloride/1,3-dioxolanes/methanol/ethanol (70/20/5/5, mass parts)
* methylene chloride/diox/acetone/methanol/ethanol (60/20/10/5/5, mass parts)
* methylene chloride/acetone/cyclopentanone/ethanol/isobutyl alcohol/cyclohexane (65/10/10/5/5/5, mass parts)
* methylene chloride/methyl ethyl ketone/acetone/methanol/ethanol (70/10/10/5/5, mass parts)
* methylene chloride/acetone/ethyl acetate/ethanol/butanols/hexane (65/10/10/5/5/5, mass parts)
* methylene chloride/methyl acetoacetate/methanol/ethanol (65/20/10/5, mass parts)
* methylene chloride/cyclopentanone/ethanol/butanols (65/20/10/5, mass parts)
(chlorine-free solvent)
The chlorine-free solvent that preferably is used for preparing acetyl fibre cellulose solution of the present invention will be described hereinafter.As long as do not have specific restriction can dissolve acylated cellulose and can curtain coating form film for being used in chlorine-free organic solvent of the present invention, thereby reach its purpose just.The chlorine-free organic solvent that can be applied to herein is selected from the group of being made up of the ester with 3-12 carbon atom, ketone, ether, pure and mild hydrocarbon.This ester, ketone, ether can have ring texture.Have two or more esters, ketone and ether functional group (that is ,-O-,-CO-and-COO-) compound also can be used as solvent.The functional group that this solvent can have other for example alcohol is a hydroxyl.The quantity of the carbon atom in having the solvent of two or more functional groups if you are using, can drop on in the compound institute restricted portion with any functional group in these functional groups.C
3-C
12The example of ester comprises ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate.C
3-C
12The example of ketone comprises acetone, methyl ethyl ketone, metacetone, diisobutyl ketone, cyclopentanone, cyclohexanone and methyl cyclohexanone.C
3-C
12The example of ether comprises Di Iso Propyl Ether, dimethoxymethane, dimethoxy-ethane, 1,4-diox, 1,3-dioxolanes, tetrahydrofuran, anisole and phenylethyl alcohol.Example with organic solvent of two or more functional groups comprises acetate 2-ethoxy ethyl ester, 2-methyl cellosolve and butoxy ethanol.
The chlorine-free organic solvent that is used in acylated cellulose can be selected from above-mentioned various viewpoints, but is preferably as follows.More specifically, the preferably main mixed solvent that constitutes by above-mentioned chlorine-free organic solvent of this chlorine-free solvent.This is the potpourri of three kinds or more kinds of different solvents, wherein first solvent is methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolanes with at least a in the diox or their potpourri, second solvent is to be selected from the group that is made of ketone with 4-7 carbon atom or acetoacetic ester and the 3rd solvent is selected from by alcohol with 1-10 carbon atom or hydro carbons, preferably has the alcohols of 1-8 carbon atom.Be that second solvent can omit under the situation of potpourri of two or more solvents at first solvent.First solvent is more preferably methyl acetate, acetone, methyl formate, ethyl formate or their potpourri.Second solvent is preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetoacetate or their potpourri.
The 3rd solvent alcohol can be straight chain, side chain or ring-type.In these alcohol, preferably undersaturated aliphatic hydrocrbon.Hydroxyl in the alcohol can be first to tertiary.The example of alcohol comprises methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, the tert-butyl alcohol, 1-amylalcohol, 2-methyl-2-butanols and cyclohexanol.As this alcohol, can also use fluorine system alcohol here.The example of fluorine-based alcohol comprises 2-fluoroethanol, 2,2,2 tfifluoroethyl alcohol and 2,2,3,3-tetrafluoro-1-propyl alcohol.In addition, this hydrocarbon can be straight chain, side chain or ring-type.Can use aromatic hydrocarbon or aliphatic hydrocarbon.Aliphatic hydrocarbon can be saturated or unsaturated.The example of hydrocarbon comprises cyclohexane, hexane, benzene, toluene and dimethylbenzene.The pure and mild hydrocarbon of the 3rd solvent can use separately or use and without any restriction with two or more the potpourri in them.The instantiation of the alcohol of the 3rd solvent comprises methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, cyclohexanol, cyclohexane and hexane.In these alcohol, particularly preferably be methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol and 1-butanols.
Gross mass based on this potpourri, mixing ratio about above-mentioned three kinds of solvents, the mixing ratio of first solvent, second solvent and the 3rd solvent is respectively, preferred 20-95 quality %, 2-60 quality % and 2-30 quality %, more preferably 30-90 quality %, 3-50 quality % and 3-25 quality %, preferred especially 30-90 quality %, 3-30 quality % and 3-15 quality %.For the detailed description that is used in chlorine-free organic solvent of the present invention, can be with reference to Kokai GihoNo.2001-1745, March 15 calendar year 2001, pp.12-16, Janpan Institute of Inventionand Innovation.The example of the combination of chlorine-free organic solvent comprises following prescription, but the present invention is not limited to this.
* methyl acetate/acetone/methanol/ethanol/butanols (75/10/5/5/5, mass parts)
* methyl acetate/acetone/methanol/ethanol/propanol (75/10/5/5/5, mass parts)
* methyl acetate/acetone/methanol/butanols/cyclohexane (75/10/5/5/5, mass parts)
* methyl acetate/acetone/butanols (81/8/7/4, mass parts)
* methyl acetate/acetone/butanols (82/10/4/4, mass parts)
* methyl acetate/acetone/butanols (80/10/4/6, mass parts)
* methyl acetate/methyl ethyl ketone/methyl alcohol/butanols (80/10/5/5, mass parts)
* methyl acetate/acetone/methyl ethyl ketone/ethanol/isopropyl alcohol (75/8/5/5/7, mass parts)
* methyl acetate/cyclopentanone/methanol/isopropanol (80/7/5/8, mass parts)
* methyl acetate/acetone (85/10/5, mass parts)
* methyl acetate/cyclopentanone/acetone/methanol/butanols (60/15/14/5/6, mass parts)
* methyl acetate/cyclohexanone/methyl alcohol/hexane (70/20/5/5, mass parts)
* methyl acetate/methyl ethyl ketone/acetone/methanol/ethanol (50/20/20/5/5, mass parts)
* methyl acetate/1,3-dioxolanes/methanol/ethanol (70/20/5/5, mass parts)
* methyl acetate/diox/acetone/methanol/ethanol (60/20/10/5/5, mass parts)
* methyl acetate/acetone/cyclopentanone/ethanol/isobutyl alcohol/cyclohexane (65/10/10/5/5/5, mass parts)
* methyl formate/methyl ethyl ketone/acetone/methanol/ethanol (50/20/20/5/5, mass parts)
* methyl formate/acetone/ethyl acetate/ethanol/butanols/hexane (65/10/10/5/5/5, mass parts)
* acetone/methyl acetoacetate/methanol/ethanol (65/20/10/5, mass parts)
* acetone/cyclopentanone/methyl alcohol/butanols (65/20/10/5, mass parts)
* acetone/1,3-dioxolanes/ethanol/butanols (65/20/10/5, mass parts)
* 1,3-dioxolanes/cyclohexanone/methyl ethyl ketone/methyl alcohol/butanols (55/20/10/5/5/5, mass parts)
In addition, can use the acylated cellobiose cellulose solution for preparing by following method.
* comprise with methyl acetate/acetone/butanols (81/8/7/4, mass parts) and prepare acylated cellobiose cellulose solution, filtration and concentrate this solution, the method for adding 2 mass parts butanols in this solution then
* comprise with methyl acetate/acetone/butanols (84/10/4/2, mass parts) preparation acylated cellobiose cellulose solution, filter and concentrate this solution, in this solution, add the method for 4 mass parts butanols then
* comprise with methyl acetate/acetone (84/10/6, mass parts) preparation acylated cellobiose cellulose solution, filtration and concentrated this solution, in this solution, add the method for 5 mass parts butanols then
Except above-mentioned chlorine-free organic solvent of the present invention,, be used in dope of the present invention and also comprise methylene chloride with the amount Jia Qinei of 10 quality % based on organic molten gross mass of the present invention.
(performance of acylated cellobiose cellulose solution)
From the applicability viewpoint of film curtain coating (flow casting), acylated cellobiose cellulose solution of the present invention is preferably with 10-30 quality %, more preferably the amount of 13-27 quality %, preferred especially 15-25 quality % comprises the acylated cellulose that is incorporated in the above-mentioned organic solvent.The concentration of acylated cellobiose cellulose solution is adjusted to predetermined scope can carry out at dissolving step.Alternatively, adjust to predetermined concentration range in the concentration step that the acylated cellobiose cellulose solution that makes with low concentration (for example, 9-14 quality %) in advance can be described below.Alternatively, the acylated cellobiose cellulose solution that makes with high concentration in advance can be adjusted to predetermined lower concentration range with it by adding various adjuvants inwards.Can use any in these methods, as long as can reach predetermined concentration range.
In the present invention; dissolubility angle from solvent; the molecular weight of the acylated cellulose of the association of concentration dilution in the acylated cellobiose cellulose solution of 0.1-5 quality % is being preferably 150 with the organic solvent with same recipe; 000-15,000,000; more preferably 180; 000-9,000,000.In order to determine the molecular weight of association product, can use the static light scattering method.The preferred feasible consistent inertia of determining square radius is more preferably implemented dissolving at 10-200nm in the scope of 20-200nm.In addition, preferably make second virial coefficient-2 * 10
-4To+4 * 10
-4, more preferably-2 * 10
-4To+2 * 10
-4Scope in implement the dissolving.
The definition of molecular weight, inertia square radius and the second virial coefficient of association product will be described hereinafter.These performances are measured in the following manner by the static light scattering method.For the convenience of equipment, measurement is to carry out in the scope of dilution, but these tests have reflected the characteristic of the dope in high concentration range of the present invention.
At first, acylated cellulose is dissolved in the solvent identical and prepares the solution that concentration is 0.1 quality %, 0.2 quality %, 0.3 quality % and 0.4 quality % respectively with the solvent that is used for dope.Before use the acylated cellulose preparing to weigh was moisturized preventing down at 120 ℃ in dry 2 hours.Acylated cellulose that will be so dry is weighed under 25 ℃ and 10%RH then.Carry out the dissolving of acylated cellulose according to employed identical method (normal-temperature dissolution method, hot-cold lysis method, high temperature welding process) in the dope dissolving.Next, be the Teflon filtrator of 0.2 μ m by the aperture, with these solution of solvent filter.Under 25 ℃, use DLS-700 type light scattering device (by Otsuka Electronics Co., Ltd. produces) then, spend to the static light scattering of the solution of per 10 each these spline filter of degree measurement of 140 degree from 30.Then by the such data that obtain of Berry drafting method analysis.For analyzing the definite of needed refractive index, the refractive index of this solvent is measured by Abbe refractometer.For determining of the concentration gradient (dn/dc) of refractive index, use DRM-1021 type differential spectrophotometer (by OtsukaElectronics Co., Ltd. produces) to measure employed identical solvent and solution in light scattering measurement.
(preparation of dope)
Preparation according to the acylated cellobiose cellulose solution (dope) of the example as resin solution of the present invention will be described hereinafter.Method for the dissolving acylated cellulose does not limit particularly.The dissolving of acylated cellulose can at room temperature be carried out.Alternatively, can use hot-cold lysis method or high-temperature digestion method.Alternatively, these dissolving methods can be used in combination.For the details of preparation acylated cellobiose cellulose solution, can be with reference to JP-A-5-163301, JP-A-61-106628, JP-A-58-127737, JP-A-9-95544, JP-A-10-95854, JP-A-10-45950, JP-A-2000-53784, JP-A-11-322946, JP-A-11-322947, JP-A-2-276830, JP-A-2000-273239, JP-A-11-71463, JP-A-04-259511, JP-A-2000-273184, JP-A-11-323017 and JP-A-11-302388.Above-mentioned method of dissolving acylated cellulose in organic solvent also can be applied among the present invention, as long as it falls in the scope of the present invention.For the details of these methods, can be with reference to Kokai GihoNo.2001-1745, March 15 calendar year 2001, pp.22-25, Janpan Institute ofInventionand Innovation.Then acylated cellulose rich liquor solution of the present invention is concentrated and filters.Details for these methods can be with reference to Giho No.2001-1745, March 15 calendar year 2001, the 25th page, Janpan Institute of Invention and Innovation.Under the situation of at high temperature dissolving, in most of the cases this temperature is higher than the boiling point of employed organic solvent.In this case, dissolving is carried out under pressure.
From the viewpoint of curtain coating, the viscosity of this acylated cellulose and the dynamic elastic modulus of storing preferably drop in the following scope.Use and have CLS500 type flow graph (by TA Instruments produce) the measurement 1mL sample solution of diameter as 4cm/2 ° steel pricker.About measuring condition, this measurement is to measure to determine 40 ℃ of static non-Newtonian viscosity n* (Pas) and-5 ℃ of storage elastic modulus G ' (Pa) with 2 ℃ of per minutes in the step that heats up in-10 ℃-40 ℃ scope.Before measurement, in advance sample solution is remained on the measurement initial temperature.In the present invention, this sample solution is preferably 1-400Pas 40 ℃ viscosity, more preferably 10-200Pas, and be 500Pa or more at 15 ℃ dynamic storage elastic modulus, more preferably 100-1,000,000Pa.The low-temperature dynamic storage elastic modulus of sample solution is preferably big as much as possible.For example, if the temperature of curtain coating stilt is-5 ℃, then the low-temperature dynamic storage elastic modulus at-5 ℃ of these sample solutions is preferably 10,000-1,000,000Pa.If the temperature of curtain coating stilt is-50 ℃, then the low-temperature dynamic storage elastic modulus at-50 ℃ of these sample solutions is preferably 10,000-5,000,000Pa.
In the present invention, state in the use under the situation of concrete acylated cellulose, obtained the high concentration dope.Like this, do not rely on concentration method, can obtain to have the high concentration acylated cellobiose cellulose solution of advantages of excellent stability.In order further to implement dissolving, acylated cellulose can be dissolved in the low concentration.The solution concentration that will prepare so then by method for concentration.For example, can use low concentration solution is incorporated in housing and the gap between the swing-around trajectory around the rotating vane of enclosure interior hoop rotation, the temperature difference that between solution and casing, forms simultaneously this solution that volatilizees, thereby the method for acquisition highly concentrated solution (referring to, for example, JP-A-4-259511).Alternatively, can use by nozzle the low concentration solution of heating is blown into container so that solvent flash distillation on the distance from the nozzle to the container inner wall, take out the solvent of volatilization from container simultaneously and take out from the bottom of container formed highly concentrated solution method (referring to, for example, US2,541,012, US2,858,229, US4,414,341, US4,504,355).
Before curtain coating, preferably pass through suitable filtering material for example wire netting and flannel, by removing by filter for example undissolved material of impurity, dust and impurity.For the filtration of acylated cellobiose cellulose solution, preferably use the filtrator of absolute filtering accuracy as 0.1-100 μ m.More preferably, use the filtrator of absolute filtering accuracy as 0.5-25 μ m.The thickness of filtrator is preferably 0.1-10mm, more preferably 0.2-2mm.In this case, filter preferably at 1.6MPa or lower, more preferably 1.2MPa or lower, further preferred 1.0MPa or lower carries out under preferred especially 0.2MPa or the lower pressure.As filtering material, can preferably use any known material for example glass fibre, cellulose fibre, filter paper and fluororesin, for example tetrafluoroethylene resin here.Particularly, preferred pottery, the metal etc. of using.The viscosity of the acylated cellulose before film forming can be arbitrarily, as long as this acylated cellobiose cellulose solution can be by curtain coating in film forming procedure, and is preferably 10Pas-2 usually; 000Pas; more preferably 30Pas-1,000Pas, further preferred 40Pas-500Pas.Temperature to this acylated cellobiose cellulose solution before film forming is not particularly limited, as long as it is the curtain coating temperature, still is preferably-5 ℃-+70 ℃, more preferably-5 ℃-+55 ℃.
＜film forming 〉
According to optical resin film of the present invention, for example cellulose acylate film can obtain by making above-mentioned acylated cellulose solution film forming.As film build method and film formation device, can use solution casting/film build method and solution casting/film formation device in the related art method of any production cellulose acylate film here respectively.The dope (acylated cellobiose cellulose solution) that will prepare in dissolver (cellar for storing things) is stored in to be stored in the cellar for storing things, carries out last adjustment so that remove the bubble that is included in the dope.Then, by can the dope of adjusting like this being transported to the pressure die from the dope discharge port according to the pressure constant speed gear-type pump of rotational speed with high precision constant speed transport liquid.Crack by pressure die then, with this dope equably curtain coating on the curtain coating part of the metal support that changes of not stopping transport.When metal support basically curtain coating one circle time, then half-dried dope film (being also referred to as " blank ") is peeled off from metal support.Clamped by clip at its two ends then and keep its width, the dry blank that obtains like this by in the stenter transportation.Next, transport this blank by one group of roller in the drying device and finish drying.By up-coiler this blank is rolled into predetermined length then.The combination of stenter and one group of roller changes according to purpose.At the solution casting/film build method of the function and protecting layer that is used for electronic console,, usually apparatus for coating is joined in solution casting/film formation device for the film surface property of lower floor, antistatic backing, disappear dizzy layer and protective seam for example.To describe various production stages briefly hereinafter, but the present invention is not limited to this.
At first, in order to be equipped with cellulose acylate film by the solvent cast legal system, with acylated cellobiose cellulose solution (dope) curtain coating of preparation like this to cylinder or be with so that evaporating solvent formation film.Preferred adjustment will be by the concentration of the dope of curtain coating so that solid content be 5-40 quality %.Preferably drum or band quilt be mirror polish in advance.Preferably this dope curtain coating being 30 ℃ or lower cylinder or being with in surface temperature, is on-10 to 20 ℃ the metal support particularly preferably in temperature.In addition, the method that is disclosed in JP-A-2000-301555, JP-A-2000-301558, JP-A-07-032391, JP-A-03-193316, JP-A-05-086212, JP-A-62-037113, JP-A-02-276607, JP-A-55-014201, JP-A-02-11511 and JP-A-02-208650 can be used among the present invention.
(multilayer curtain coating)
This acylated cellobiose cellulose solution can with the form of individual layer by curtain coating on smooth zone or cylinder as metal support.Alternatively, can be on metal support with two or more acylated cellulose solution castings.In curtain coating under the situation of multiple acylated cellobiose cellulose solution, the solution that contains acylated cellulose can be by a plurality of curtain coating mouth curtain coatings prepared layer zoarium on metal support that distributes with a determining deviation along the metal support rotation direction.For example, can use and be disclosed in JP-A-61-158414, any method among JP-A-1-122419 and the JP-A-11-198285.Alternatively, can come curtain coating acylated cellulose solution film forming by two curtain coating mouths.For example, can use to be disclosed in JP-B-60-27562 JP-A-61-947245, JP-A-61-104813, any method among JP-A-61-158413 and the JP-A-134933.As disclosed among the JP-A-56-162617, can use the method that comprises while curtain coating high viscosity acylated cellobiose cellulose solution and low viscosity acylated cellobiose cellulose solution, its medium-high viscosity acylated cellulose solution is surrounded by low viscosity acylated cellobiose cellulose solution.In addition, as disclosed among JP-A-61-94724 and the JP-A-61-947245, to be external solution contain the pure composition of high-load more as poor solvent than internal solution to optimized technical scheme.Alternatively, can use two curtain coating mouths so that peel off by the film of first curtain coating interruption-forming on metal support, and on a side of the film that contacts with metal support, carry out the curtain coating second time from metal support.For example, can use the method that is disclosed among the JP-B-44-20235.To can be identical or different by the acylated cellobiose cellulose solution of curtain coating and this do not had concrete qualification.In order to make a plurality of acylated cellulose layers functionalized, can will extrude according to the acylated cellobiose cellulose solution of function prescription by each curtain coating mouth.The curtain coating of acylated cellobiose cellulose solution can be followed the curtain coating of other functional layer (for example, adhesive phase, dye coating, antistatic layer, dizzy layer, UV-absorbing layer, polarizing layer disappear).
To have the film of wishing thickness in order forming, to be necessary and to have high concentration and full-bodied acylated cellobiose cellulose solution is extruded from the individual layer solution of correlation technique.In this case, often cause the problem of the stability that the acylated cellulose performance is gone on business, thereby formed the solid that causes the flatness that produces granular structure or difference.In order to address these problems, can pass through a plurality of acylated cellobiose cellulose solutions of curtain coating mouth curtain coating, this makes and might simultaneously high viscosity solution be extruded on the metal support.By this way, can prepare film with improved flatness and good surface property.In addition, the use of highly enriched acylated cellobiose cellulose solution reduces the speed of production that dry load can improve film thereby it might be reached.Under the situation of casting method altogether, the thickness of internal layer solution and outer solution is not specifically limited, but the thickness of outer solution is preferably the 1-50% of gross thickness, more preferably 2-30%.Under three layers of curtain coatings altogether or more multi-layered situation, the layer that contact with metal support with contact with air layer the summation of thickness be defined as outer field thickness.Under the situation of curtain coating altogether, can with above-mentioned adjuvant with variable concentrations for example plastifier, ultraviolet light absorber and matting agent the acylated cellobiose cellulose solution altogether curtain coating be cellulose acylate film with laminate structures.For example, can prepare cellulose acylate film with skin/core/cortex construction.For example can or only it be attached in the cortex in conjunction with a large amount of matting agents.Plastifier and ultraviolet light absorber can be attached in the sandwich layer or only than with the amount more than cortex and be attached in the sandwich layer.For example, can be with at least a being attached in the cortex in low volatility plastifier and the ultraviolet light absorber, and the ultraviolet light absorber that has the plastifier of good plasticity or have a good ultraviolet-absorbing can be attached in the sandwich layer.In another optimized technical scheme, can tightly be incorporated in the cortex on the metal support side peeling off promoter.In order to make solution casting by the chilling roll method by the cool metal stilt, also preferred this cortex contains more alcohol as poor solvent than sandwich layer.Cortex has different Tg values with sandwich layer.The Tg of preferred sandwich layer is lower than the Tg of cortex.In addition, in the process of curtain coating, the viscosity that contains the solution of acylated cellulose can be from cortex to the sandwich layer difference.The viscosity of preferred cortex is lower than the viscosity of sandwich layer.Yet the viscosity of sandwich layer can be lower than the viscosity of cortex.
(curtain coating)
The example of solution casting method comprises: comprise by compressing die orifice prepared dope evenly is expressed into method on the metal support, comprise the method for the thickness of the dope that uses scraper to adjust the curtain coating on the metal support, and the method that comprises the thickness of the roller adjustment curtain coating dope that use is rotated in the opposite direction.In these casting methods, pressure die method preferably.The example of pressure die comprises coat hunger type pressure die and T die orifice type pressure die.Can preferably use any in these pressure dies.Except top mentioned method, can be used for the various conventional methods of curtain coating/film forming triacetyl cellulose solution.Consider the boiling point difference between the employed solvent, by pre-determining various conditions, can give play to the list of references of being quoted in the above in the identical effect of disclosed content.As being used in the cycle operation metal support of producing cellulose acylate film of the present invention, can use by chromium plating to have the stainless steel band (also being called as " travelling belt ") that minute surface is decorated by bright finished cylinder or by polishing.The one or more pressure dies that are used to produce cellulose acylate film of the present invention can be placed on above the metal support.Preferably, the quantity of pressure die is 1 or 2.Under the situation that two or more pressure dies are provided, can be assigned on these moulds with the dope that various ratios will be prepared curtain coating.Can use a plurality of accurate constant rate of speed gear-type pumps with this dope with specific ratio with deliver to these moulds there.The temperature of acylated cellobiose cellulose solution that will curtain coating is preferably 55 ℃, more preferably 25-50 ℃.In this case, the temperature of acylated cellobiose cellulose solution can all be identical in all steps, can be different between step and step perhaps.Under latter event, if before by curtain coating soon, the temperature of acylated cellobiose cellulose solution is the temperature of wishing, then it is enough.
(drying steps D1)
In producing cellulose acylate film; general example in the method for dry dope on the metal support comprises: comprise on the blank that hot-air is blown on the front surface that is positioned at metal support (cylinder or band); promptly; metal support or cylinder or with on the back side on the front surface of blank on method; comprise the controlled liquid of temperature is contacted with the back side of band or cylinder; this is the side with dope curtain coating surface opposite, so that transfer heat to cylinder or transmission brings the control surface method of temperature.In these drying means, back side liquid thermal conductivity method preferably.The surface temperature of metal support can be arbitrarily before curtain coating, as long as it is not higher than the boiling point that is used in the solvent in this dope.Yet, in order to promote drying or to eliminate flowability on the metal support, preferably the lip-deep temperature of metal support is pre-determined and is low 1-10 ℃ of the boiling point of the solvent minimum than the boiling point in employed solvent.Yet, be cooled and do not need at the curtain coating dope and must not use this qualification under the dry situation about peeling off from metal support.
Step D0 represents to peel off the film of such curtain coating and this film is sent to stenter step partly in the present invention.At step D0,, preferably control temperature for control in stretching remains in the amount of the solvent in the film.
Film at step D0 transports physical property and the amount of residual solvent and the Temperature Influence of step D0 that tension force is subjected to dope, but is preferably 30N/m
2-300N/m
2When film transport tension force surpass above beyond the restricted portion time, the uniformity coefficient of film is affected, and has remotely caused show inhomogeneous.
The ratio of good solvent and poor solvent preferably is limited at and prevents in the preferred range because the film that transport point causes prolongs when step D0 finishes.When step D0 finished, the mass ratio of the quality of poor solvent/(quality of the quality+poor solvent of good solvent) * 100 (%) was preferably 15 quality %-95 quality %, more preferably 25 quality %-95 quality %, preferred especially 30 quality %-95 quality %.
(preferred production process 1 among the present invention)
Will be in conjunction with Figure 11 and 12 stretching step of describing according to above-mentioned preferred production process 1 of the present invention.
In Figure 11, steps A comprises clamping from film transports the film that step D0 (not having to show) transports.Following step B is included in a lateral direction (perpendicular to the direction of the curtain coating direction of film) with this film that stretches of the stretching angle shown in Figure 12.At step C, finish the stretching of film, next at nipped this film that transports simultaneously.In some cases, can make this film lax.
(amount of residual solvent when step B begins to stretch)
When step B begins, preferably the amount of residual solvent is adjusted to 5 quality %-90 quality %, more preferably 10 quality %-90 quality %, most preferably in the scope of 10 quality %-40 quality %.
Known in step perpendicular to the carriage direction stretched film, in distribution (distribution of the arrangement angles) deterioration of film optics slow axis transversely.The mode that is in good state for distribution this film that stretches with arrangement angles, the concentration of supposing the good solvent in steps A, B and C is respectively Ma, Mb and Mc, then Ma is preferably greater than 2,000ppm, more preferably greater than 3,000ppm most preferably surpasses 60% of good solvent vapo(u)rous concentration, Mb is preferably greater than 2,000ppm, more preferably greater than 3,000ppm, most preferably surpass 60% of good solvent vapo(u)rous concentration, and Mc preferably is less than 60% of good solvent vapo(u)rous concentration, more preferably less than 3, and 000ppm, most preferably be less than 2,500ppm.
(content of poor solvent (%) in the solvent in residuing in film)
Stretching step has the ratio of the good solvent and the poor solvent of hope.When the end of steps A, B and C, the mass ratio of the quality of residual poor solvent/(quality of the poor solvent of the quality of residual good solvent+residual) * 100 (%) is preferably 15 quality %-95 quality %, more preferably 25 quality %-95 quality %, most preferably 30 quality %-95 quality %.In addition, when the end of steps A, B and C, the quality of the poor solvent of the mass ratio of residual poor solvent+residual) * 100 (%) can be identical or different.
(pre-determining of the amount of the film temperature of steps A, B and C and residual solvent)
In the drawing process of film, when still being soft, it is stretched at this film of step B.At steps A and C, the matrix of film is hard during preferably than step B.By controlling diaphragm temperature suitably with remain in the steam condition that the amount of the solvent in the film can obtain to wish.
The environment temperature of each step is subjected to residuing in the influence of the quantity of solvent in the film, but preferably is 30 ℃-40 ℃ when steps A, or is 30 ℃-140 ℃ when step B and C.Specifically, remain in the time marquis of 0.4-0.8 of the amount of the solvent in the film when the amount that remains in the solvent in the film when step B finishes begins for step B, environment temperature is preferably 110 ℃-140 ℃ during step B.When beginning for step B, the amount that remains in the solvent in the film when step B finishes remains in the time marquis of 0.4-0.8 of the amount of the solvent in the film, film temperature when step B begins is preferably 30 ℃-140 ℃, and film temperature is preferably 70 ℃-140 ℃ when step B finishes.
The stretching time of step B preferably has the uniformity coefficient that preferred range improves film.Specifically, stretching time is preferably 1-10 second, more preferably 4-10 second.
In addition, can carry out the stretching of film with constant rate of speed or rate of change, but draw speed be 50%/minute to 500%/minute, preferred 100%/minute to 400%/minute, most preferably 200%/minute to 300%/minute.
In the present invention, as previously mentioned, suppose in the average rate of drying of clamping step and stretching step to be that the average rate of drying of A%/second and relaxation step is B%/second,, can realize that the present invention has the film that little delay distributes when film is 1.9-4.2 when being dried with A/B.
Can make the stretched delay of adjusting it of cellulose acylate film according to the present invention.In addition, can reasonably make this cellulose acylate film through cross directional stretch.For the details of these drawing process, can be with reference to JP-A-62-115035, JP-A-4-152125, JP-A-4-284211, JPA-A-4-298310 and JP-A-11-48271.According to these methods, the cellulose acylate film that stretching is produced increases its interior length of delay of face.
The stretching of film can only vertical or horizontal single shaft ground carry out or on this both direction simultaneously or continuously twin shaft carry out.About the birefringence of blooming, the lateral refraction rate of this blooming is preferably greater than the longitudinal refractive index of this blooming.Correspondingly, preferably in the horizontal than this film that stretches more in the vertical.The stretching of blooming can form in the step at film and carry out.Alternatively, rolled-up nature fabric (raw fabric) can be stretched.
Method as the Re that is used to control optical resin film of the present invention, preferred this optical resin film that stretches under the temperature that is included in 25 ℃-100 ℃ of glass transition temperatures that are higher than it that uses, that is to say, the glass transition temperature of supposing this film is Tg, then at (Tg+25 ℃) this film that stretches to the temperature of (Tg+100 ℃).
On the other hand, the transmissivity of this blooming is preferably 85% or more, and more preferably 90% or more.Even when using identical materials, use the blooming that drawing process of the present invention also might obtain to have high transmittance.The present inventor infers when with this blooming of drawing by high temperature the time, and the impurity in the polymeric material is evaporated, thereby has reduced the dispersion factor in the film.
With reference to acylated cellulose, at high temperature stretch hereinafter in various wavelength coverages, to obtain the mechanism of the Re value of hope as the best-of-breed technology scheme.
Form acylated cellulose by constituting main chain by the glucopyranose ring and constituting side chain by acyl group.As the time marquis that the film that is made by acylated cellulose is stretched, main chain shows Re in the draw direction extension.As the result of further investigation, the present inventor find when stretching Tg under 165 ℃ of-240 ℃ of high temperature be the time marquis of 140 ℃ cellulose acylate film, the Re at 450nm place is reduced and the Re at 650nm place is enhanced.
In addition, show the X-ray refraction peak that derives from crystallization through the cellulose acylate film that stretches like this with identical high temperature.Infer crystallization like this and caused that thereby the permutations of main chain and side chain has caused the wavelength dependency of Re.
On the other hand, in order to eliminate the aberration of liquid crystal indicator, control Rth also is very important.As the method for control Rth, the preferred use comprises the method for hereinafter described diffusion liquid crystal layer or comprises the method for using adjuvant.
(preferred production process 2 among the present invention)
Such as previously mentioned, as the result of further investigation, the present inventor finds to use stretching step that comprises stretched film and the production method of shrinking the collapse step of this film, the blooming that might obtain to have above-mentioned optical physics performance.
The preferred especially in the present invention stretching step of using the carriage direction stretched film that is included in film and by the method for the production blooming of the collapse step of shrink film when laterally clamping, the method for production blooming that perhaps is included in the stretching step of cross directional stretch film and shrinks the collapse step of this film at the carriage direction of film.
At first, description is included in film the carriage direction stretched film stretching step and by the method for the production blooming of the collapse step of shrink film when laterally clamping.
In this case, film is that carriage direction at this film is stretched.As the method that is used in the carriage direction stretched film of film, the preferred use comprises that adjusting film transports the speed of roller so that the speed of rolling of film is higher than the method for the peeling rate of film.
In this case, by transporting film in the horizontal clamping of the stenter that is reduced gradually by width at film, can make this film be substantially perpendicular to the draw direction contraction.
In more detail, by keep with chain, screw type, scaling type or linear electric machine type stenter and the width of stenter reduce gradually in the carriage direction stretched film, can be when stretching, this film is shunk being substantially perpendicular to draw direction.
On the other hand, according to the stretching step that is included in this film of cross directional stretch and the method that is used to produce blooming of shrinking the collapse step of this film at the film carriage direction, this film can stretch when keeping with chain, screw type, scaling type or linear electric machine type stenter, along with this film flows at carriage direction, the distance of the clip of stenter is reduced gradually.
According to said method, can carry out a part of stretching step and collapse step simultaneously at least.
Simultaneously shrink this film and increase the stretching device of the thickness of this film as especially effectively being implemented in the stretch stretching step of this film of longitudinal direction or horizontal direction, preferably use FITZ type stretching device (by Ichikin Industry Co., Ltd.) in other direction.For the details of this stretching device, can be with reference to JP-A-2001-38802.
The stretching factor of stretching step and the contraction factor of collapse step can at random be selected by delay Re and thickness direction retardation Rth in the face.Yet at the stretching factor of collapse step with at the contraction factor of collapse step respectively preferred 10% or more and 5% or more.
Employed in this article term " stretching factor " mean draw direction stretch the back with stretch before the length growth rate of film length, " contraction factor " means the shrinkage factor of film length before shrinkage direction shrinks back and contraction.
Stretching factor is preferably 10%-60%, preferred especially 20%-50%.On the other hand, contraction factor is preferably 5%-40%, preferred especially 15%-35%.
For the optical physics performance that obtains to wish, stretch and collapse step preferably at (glass transition temperature of film during processing+(5-100) ℃), be more preferably and under the temperature of (glass transition temperature of film during processing+(10-80) ℃), carry out.
Employed in this article term " glass transition temperature (Tg) " mean from two with below condition under, the point of crossing of the line of the contact of a curve of the inflection temperature of heat absorption (heat release) the curve low temperature side drawn by the measurement of using difference formula scanning calorimeter (DSC) determines.
Container: the enclosure-type resealable container (70 μ ml) that makes by stainless steel
Measurement pattern: Modulated DSC
Scanning temperature range :-50 ℃-200 ℃
Programming rate: 2 ℃/minute
Cooling rate: 20 ℃/minute
Amplitude in intensification: ± 1 ℃
Amplitude cycle: 80 seconds
Employed in this article term " treatment temperature " means the temperature on the film surface of measuring by the noncontact infrared thermometer.
Can in the film of such curtain coating, leave solvent the time marquis or can dry and batch after stretch and shrink.Stretching can or be carried out in a plurality of stages a stage.When stretching is to carry out in a plurality of stages, if on the product of the stretching factor of each stretching step falls in the restricted portion then be enough.Collapse step also can be carried out in a stage or a plurality of stage.
Draw speed is preferably 5%/minute-1,000%/minute, most preferably 10%/minute-500%/minute.Stretch preferably by warm-up mill and/or by from the heat of radiant heat source (for example, IR well heater) or carry out with hot-air.In addition, in order to improve temperature homogeneity, can provide calibration cell.Comprise at uniaxial tension under the situation of roller stretching that the distance between the roller (L) is preferably 2.0-5.0 with the ratio L/W of the width (W) of flap.Contraction speed is preferably 5%/minute-1,000%/minute, more preferably 10%/minute-500%/minute.In addition, draw speed and contraction speed can be kept constant.Alternatively, can stretch with the speed that changes and shrink.
Preferably before stretching step, preheat step.Stretching step can be immediately following after heat treatment step.
Thermal treatment is preferably carried out under the temperature of 10 ℃ of the glass transition temperatures that is higher than cellulose acylate film 20 ℃ of glass transition temperatures that is lower than cellulose acylate film.Thermal treatment was preferably carried out 1 second to 300 hours.Heating means can comprise section heating or the part heating of using infrared heater.In the process of heat treatment step or when finishing, two edges of this film can be clipped.Preferred recovery stage tail material is used for recycling.
(can be applied to the example of the production technology among the present invention)
In the production of film of the present invention, can suitably use following technology.
For stenter, JP-A-11-077718 proposed can by suitably control dry gas blowing method, air blowing angle, roll velocity distribution, roll speed, gas velocity, temperature difference, up and down airflow velocity ratio, use the high specific heat dry gas to wait to carry out the drying of the blank that width limited by stenter, so that can improve the speed of solution casting method or can guarantee to prevent for example decline of flatness of quality in the expansion process of blank width.
In addition, JP-A-11-077822 discloses and has related in order to prevent unevenness, in the hot relaxation step of the thermoplastic resin that stretching step is stretched, and the invention of heat-treating with film thermal gradient in a lateral direction.
In addition, JP-A-4-204503 discloses and has related in order to prevent unevenness, will remain on the invention of the scope in-draw film of 2%-10% according to the solvent that solid content calculated.
In addition, JP-A-2002-248680 discloses and has comprised that stenter is clamped width D remains on (33/log (draw ratio) * log (volatilization content)) or following stretched film, so as can to suppress since clamp width restriction produced curls, thereby promote the invention that the film after the stretching step transports.
In addition, JP-A-2002-337224 disclose relate to for obtain that the high speed mantle transports and the purpose that stretches the first half stage with the pin and the method for transporting with the stenter of clip in the general stage in the back.
In addition, JP-A-2002-187960 discloses an invention: in order to improve field-of-view angle performance and field-of-view angle simply, comprise cellulose esters rich liquor solution curtain coating on the curtain coating stilt, residual moisture content in blank is 100 quality % or still less then, the time marquis of 10-100 quality % particularly, this blank (film) is peeled off from the curtain coating stilt with the traction rate of 1.0-4.0 at least one direction, so that formed film has the optics biaxiality.In its disclosed optimized technical scheme, the residual moisture content in blank is 100 quality % or still less, the time marquis of 10-100 quality % particularly, at least one direction with the traction rate of 1.0-4.0 this blank that stretches.Other examples of drawing process comprise: a kind of peripheral speed that makes a plurality of rollers that comprises is different so that by utilizing the method for this film of peripheral speed difference axial tension between the roller, the blank that the stretching both sides are extended at moving direction by the fixing interval of clip or pin so as this blank by the method for axial tension, comprise the blank that laterally outwards moves that the stretching both sides are fixed so as this blank by the method for cross directional stretch, comprise horizontal outside and axially movable blank that the stretching both sides are fixed so as this blank by the method for horizontal and vertical stretching, and their combination.Also disclose in the stenter method, when clamping part is by the Linear Driving driven by program time, can carry out smooth stretching, this makes may advantageously eliminate for example danger of fracture.
In addition, JP-A-2003-014933 discloses following invention: comprise that preparation contains resin, the dope A of adjuvant and organic solvent and the dope B that comprises resin and do not contain adjuvant or have the amount that is less than the adjuvant among the dope A, the mode that forms sandwich layer and dope B formation top layer with dope A is total to curtain coating on stilt with dope A and dope B, the evaporation organic solvent is up to peeling off this blank from stilt, peel off this blank from stilt, residual solvent levels in resin molding is the time marquis of 3-50 quality % then, prepares and has seldom that adjuvant oozes out with the traction rate of 1.1-4.3 this blank that stretches at least one direction, there is not splitting, the good smoothness and the good transparency delay film (retarder film).In an optimized technical scheme, peel off this blank from stilt, then at least one side with the temperature of the draw ratio of 1.1-3.0 and 140 ℃-200 ℃ this blank that stretches.In further optimized technical scheme, preparation contains the dope A of resin and organic solvent and contains the dope B of resin, particulate material and organic solvent.Mode with dope A formation sandwich layer and dope B formation top layer is total to curtain coating on stilt with dope A and dope B then.Evaporate organic solvent then up to peeling off this blank from stilt.Peel off this blank from stilt, the residual solvent levels in the resin molding is the time marquis of 3-50 quality % in drawing process then, at least one direction with the draw ratio of 1.1-3.0 and dawn under 140 ℃-200 ℃ temperature, this blank stretches.In further optimized technical scheme, preparation contains the dope A of resin, organic solvent and adjuvant, the dope C that contains resin and do not contain adjuvant or have the dope B of the adjuvant that is less than among the dope A and contain resin, particulate material and organic solvent.Form sandwich layer with dope A then, the mode that dope B forms top layer and dope C formation opposite side top layer is total to curtain coating on stilt with dope A, dope B and dope C.Evaporate organic solvent then up to peeling off this blank from stilt.Peel off this blank from stilt then, the residual solvent levels in the resin molding is the time marquis of 3-50 quality % in drawing process then, with at least one axial direction with the draw ratio of 1.1-3.0 this blank that stretches.In further optimized technical scheme, at least one direction with the draw ratio of 1.1-3.0 and under 140 ℃-200 ℃ temperature, this blank stretches.In further optimized technical scheme, quality based on resin, the amount that is attached to the adjuvant of dope A and dope B is respectively 1-30 quality % to 0-5 quality %, and this adjuvant is plastifier, ultraviolet light absorber or postpones controlling agent and methylene chloride or methyl acetate and be attached among dope A and the dope B with 50 quality % or more amount as organic solvent.
In addition, JP-A-2003-014933 discloses as drawing process, preferred use comprise use be called as stenter, be used to the drawing process of cross directional stretch both sides with the cross directional stretch machine of the fixing blank of the clip of lateral magnification or pin.Disclose also that biaxial stretch-formed machine carries out longitudinal stretching or contraction when being included in carriage direction (vertically) spacing increases or reduce pin or clip by use.Further disclose when clamping part be marquis during by the Linear Driving driven by program, can successfully stretch, this makes might advantageously eliminate for example danger of fracture.Further disclose,, can also use the peripheral speed of a plurality of rollers different so that by utilizing this film of difference longitudinal stretching of the peripheral speed between the roller as the longitudinal stretching method.Further disclose, these stretching step go in the compound substance.Further disclose, stretching step can be carried out in two or more stage discontinuous with longitudinal stretching-cross directional stretch-longitudinal stretching or longitudinal stretching-longitudinal stretching.
In addition, JP-A-2003-004374 discloses following invention: relate to use and comprise that width is narrower than the drying device of the exsiccator of blank width, thereby prevented blank foaming in the process of stenter drying so that come from the both sides that the hot gas of exsiccator do not impact blank, but improved the release property of blank and prevented the generation of dust.
In addition, JP-A-2003-019757 discloses following invention: provide deep bead in the inboard, two limits of blank and do not prevented blank foaming in the process of stenter drying so that dry air impacts the stenter retaining part thereby relate to, but improved the release property of blank and prevented the generation of dust.
In addition, JP-A-2003-053749 discloses following invention: the dry thickness of supposing the film both sides that kept by the pin stenter is that the average dry thickness of the product section of X μ m and film is T μ m, satisfy relation (1) 40≤X≤200, when T is 60 or marquis still less the time, (2) 40+ (T-60) * 0.2≤X≤300, when T greater than 60 when being no more than 120 marquis and (3) 52+ (T-120) * 0.2≤X≤400, the marquis stablize and transports and drying when T is less than 120.
In addition, JP-A-182654 discloses following invention: being included in provides heating chamber and cooling chamber to prevent that the multistage stenter from causing wrinkling so that cool off the clip chain respectively in the exsiccator of multistage stenter of tenter frame apparatus.
In addition, JP-A-9-077315 discloses following invention: relate to and use inner pin to have the pin stenter that big density exterior pin has little density, so that can prevent the fracture of blank, wrinkling and bad transportation.
In addition, JP-A-9-085846 discloses following invention: relate to and use the stenter drying device of arranging, so that not long ago in engage blank, make to be used in by the blast-cold device that the pin that keeps the blank both sides is cooled to below the blowing temperature of blank and the gelling temp that is cooled to the conduit type refrigeratory that will sell adds 15 ℃ temperature, thereby prevent to foam or adhere on the holding unit in the stenter.
In addition, JP-A-2003-103542 discloses following invention: relate to being included in the pin stenter and cool off insert structure, so that the surface temperature of blank is no more than the gelling temp of blank, thus the solution film forming method of anti-shotpin stenter slippage and elimination impurity.
In addition, JP-A-11-077718 discloses following invention: relate to utilization with the speed of rolling of 0.5-20 (40) m/s, 10% or littler transverse temperature distributes, the air velocity of blank up and down of 0.2-1 than and the dry gas of 30-250J/Kmol than the stenter blank drying means that carries out, improve the speed of solution casting method and prevent that quality is for example the destruction by the planarity in the stenter process extending transversely to blank.Preferred stenter drying condition is disclosed according to residual solvent levels.Specifically, reach between the time of 4 quality % in time of peeling off blank from stilt and the residual solvent levels the blank, will from blowing nozzle to be blown into that the angle pre-determines be 30 °-150 °.Lip-deep when rolling velocity distribution and be based on the upper limit of the speed of rolling when what be positioned at bearing of trend that dry gas blows into, in the process that dries up the pathogenic dryness body, it is 20% or still less that the difference of upper and lower bound is pre-determined.When the residual solvent levels in the blank is to be no less than 130 quality % to the time marquis who is not more than 70 quality %, will pre-determine to being not less than 0.5m/sec from the wind speed that the blow dried machine blows to the dry gas on the blank surface to being not more than 20m/sec.When residual solvent levels for being not less than 4 quality % marquis when being less than 70 quality %, in order to be not less than air-dry dry this blank of dry gas that 0.5m/sec blows out to the speed that is not more than 40m/sec.When the Temperature Distribution of blank dry gas transversely was based on the upper limit of gas temperature, it was 10% or littler that the difference of upper and lower bound is pre-determined.When the residual solvent levels in the blank is not less than 4 quality % to the time marquis who is not more than 200 quality %, the flowing velocity that will be positioned at the dry gas that the blowing nozzle of the blow dried machine of the blank upper and lower that betransported blows out pre-determines to being not less than 0.2 to being not more than 1 than q.In another technical scheme, as dry gas, having used at least a mean specific heat here is to be not less than 31.0J/Kmol to the gas that is not more than 250J/Kmol.Can use that to comprise the concentration that exists with liquid usually be 50% or the dry gas of lower organic compound at saturated vapor pressure.
In addition, JP-A-11-077719 discloses following invention: relate to using and comprise the TAC process units with the tenter clip gap that is attached to its inner heating part, so that the production that planarity or extendability can not contaminated things and destroying.In optimized technical scheme, the position and the clip that discharge blank at the clip of stenter carry between the position of blank once more, are provided for removing the device that results from the impurity on clip and the blank contact portion.Impurity is removed by utilizing spraying gas or liquid or brush.In clip or pin and process that blank contacts, the surplus of blank is for being no less than 12 quality % to no more than 50 quality %.The surface temperature of clip or pin and blank contact portion preferably is not less than 60 ° to being not more than 200 ° (more preferably being not less than 80 ° to being not more than 120 °).
In addition, JP-A-11-090943 discloses following invention: suppose that Lr is the random length Lt (m) of stenter and has the ratio Ltt/Lt that keeps the summation Ltt that transports length (m) of blank part with the tenter clip gap of Lt equal length, comprise that using Lr to be not less than 1.0 improves flatness to the tenter clip gap that is not more than 1.99, eliminate because tearing the debase that is caused and boost productivity in the stenter.In an optimized technical scheme, placement keeps the part of blank and does not have transverse observation to arrive any slit.
In addition, JP-A-11-090944 discloses following invention: the inlet front that is included in stenter provides the plastic foil process units of blank transverse relaxation restraining device to eliminate the planarity defective, and the introducing instability that relaxes and caused owing to blank in the process that blank is incorporated into stenter.In an optimized technical scheme, this lax restraining device is the rotation roller with the rotation of 2 °-60 ° lateral magnification angle.Air suction device is provided above blank.Also providing can be from the fan blower of blank air blowing.
JP-A-11-090945 discloses following invention: relate to the TAC production method of introducing with horizontal direction for the blank that prevents to destroy quality and diminish the lax generation of throughput rate, comprise to strip down from stilt.
In addition, JP-A-2000-289903 discloses following invention: relate to when peeling off blank and solvent is provided for transporting the conveyer of this blank when being 12wt%-50wt% in the cross directional stretch blank, the blank width detecting unit wherein is provided, blank holding unit and two or more variable-flexibility point, and the width of the calculated signals blank that produces by the blank width detecting unit changes the position of flexible point, thereby the film that preparation has stable physical performance.
JP-A-2003-033933 has proposed at least the above and below in the left and right edges of the blank of the right and left of approaching the stenter intake section, be provided for preventing at the curling guide plate of the edge of blank generation blank, and the surface of the guide plate opposite with blank be by the value part that contacts with blank be arranged in the blank carriage direction on the metal part that contacts of blank be grouped into, clamp performance and prevent blank fracture in the time bar that prolongs to improve.In an optimized technical scheme, will be arranged on the downstream that the upstream that blank transports and the metal part branch that will contact with blank are arranged on the blank carriage direction with the resin portion branch that contacts with respect to the blank on the guide plate of blank.Drop (comprising gradient) between the resin that contacts with blank on guide plate part and the metal part branch that contact with blank is 500 μ m or still less.The resin that contacts with blank on guide plate part and the distance of metal part on the width 2mm-150mm that respectively does for oneself.The resin that contacts with blank on guide plate part and the distance of metal part on the blank carriage direction 5mm-120mm that respectively does for oneself.The resin of the guide plate that contacts with blank partly by with the substrate of plastic resin treatment guide metal or in the guide metal substrate coating resin provide.The value part of the guide plate that contacts with blank is made of simple resinite.Distance on the right and left of blank relative between the lower guide plate is 3mm-30mm.The right and left of blank relative on distance between the lower guide plate laterally and inwardly increase with width 2mm or the more ratio of every 100mm.On the right and left of blank relative lower guide plate each all have the length of 10mm-300mm.Lower guide plate is set makes them in the carriage direction displacement.Displacement between the last lower guide plate is-200 to+200mm.Surface with respect to the last guide plate of blank is separately by resin or metal structure.With respect to the surface of the last guide plate of blank be by
Constitute.The metal that contacts with blank is partly made by stainless steel.The surfaceness with respect to the guide plate of blank or resin part and/or metal part that contacts with blank is 3 μ m or still less.The last lower guide plate that curls that preferably will be used to prevent the blank on the blank edge is placed on the end of the stilt of peeling off blank and blank is incorporated between the position of stenter, more preferably approaches the inlet of stenter.
JP-A-11-048271 discloses following invention: be included in solvent in the blank when being 12 quality %-15 quality %, the blank that uses stretching device to stretch and be stripped from, dry this blank, then the solvent in blank be 10 quality % or lower in the working pressure machine suppress this blank in its both sides with the pressure of 0.2-10KPa, to prevent the fracture or inhomogeneous in the dry process in stenter of this blank.In an optimized technical scheme, the solvent in blank be 4 quality % or higher in, stop stretching to film.Using niproll suppressing on the blank both sides under the situation of blank (film), preferably use 1-8 to niproll.The temperature of suppressing is preferably 100 ℃-200 ℃.
In addition, JP-A-2002-36266, this invention relates to that thickness is provided is the thin TAC of high-quality of 20 μ m-85 μ m, discloses to pre-determine along the Tension Difference that carriage direction acts on blank to be 8N/mm2 or lower.It also discloses after strip step, next carries out the preheating step of this blank of preheating, next uses the stretch stretching step of this blank of stenter, next makes the lax relaxation step of blank with the amount of tension that is less than stretching step.
In addition, JP-A-2002-225054, it plans the sotck thinkness of hope is reduced in the scope of 10 μ m-60 μ m, reduce the quality of blank and reach good persistence, for example moisture permeability discloses, when the solvent in blank reaches 10 quality %, clamp the blank that strips down from stilt so that the width of blank can be kept constant at the edge of blank with clip, thereby suppressing drying shrinkage and/or the blank cross directional stretch is formed plane calibration (S) is the film of 0.0008-0.0020, wherein S is that (wherein Nx represents the refractive index of direction film in the face by equation S={ (Nx+Ny)/2}-Nz, show the highest refractive index along this direction, Ny represents to be illustrated in perpendicular to the refractive index on the direction in the face of Nx and Nz the refractive index of the film on the thickness direction) expression.Also disclose curtain coating and the time between peeling off was predefined for 30 seconds-90 seconds.Blank horizontal and/or that longitudinal stretching strips down from stilt is further disclosed.
In addition, JP-A-2002-341144 discloses the solution film forming method that comprises stretching step, and the mass concentration that wherein postpones to increase reagent towards the center of film width has higher optical profile, suppresses optical heterogeneity.
In addition, JP-A-2003-071863, this invention is planned to obtain unambiguous film, is used as polarization board protective film if disclose this blank, and the lateral traction ratio is preferably 0%-100%, more preferably 5%-20%, most preferably 8%-15%.Be used as slow film (retarder film) if also disclose this blank, the lateral traction ratio is 10%-40%, most preferably 20%-30% more preferably.It further discloses and can recently control Ro and this draw ratio is high more by traction, and the planarity of formed film is excellent more.It further discloses, and residual solvent levels is preferably 20%-100 quality % in the film of handling by stenter when tenter frame process begins.Its further disclose preferred when film is tensioned the residual solvent levels of dry this film in this film reach 10 quality % or lower, more preferably 5 quality % or lower.
JP-A-2002-248639, this invention plans to reduce the vertical and horizontal change in size in the storage process under high temperature and wet condition, disclose and comprised the cellulose ester membrane curtain coating on stilt, peel off continuously then and dry this film, wherein drying makes dry contraction percentage satisfy under relational expression 0≤% drying shrinkage≤0.1 * % residual solvent levels in stripping process to carry out.In an optimized technical scheme, when the residual solvent levels in the cellulose ester membrane of being stripped from is 40 quality %-100 quality %, stenter is clamped on the both sides of this film transported this cellulose ester membrane and make the residual solvent levels in the cellulose esters reduce by 30 quality % or more.The residual solvent levels of being stripped from the cellulose ester membrane at stenter conveyer entrance and exit place is respectively 40 quality %-100 quality % and 4 quality %-20 quality %.Tension force that cellulose ester membrane transported by stenter is increased to the outlet of stenter conveyer from the inlet of stenter conveyer.The horizontal tension with this cellulose ester membrane is identical basically to make the tension force that cellulose ester membrane transported by stenter.
In addition, JP-A-2000-239403 has proposed to make that the relation between the residual solvent levels X and the residual solvent levels Y in being incorporated into the process of stenter satisfies the formation that expression formula 0.3X≤Y≤0.9X carries out film in stripping process, to obtain to have the good film of little thickness and optical isotropy and planarity.
JP-A-2002-286933 for example understands and is included in the method that stretches heating condition under and comprises solvent is attached to the method that stretches in the film method as the film by curtain coating formation that stretches.Disclose also that near the preferred glass transition temperature that is not higher than resin really of stretching under heating condition value carries out, and the stretching that the formed film of curtain coating immerses in the solvent can be passed through dry this film, this film is contacted with solvent, and this film carries out so that this film by solvent impregnated, stretches then.
[physical property of optical resin film]
Hereinafter the preferred physical property of optical resin film of the present invention will be described with reference to acylated cellulose as an example.
(film thickness)
The dried thickness of the acylated cellulose that is obtained depends on purposes, but is generally 5 μ m-500 μ m, preferred 20 μ m-300 μ m, preferred especially 30 μ m-150 μ m.For optical display, particularly for the VA mode LCD, the thickness of this cellulose acylate film also is preferably 40 μ m-110 μ m.For the thickness of this film being adjusted to the value of hope, can suitably adjust the concentration of solids content in the dope, the slit in die orifice crack, the extrusion pressure of die orifice, the speed of metal support etc.The width of the cellulose acylate film of Huo Deing is preferably 0.5m-3m like this, more preferably 0.6n-2.5m, further preferred 0.8m-2.2m.The length of batching of each volume is preferably 100m-10,000m, and more preferably 500m-7,000m, further preferred 1,000m-6,000m.In coiling process, preferably carry out embossing at least one edge of this film.The width of embossing is preferably 3mm-50mm, more preferably 5mm-30mm.The height of embossing is preferably 0.5 μ m-500 μ m, more preferably 1 μ m-200 μ m.Can embossing on one or two surface of this film edge.
(optical property of cellulose acylate film)
It is to postpone in the face at λ place and the delay of thickness direction that employed in this article term " Re λ " and " Rth λ " are illustrated respectively in wavelength.Re (λ) incides in " KOBRA 21ADH " (by Ouji ScienceInstrumentsCo., Ltd. produces) by to make wavelength be λ nm light with the direction perpendicular to film to measure.Rth λ is by KOBRA 21ADH, based at Re λ that to make wavelength be λ nm light measures on 11 points with the direction incident of 10 angle tilts in+50 ° the scope in the normal direction-50 of film °, wherein slow axis (measuring by " KOBRA 21ADH ") is as sloping shaft (turning axle) in the face, and the mean refractive index of supposing and the film thickness of input calculate.As the mean refractive index of supposition, can use to be disclosed in " Polymer Handbook ", John Wiley﹠amp; Sons, the refractive index in Inc. and the various blooming.For cellulose acylate film, can use Abbe refractometer with unknown mean refractive index.
The mean refractive index of main blooming is exemplified below.Acylated cellulose (1.48), cycloolefine polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), polystyrene (1.59).By the mean refractive index and the film thickness of input supposition, KOBRA21ADH calculates nx, ny and nz.From nx, ny and nz calculate Nz=(nx-nz)/(nx/ny) then.
Be used under the situation of VA pattern at cellulose acylate film according to the present invention; two technical schemes have been used; that is, comprise and a slice cellulose acylate film is provided in the technical scheme of (two types) on the both sides of element and comprises the technical scheme that a slice cellulose acylate film only is provided in (a slice type) on the side of element.
Be used in the cellulose acylate film of two types, preferably have 20nm-100nm, more preferably the Re of 30nm-70nm and 70nm-300nm, the more preferably Rth of 100nm-200nm.
Be used in the cellulose acylate film of a slice type, preferably have 30nm-150nm, more preferably the Re of 40nm-100nm and 100nm-400nm, the more preferably Rth of 150nm-250nm.
For the reference direction of web-like film, preferably drop on-2 ° to 2 ° according to the angular separation of slow axis in the face of cellulose acylate film of the present invention, more preferably-1 ° to 1 °, most preferably-0.5 ° in 0.5 ° scope.Employed in this article term " reference direction " means at cellulose acylate film it is the longitudinal direction of web-like film under the situation of longitudinal stretching, perhaps at acylated cellulose by the horizontal direction under the situation of cross directional stretch.
According to cellulose acylate film of the present invention preferably have 0nm-10nm Δ Re (wherein Δ Re be the Re of 25 ℃-10%RH value with the Re of 25 ℃ of 80%RH value poor (=Re10%RH-Re80%RH) and the Δ Rth of 0nm-30nm (wherein Δ Rth be the Rth of 25 ℃-10%RH value and the Rth of 25 ℃ of 80%RH value poor (=Re10%RH-Re80%RH) reduce the tonal variation of liquid crystal indicator along with the time.
In addition, preferably under 25 ℃ and 80%RH, show 3.2% or lower equilibrium moisture content according to cellulose acylate film of the present invention, to reduce the tonal variation of liquid crystal indicator along with the time.
Liquid water content is on the cellulose acylate film sample that size according to the present invention is 7mm * 35mm, measures by CA-03 type water content meter and VA-05 type samples dried device (being produced by Mitsubishi Chemical Corporation) by Karl Fischer method.The amount (g) of using the quality (g) of sample to dewater is then determined water cut.
In addition, preferably under 60 ℃ and 95RH, show after aging 24 hours according to acylated cellulose of the present invention and be not less than 400g/m
224hr-1,800g/m
224hr (amount to into the film thickness of 80 μ m calculate) reduces the tonal variation of liquid crystal indicator along with the time.
The thickness of cellulose acylate film is big more, and then its moisture transmission is more little.The thickness of this cellulose acylate film is more little, and then its moisture transmission is big more.Do not consider the thickness of film sample, the film thickness that need amount to into 80 μ m calculates the moisture transmission of film sample.Conversion can be undertaken by equation (amounting to into thickness (μ m)/80 μ m of the moisture transmission * measurement of the moisture transmission that film thickness calculated of 80 μ m=measured).
Details for the method for the measurement moisture transmission that can be applied to this paper, can be referring to " Kobunshi no Bussei II " (Physical Properties of Polymers II, Institute ofPolymer Experiment 4, Kyoritsu Shuppan, pp.285-294:Measurement ofvapor permeability (mass method, the thermometer method, vapor method, absorption process).
The measurement of glass transition temperature is following carrying out.Specifically, will be the moisture conditioning 2 hours under 25 ℃ and 60RH of the cellulose acylate film of 5mm * 30mm according to size of the present invention.Use DVA-225 type dynamic viscoelastic instrument (Vibron) (producing) then by IT KeisoluK.K., with the programming rate of 2 ℃/min, 30 ℃-200 ℃ measurement temperature and the frequency of 1Hz are that 20mm measures this film sample through the excess moisture conditioning with the distance between the anchor clamps.With the storage elastic modulus be logarithmic axis and with temperature (℃) be linear axes, these measured values draw.When the state of film sample reduces suddenly by straight line 1 expression from solid-state areas formed storage modulus when the glass transition zone is mobile.Moving of storage modulus in the glass transition zone by straight line 2 expressions.Article two, straight line 1 and 2 temperature of intersecting each other is that the film sample shows the temperature that storage modulus descends and begins to soften suddenly when heating, that is, the state of film sample begins to move on to the temperature in glass transition zone.Like this, determined glass transition temperature T g (dynamic viscoelastic).
Preferably show the turbidity of 0.01%-2% according to cellulose acylate film of the present invention.This turbidity can followingly be measured.
Use HGM-2DP type nephelometer (by Suga TestInstuments Co., Ltd. produces) according to JIS K-6714, the cellulose acylate film sample that is 40mm * 80mm to size according to the present invention under 25 ℃ and 60%RH carries out turbidimetry.
In addition, acylated cellulose according to the present invention preferably shows the mass change of 0%-5% after aging 48 hours under 80 ℃ and 90%RH.
In addition, acylated cellulose according to the present invention preferably shows the mass change of 0%-5% after aging 24 hours under 60 ℃ and 95%RH or 90 ℃ and 5%RH.
Preferably show 50 * 10 according to acylated cellulose of the present invention
-13Cm
2/ dyne or lower photoelastic coefficient are to reduce the tonal variation of liquid crystal indicator along with the time.
The method that is used for the measuring light elasticity coefficient in addition makes size be subjected to longitudinal stretching stress for the cellulose acylate film sample of 10mm * 100mm.Under these conditions, the delay of using M150 type polarisation light ellipticity measuring instrument (producing) to measure this film sample by JASCO Corporation.Then from along with the change calculations photoelastic coefficient of answering force delay.
(optical anisotropic layer)
Optical resin film of the present invention the optical anisotropic layer that provides thereon can be provided form for example diaphragm of Polarizer.For the layout of optical anisotropic layer, preferably oriented layer and optical anisotropic layer are provided on the optical resin film in proper order with this.
Oriented layer can provide by some method, and the organic compound that for example rubs (preferred polymers), inclined deposition mineral compound and formation have the layer of microflute.In addition, known that oriented layer carries out orientation when giving the electric or magnetic field or marquis during with optical radiation.Yet, be particularly preferred by the formed oriented layer of friction polymer.Preferably the surface of this polymeric layer carries out several times by rubbing with predetermined direction with paper or cloth in friction.The preferably mutual substantially parallel setting of the absorption axes of polarizer and frictional direction.As the polymkeric substance that is used in oriented layer, preferably use polyimide, polyvinyl alcohol (PVA), be disclosed in polymkeric substance among the JP-A-9-152509 etc. with polymerizable groups.The thickness of oriented layer is preferably 0.01 μ m-5 μ m, more preferably 0.05 μ m-2 μ m.
Optical anisotropic layer also preferably has liquid-crystal compounds.Will be used in liquid-crystal compounds of the present invention and preferably have discotic compound (discotic mesogenic).Discotic liquid-crystalline molecules has the plate-like core segment as following discotic liquid-crystalline molecules (I), extends side chain from this plate-like core segment radiation.For the discotic liquid-crystalline molecules with ageing stability is provided, preferably further combined with when being heated or the group of time reaction by optical radiation.The preferred examples of above-mentioned disc liquid-crystal compounds is disclosed among the JP-A-8-50206.
Discotic liquid-crystalline molecules (I)
Near oriented layer, discotic liquid-crystalline molecules is arranged essentially parallel to the planar alignment of this film with pre-tilt angle from frictional direction.In the air surface side, discotic liquid-crystalline molecules is basically perpendicular to membrane plane and arranges.The discotic mesogenic layer has experienced as a whole and has mixed orientation.By this layer structure, can improve the field-of-view angle of TN pattern TFT-LCD.
Above-mentioned optical anisotropic layer will be normally by being coated on the oriented layer by the solution in solvent by discotic compound and other compound (and optional polymerisable monomer and Photoepolymerizationinitiater initiater), dry this coated oriented layer, the oriented layer that applies is heated to plate-like nematic phase formation temperature, by make the oriented layer process polymerization of this coating with ultraviolet radiation, cool off the oriented layer of this coating then.The plate-like nematic liquid crystal phase-solid transformation temperature that is used in disc liquid-crystal compounds of the present invention is preferably 70 ℃-300 ℃, preferred especially 70 ℃-170 ℃.
As the compound except discotic compound that is attached in the above-mentioned optical anisotropic layer, can use compatible with discotic compound can provide the tilt angle varied of hope or not damage any compound of its arrangement to the liquid crystal discotic compound.Such examples for compounds comprises that polymerisable monomer (for example; have vinyl, ethyleneoxy, acryloyl group and methacryl); the orientation control for example fluorine-containing triaizine compounds of adjuvant of surface engagement face side and polymkeric substance be acylated cellulose, acetyl propionyl cellulose, hydroxypropyl cellulose and acetobutyryl cellulose for example.Based on the quality of discotic compound, these compounds are normally with 0.1 quality %-50 quality %, and the amount of preferred 0.1 quality %-30 quality % is used.
The thickness of optical anisotropic layer is preferably 0.1 μ m-10 μ m, more preferably 0.5 μ m-5 μ m.
Alternatively, this optical anisotropic layer can be by non-liquid-crystal compounds is dissolved in the solvent, with this solvent coating on stilt, and the non-liquid crystalline polymer layer of the prepared non-liquid crystalline polymer layer preparation of dry this coating layer.As being used in non-liquid-crystal compounds of the present invention, can use polymkeric substance for example polyamide, polyimide, polyester, polyetherketone, PAEK, polyamidoimide and polyester-imide, this is because they must have good thermotolerance, and chemical resistance is with the transparency and be rich in rigidity.These polymkeric substance can use separately.Alternatively, these have in the polymkeric substance of different functional groups two or more, and for example PAEK and polyamide can use with potpourri.In these polymkeric substance, polyimide preferably, this is because it shows the high grade of transparency, parasexuality and high stretch to a high-profile.As stilt, preferably use the TAC film here.
The laminated thing that also preferably uses stenter to form with 1.05 non-liquid crystal layer of factor cross directional stretch and stilt, stilt side that then will this laminated thing adheres on the Polarizer.
In addition, this optical anisotropic layer can be the curing oriented layer that is made of the cholesteric crystal with 350nm or selection reflection wavelength still less.Can use the selection reflection wavelength that is disclosed among JP-A-3-67219, JP-A-3-140921, JP-A-5-61039, JP-A-6-186534 and the JP-A-9-133810 to drop on suitable compound in the top restricted portion as this cholesteric crystal.From solidifying the viewpoints such as stability of oriented layer, the example of the cholesteric crystal that can preferably use comprises: the nematic-mode liquid crystal polymer of cholesteric liquid crystal polymer, chiral reagent portion incorporated therein and can forming by the compound that photopolymerization or thermal polymerization form the prepared cholesteric of compound of such liquid crystal polymer takes place.
In this case, this optical anisotropic layer can comprise that the method that cholesteric crystal is coated on the stilt forms by for example.In this case, poor for control phase as required, can use the method that comprises the multilayer that is coated with identical or different cholesteric crystal.The coating of cholesteric crystal can for example woodburytype, compression moulding and infusion process be carried out by any suitable method.As above-mentioned stilt, can use suitable material for example TAC film and other polymer film.
In the process that forms above-mentioned optical anisotropic layer, carried out making the program of liquid crystal molecule orientation.The method that makes the liquid-crystal compounds orientation there is not concrete qualification.Anyly be used to make the suitable method of liquid-crystal compounds orientation to be employed.The example of such method comprises liquid crystal is coated on the alignment film, makes the method for this liquid crystal aligning then.Like this example of the alignment film of Xing Chenging comprise the friction film that makes by organic compound for example alignment film, mineral compound the inclined deposition film, have the film of microflute and by the Langmuir-Blodgett method by the organic compound deposit of the LB film that forms of ω-tricosanic acid, octacosyl ammonio methacrylate and methyl stearate for example.
In addition, can use at alignment film with generation orientation in the optical radiation.On the other hand, can use and comprise that liquid crystal is coated on the stretched film, make the method (JP-A-3-9325) of this liquid crystal aligning then and be included in the method that makes liquid crystal aligning under electric field or the magnetic field that applies.The orientation of liquid crystal molecule is preferably even as far as possible.Above-mentioned cured layer preferably has the fixing liquid crystal molecule of such orientation.
Optical resin film according to the present invention for example cellulose acylate film do not have concrete restriction as under the situation of polarizer diaphragm for the method that is used to prepare this Polarizer.Can use any method commonly used.For example, can make optical resin film of the present invention through alkali treatment, the polyvinyl alcohol water solution with full saponification adheres to it by polyvinyl alcohol film being immersed on the polarizer prepared in the iodine solution then, and this film then stretches.The adhesion process that above-mentioned alkali treatment can be disclosed among JP-A-6-94915 and the JP-A-6-118232 replaces.The example of the bonding agent that the processed surface of diaphragm is adhered to mutually with Polarizer comprises for example polyvinyl alcohol (PVA) and polyvinyl butyral and vinyl glue butyl acrylate for example of polyvinyl alcohol-based adhesives.This Polarizer comprises polarizer and is used to protect the diaphragm of these Polarizer both sides.In addition, diaphragm can adhere on the side of Polarizer and diffusion barrier can adhere on its opposite side.Using diaphragm film and diffusion barrier is in order to protect the purpose of Polarizer in the step of checking this product in the transportation of Polarizer.In this case, in order to protect the surface of Polarizer, diaphragm is adhered to Polarizer and is adhered on that side opposition side of liquid crystal cell.In order to cover the adhesive phase that adheres on the liquid crystal cell, diffusion barrier is adhered on the Polarizer that Polarizer is adhered to that side of liquid crystal cell.
About will according to optical resin film of the present invention for example acylated cellulose adhere on the polarizer, the transmission shaft of this polarizer and slow axis according to acylated cellulose of the present invention are overlapped each other arrange.
Intersect degree of accuracy greater than 1 ° time marquis when the absorption axes (passing the axle of transmission shaft) of cellulose acylate film according to the present invention and polarizer; the Polarizer for preparing under Nicol crossed shows the polarity that degenerates so that the generation light leak can not provide sufficient black level or contrast when combining with liquid crystal cell under Nicol crossed.Correspondingly, be 1 ° or still less according to the direction drift angle each other of the transmission shaft of the direction of the principal refractive index nx of cellulose acylate film of the present invention and Polarizer, preferred 0.5 ° or still less.
(surface treatment)
Can randomly make according to optical resin film of the present invention, for example, cellulose acylate film of the present invention is through surface treatment, so that the fusible raising between cellulose acylate film and the various functional layer (for example, undercoat and backing layer).Adaptable in this article surface-treated example comprises glow discharge processing, ultraviolet radiation, corona treatment, flame treatment and acid or alkali treatment.Adaptable in this article glow discharge is handled and is comprised and can use 10
-3The low-voltage plasma that the infrabar of-20 holders produces down, the plasma that further preferred atmosphere is depressed.Excitation of plasma gas is under these conditions can be by the gas of excitation of plasma.Such excitation of plasma gas comprises for example tetrafluoromethane of argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, fluorocarbons, and their potpourri.。For the details of these excitation of plasma gases, can be with reference to Kokai Giho No.2001-1745, March 15 calendar year 2001, pp.30-32, Janpan Institute of Invention and Innovation.In the plasma treatment under the atmospheric pressure of noticing recently,, used the radiation energy of 20-500Kgy under the electric field of 000Kev at 10-1.Preferably under the electric field of 30-500Kev, used the radiation energy of 20-300Kgy.In these surface treatments, particularly preferably be alkaline saponification, this surface treatment for cellulose acylate film is very effective.
This alkalescence saponification is handled preferably by the cellulose acylate film direct impregnation is carried out on the cellulose acylate film in the saponification solution groove or by solution is coated in.Here the example of adaptable coating process comprises dip coated method, shielding rubbing method, extrusion coated method, rod rubbing method and E type rubbing method.As the solvent of alkaline saponification coating solution, preferred here option table reveals the excellent wetting capacity energy and can keep the good surface appearance of this cellulose acylate film and not have to make because saponification solution is coated on this cellulose membrane at county level its surface roughening.Specifically, preferably use pure series solvent.Especially preferably use isopropyl alcohol.In addition, can use the aqueous solution of surfactant as solvent.Alkali in the alkalescence saponification coating solution preferably can be dissolved in the alkali in the above-mentioned solvent, is more preferably KOH or NaOH.The pH value of saponification coating solution is preferably 10 or more, and more preferably 12 or more.In this alkalescence saponification process, preferably at room temperature carried out this reaction 1 second-5 minutes, more preferably 5 seconds-5 minutes, preferred especially 20 seconds-3 minutes.This washs by the cellulose acylate film of alkaline saponification with sour water then in preferred water or elder generation on the surface that has been coated with saponification solution.
In addition, Polarizer of the present invention preferably includes lip-deep hard conating, antiglare layer and the antireflection film that is arranged on the diaphragm on this Polarizer one side.Specifically, Polarizer is being used in the process of liquid crystal indicator, is being positioned at liquid crystal cell and watches the diaphragm of side to preferably include functional membrane thereon antireflection film for example is provided.As functional membrane, preferably provide hard conating here, at least a in antiglare layer and the anti-reflection layer.
Fig. 7 be graphic formula the figure (for the purpose of explaining has also shown the glass that is used for liquid crystal cell) of cross-sectional configurations of an example of Polarizer of the present invention described.In Fig. 7, diaphragm 72 and 73 is provided on each face of polarizer 71.One of at least has an optical resin film of the present invention in the diaphragm 72 and 73.Use adhesive phase 74 that Polarizer 70 is adhered to and be used for the on glass of liquid crystal display cells 75.Fig. 8 be graphic formula the figure of cross-sectional configurations of another example of Polarizer of the present invention described.The technical scheme of Fig. 8 has the functional membrane 81 on the top mentioned Polarizer that is provided in Fig. 7.
There is no need provides each layer with individual course.For example, can be by on anti-reflection layer with anti-dazzle function or hard conating, providing antiglare layer so that this anti-reflection layer can be simultaneously as anti-reflection layer and antiglare layer.
(anti-reflection layer)
In the present invention, the preferred order of using the order that is laminated on the protective seam to comprise the anti-reflection layer of light scattering layer and low-index layer or being laminated on the protective seam comprises middle index layer, the anti-reflection layer of high refractive index layer and low-index layer.To provide the preferred examples of such anti-reflection layer below.
Below description is provided in the preferred examples of the anti-reflection layer that comprises light scattering layer and low-index layer on the protective seam.
This light scattering layer preferably has the delustring particle that is scattered in it.The refractive index of the material in the light scattering layer except the delustring particle is preferably 1.50-2.00.The refractive index of low-index layer is preferably 1.20-1.49.In the present invention, this diffusion layer has anti-dazzle performance and hard conating performance simultaneously.This light scattering layer can be by individual layer or for example 2-4 the layer formation of a plurality of layer.
The surfaceness in this reflection horizon of decision design is so that center line average roughness Ra is 0.08-0.40 μ m, 10 mean roughness Rz are 10 times of Ra or lower, mean distance Sm between the peak valley is 1-100 μ m, the standard deviation of the height at peak and deepest part is 0.5 μ m or still less in irregularity, the standard deviation of the mean distance Sm between the peak valley and center line as a reference be 20 μ m or still less and the inclination angle be that the ratio on the surface of 0-5 degree is 10% or more, this might obtain enough anti-dazzle performances and visually uniform matte finish.In addition, when catoptrical tone under illuminant-C comprises the b* value of-2 to 2 a* value and-3 to 3 and is that the ratio of 380nm-780nm place minimal reflection and maximum reflection is 0.5-0.99 at wavelength, catoptrical tone is neutrality advantageously.In addition, be 0-3 when under illuminant-C the b* value of transmitted light being pre-determined, the yellow hue that is used in the white demonstration of display device has advantageously been reduced.In addition, when the grid that with size is 120 μ m * 40 μ m be placed between planar light source and the antireflection film of the present invention in case the standard deviation that measured brightness disperses on film be 20 or still less in, can advantageously eliminate the flash of light that when film of the present invention is applied to the high precision panel, is produced.
When the optical property according to anti-reflection layer of the present invention is that direct reflection is 2.5% or still less, transmissivity be 90% or more and 60 ° of glossiness be 70% or still less the time, can suppress outside reflection of light, make it might advantageously improve visuality.Particularly, direct reflection more preferably 1% or still less, most preferably 0.5% or still less.When turbidity is 20%-50%, interior turbidity is 0.3-1 with the ratio of total turbidity, from up to the turbidity of light scattering layer to being 15% or still less in the reduction that forms the turbidity that low-index layer forms later on, the sharpness of transmission image can advantageously reach the flash of light that prevents on the high precision LCD panel and eliminate literal fuzzy when to be 20%-50% and perpendicular projection optical transmission rate with the ratio of the transmissivity of transmitted light on 2 ° of directions of offset from perpendicular be 1.5-5.0 when light comb width is 0.5mm.
(low-index layer)
The refractive index that can be applied to low-index layer of the present invention is preferably 1.20-1.49, more preferably 1.30-1.44.In addition, from reducing the viewpoint of reflectivity, the numerical formula below preferably this low-index layer advantageously satisfies.
(m/4)λ×0.7＜n
1d
1＜(m/4)λ×1.3
Wherein m represents positive odd number; n
1The refractive index of expression low-index layer; And d
1The thickness (mm) of expression low-index layer.λ is the wavelength in the 500nm-550nm scope.
The material that constitutes low-index layer will be described below.
This low-index layer preferably includes fluoropolymer incorporated therein as the low-refraction cementing agent.As such fluorine based polymer, preferably use kinetic friction coefficient to be 0.03-0.20 here, with the contact angle of water be that 90-120 ° and pure water yaw angle are 70 ° or littler heat or the crosslinkable fluoropolymer of ionizing radiation.In the process that image display is installed,, after be bonded and sealed bar or Notepaper, can advantageously more easily peel off this Polarizer along with the peeling force decline of Polarizer of the present invention and commercial binder adhesive tape.The preferred 500gf of peeling force of the Polarizer of measuring by cupping machine or still less, more preferably 300gf or still less, most preferably 100gf or still less.The skin hardness of being measured by micro Vickers hardness meter is high more, and then this low-index layer is difficult to destroyed more.The skin hardness of low-index layer is preferably 0.3GPa or more, more preferably 0.5GPa or more.
The example that is used in the fluoropolymer in the low-index layer comprises the hydrolysate and the dehydrating condensation product (for example, (17 fluoro-1,1,2,2-tetrahydrochysene decyl) triethoxysilane) of the silane compound that contains perfluoroalkyl.Other example of fluoropolymer comprises fluorine-containing monomer unit and is used to provide the fluorinated copolymer of the formation unit of activity of cross-linking reaction as constituent.
The instantiation of fluorochemical monomer comprises that fluoroolefins (for example, fluorothene, vinylidene fluoride, tetrafluoroethene, perfluoro capryl ethene, hexafluoropropylene, perfluor-2,2-dimethyl-1, the 3-dioxole), (methyl) acrylic acid part or all of fluorinated alkyl ester derivant (for example, Biscoat 6FM (producing), M-2020 (by DAIKIN INDUSTRIES, Ltd. produces) by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) and all or part of vinyl acetate of fluoridizing.In these fluorochemical monomers, perfluoroolefine preferably.In these fluorochemical monomers, the viewpoint from refractive index, resolvability, transparency, availability etc. particularly preferably is hexafluoropropylene.
Be used to provide the example of the formation unit of activity of cross-linking reaction to comprise; the monomer that had before had a self-crosslinking functional group by polymerization is the formation unit that obtains of (methyl) glycidyl acrylate and glycidyl vinyl ether for example; has carboxyl by polymerization; hydroxyl; amino; the monomer of sulfo group etc. (for example; (methyl) acrylic acid; (methyl) methyl acrylate; (methyl) hydroxyalkyl acrylate; allyl acrylate; the hydroxyethyl vinyl ether; hydroxy butyl vinyl ether; maleic acid; crotonic acid) the formation unit that is obtained; and by the polyreaction reaction of acryloyl chloride and hydroxyl (for example, by) with the activity of cross-linking reaction group for example (methyl) acryloyl group be incorporated into these formation formation unit that the unit obtained.
Except above-mentioned fluorine-containing monomer unit be used to provide the formation unit of activity of cross-linking reaction, from the dissolubility solvent, viewpoints such as the transparency of film, suitably the copolymerization monomer of contain fluorine atoms not.The monomeric unit that can be used in combination with above-mentioned monomeric unit is not limited particularly.The example of these monomeric units comprises that olefines (for example, ethene, propylene, different propylene, vinyl chloride, vinylidene chloride), esters of acrylic acid (for example, methyl acrylate, ethyl acrylate, 2-EHA), methyl acrylic ester (for example, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, Ethylene glycol dimethacrylate), styrene derivative (for example, styrene, divinyl ether, vinyltoluene, α-Jia Jibenyixi), vinyl ethers (for example, methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether), vinyl esters (for example, vinyl acetate, propionate, vinyl cinnamate), acrylic amide (for example, N tert butyl acrylamide, N-cyclohexyl acrylamide), Methacrylamide, and acrylic nitrile derivates.
As disclosed among JP-A-10-25388 and the JP-A-10-147739, above-mentioned polymkeric substance can suitably be used in combination with hardening agent.
(light scattering layer)
Light scattering layer is to form for the light scattering property that shows one of at least in providing by surface scattering and scattering-in to this film and for the purpose of the hard conating of the scratch-resistant that improves this film.Correspondingly, light scattering layer comprises that incorporated therein being used to provides the bonding agent of hard conating performance, is used to provide the delustring particle of light dispersiveness and chooses wantonly be used to improve refractive index, prevents crosslinked contraction and the inorganic filler that improves intensity.In addition, the light scattering layer that forms so also provides antiglare layer as antiglare layer to this Polarizer.
For the hard conating performance is provided, the thickness of light scattering layer is 1-10 μ m, more preferably 1.2-6 μ m.When the thickness of light scattering layer was too little, formed Polarizer showed and lacks the hard conating performance.On the contrary, when the thickness of light scattering layer was too big, formed Polarizer showed the curling resistance of decline or fragility is worsened and caused inadequate processability.
Be combined in bonding agent in the light scattering layer and preferably have saturated hydrocarbon chain or polyether chain, more preferably have the polymkeric substance of saturated hydrocarbon chain as main chain as the polymkeric substance of main chain.This bonding agent preferably has cross-linked structure.As having the binder polymer of saturated hydrocarbon chain as main chain, preferred here (being total to) polymkeric substance that uses monomer with two or more ethylenically unsaturated groups.In order to provide higher refractive index, can select to contain aromatic ring or at least one and be selected from those of atom in the group of forming by the halogen atom except fluorine, sulphur atom, phosphorus atoms and nitrogen-atoms to this binder polymer.
Example with monomer of two or more ethylenically unsaturated groups (for example comprises polyvalent alcohol and (methyl) acrylic acid ester class, two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid butanediol ester, two (methyl) acrylic acid hexanediol ester, 1,4-cyclohexane diacrylate, four (methyl) acrylic acid pentaerythritol ester, three (methyl) acrylic acid pentaerythritol ester, trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, five (methyl) acrylic acid dipentaerythritol ester, four (methyl) acrylic acid dipentaerythritol ester, five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid pentaerythritol ester, 1,2,3-cyclohexane four (methyl) acrylate, the polyurethane polyureas acrylate, the polyester polyacrylate), the modified product of above-mentioned oxirane, vinyl benzene and its derivant are (for example, 1, the 4-divinylbenzene, 4-vinyl benzoic acid-2-acryloyl ethyl ester, 1,4-divinyl cyclohexanone), vinyl sulfone (for example, divinylsulfone), acrylamide (for example, and Methacrylamide methylene diacrylamine).Above-mentioned monomer can be used in combination with two or more.
The instantiation of high refractive index monomers comprise two (4-methacryl thiophenyl) thioether, vinyl naphthalene, ethenylphenyl thioether and 4-methacryloxy phenyl-4 '-the methoxybenzene thioether.These monomers equally also can be used in combination with two or more.
Polymerization with monomer of these ethylenically unsaturated groups can be in the presence of optical free radical polymerization initiator or hot radical polymerization initiator, by carrying out with ionizing radiation or heating.
Correspondingly; anti-reflection layer can contain the monomer with ethylenically unsaturated group by comprising preparation; the coating solution of delustring particle and inorganic filler; this coating solution is coated on the protective seam, then with ionizing radiation or heat the method that this coating causes polyreaction and curing and form.As such Photoepolymerizationinitiater initiater etc., can use any known such a compound here.
As having the polymkeric substance of polyethers, preferably use multi-group epoxy compound's ring-opening polymerization product here as main chain.Multi-group epoxy compound's ring-opening polymerization can be undertaken by heating to multi-group epoxy compound's radiation or to the multi-group epoxy compound with ionizing radiation by generating in photic acid in the presence of body or the thermic acid generation body.Correspondingly; anti-reflection layer can contain multi-functional epoxy compound by comprising preparation; photic acid generates body; the coating solution of little smooth particle and inorganic filler; this coating solution is coated on the protective seam, then with this coating of ionizing radiation radiation or heat the method that this coating causes polyreaction and curing and form.
Replace or except monomer with two or more ethylenically unsaturated groups, can use monomer to come crosslinkable functionality in the conjugated polymer with crosslinkable groups so that the crosslinkable functionality reaction bonded cross-linked structure in the binder polymer.
The example of crosslinkable functionality comprises isocyanate group, epoxy radicals, '-aziridino, oxazolinyl, aldehyde radical, carbonyl, diazanyl, carboxyl, methylol and active methylene group.Methylol, ester class, carbamate and the metal alkoxide that also can use vinyl sulfonic acid, acid anhydrides, cyanacrylate derivant, melamine, etherificate for example tetramethoxy-silicane as the monomer of introducing cross-linked structure.Can use the functional group's blocked isocyanate group for example that shows crosslinkable owing to decomposition reaction.In other words, in the present invention, crosslinkable functionality can be self be not reactivity but since decomposition reaction can become reactivity.
These binder polymers with crosslinkable functionality can be coated and can be heated and form crosslinked structure.
For anti-dazzle performance is provided to himself; this light scattering layer comprises the delustring particle of portion incorporated therein; this particle has the mean grain size that is not more than filler particles and this particle diameter at 1-10 μ m, in the scope of preferred 1.5-7.0 μ m, and for example inorganic particulate compounds and particulate resin.
The instantiation of above-mentioned delustring particle comprises inorganic particulate compounds for example particulate silica and particle TiO
2, for example particle propylene, particle exchange propylene, particle polystyrene, particle cross-linked styrene, particle melamine resin and particle benzoguanamine resin with particulate resin.In these particulate resin, preferably particle cross-linked styrene, particle crosslink propylene, particle crosslink propylene styrene and particulate silica.The delustring particle can be sphere or atypic.
Two or more delustring particles with different-grain diameter can be used in combination.Delustring particle with greater particle size can be used to provide the light scattering layer with anti-dazzle performance.Delustring particle with greater particle size can provide the light scattering layer with other optical property.
In addition, delustring particle grain size distribution is monodispersed most preferably.Various particle grain size are preferably approaching mutually as much as possible.For example, be defined as under the situation of coarse particles greater than mean grain size 20% or more particles at diameter, the ratio of these coarse particles be preferably total number of particles 1% or still less, more preferably 0.1% or still less, further preferred 0.01% or still less.Size distribution drops on the delustring particle in the top institute restricted portion, can by to the delustring particle of conventional synthetic method acquisition suitably classification obtain.By quantity that increases classification step or the degree of strengthening classification, can obtain to have the matting agent of better distribution.
Above-mentioned delustring particle is to be 10-1 with the ratio of delustring particle in light scattering layer, 000mg/m
2, more preferably 100-700mg/m
2Mode be attached in the light scattering layer.
For the measurement of delustring particle size distribution, can use the safe counting method of Cauer.The size distribution that to measure like this converts the granule number distribution to then.
Except above-mentioned little smooth particle, this light scattering layer preferably include be attached to mean grain size that the oxide by being selected from least a metal in the group of being made up of titanium, zirconium, aluminium, indium, zinc, tin and antimony in it makes be 0.2 μ m or still less, preferred 0.1 μ m or still less, be more preferably 0.06 μ m or inorganic particle still less improves its refractive index.In order to improve refractive index difference according to the delustring particle, the light scattering layer that comprises the high index of refraction delustring particle of combination in it preferably includes the Si oxide that is attached in it and keeps its refractive index a little somewhat low.The preferred particle diameter of particulate Si oxide is identical with above-mentioned inorganic filler.
The instantiation that is attached to the inorganic filler in the light scattering layer comprises TiO
2, ZrO
2, Al
2O
3, In
2O
3, ZnO, SnO
2, Sb
2O
3, ITO and SiO
2From improving the viewpoint of refractive index, in these inorganic fillers, particularly preferably be TiO
2And ZrO
2The surface that preferably makes inorganic particle is through silane coupled processing or titanium coupling processing.For this purpose, preferably use bonding agent seed lip-deep to have the surface treatment of the functional group of reactivity with it.
Based on the gross mass of light scattering layer, in conjunction with the amount of inorganic filler be preferably 10%-90%, more preferably 20%-80%, preferred especially 30%-75%.
Thereby such filler has the particle diameter that is enough to less than light wavelength does not cause scattering.Have the suspending liquid that in bonding agent, has disperseed such adjuvant like this and show as the uniform material of optics.
Total refractive index of the potpourri of bonding agent and inorganic particle is preferably 1.50-2.00 in the light scattering layer, more preferably 1.51-1.80.For the total refractive index with this potpourri pre-determines in the above in the restricted portion, can suitably select the kind and the ratio of bonding agent and inorganic filler.How to select these factors can be in advance through overtesting easily up to.
For the surface appearance that keeps light scattering layer is evenly for example even and prevent point defect in coating and drying, the coating solution that is used to form light scattering layer comprises that fluorine incorporated therein is that surfactant and silicon are one or both in the surfactant.Particularly, preferably using fluorine is surfactant, this be because its can make with less amount be used for showing eliminate surface imperfection for example be coated with drying in unevenness and the effect of the point defect of antireflection film of the present invention.Expect that such fluorine is the inhomogeneity while of surfactant in the raising surface appearance, makes coating solution be suitable for high-speed coating, thereby has improved throughput rate.
Hereinafter description is laminated in the antireflection film that order on the diaphragm comprises middle index layer, high refractive index layer and low-index layer.
Design comprises and being laminated on the diaphragm that order has the antireflection film of the layer structure of index layer at least one, high refractive index layer and low-index layer (outermost layer), so that have the refractive index that satisfies the following relationship formula.
The refractive index of the refractive index＞low-index layer of the refractive index＞diaphragm in the refractive index＞middle layer of high refractive index layer
In addition, can between diaphragm and middle index layer, provide hard conating.In addition, antireflection film can comprise stacked middle refractive index hard conating, high refractive index layer and low-index layer mutually.
The example of such anti-reflection layer comprises and is disclosed among JP-A-8-122504, JP-A-8-110401, JP-A-10-300902, JP-A-2002-243906 and the JP-A-2000-111706 those.
In addition, each layer can have other function.The example of these layers comprises antifouling low-index layer and antistatic high refractive index layer (being disclosed in JP-A-10-206603, JP-A-2002-243906).
The turbidity of anti-reflection layer is preferably 5% or lower, and more preferably 3% or lower.Preferably be not less than H by intensity, more preferably be not less than 2H, most preferably be not less than 3H according to the definite anti-reflection layer of the pencil hardness test method of JIS K5400.
(high refractive index layer and middle index layer)
The layer that has high index of refraction in anti-reflection layer is to be that the cured layer of 100nm or littler high index of refraction inorganic particulate compounds and substrate adhesive forms by containing mean grain size.
As the high index of refraction inorganic particulate compounds, can use refractive index is 1.65 or more, preferred 1.9 or more mineral compound.The example of such high index of refraction inorganic particulate compounds comprises the oxide of Ti, Zn, Sb, Sn, Zr, Ce, Ta, La and In and the composite oxides of these metallic atoms.
For such particulate material is provided, need satisfy following requirements.For example, must carry out surface treatment to the surface of particle and (for example, be disclosed in JP-A-11-295503, JP-A-11-153703, with the silane coupling agent among the JP-A-2000-9908, be disclosed in ionic compound or organic metal coupling agent among the JP-A-2001-310432).In addition, this particle must have and comprises the nucleocapsid structure (be disclosed in JP-A-2001-166104) of high refractive index particle as core.Can use simultaneously specific spreading agent (be disclosed in JP-A-11-153703, US6,210,858B1, JP-A-2002-277609).
The example that matrix forms material comprises known thermoplastic resin, thermoset resin etc.
Matrix forms the material preferred examples and comprises: have the compositions that contains the polyfunctional compound two or more at least in free radical polymerizable groups and the cationic polymerizable group, have the organometallics that comprises hydrolyzable groups and have at least a composition that is selected from the group that the composition by the partial condensate that contains it constitutes.
The example of these materials comprises the compound that is disclosed among JP-A-2000-47004, JP-A-2001-315242, JP-A-2001-31871 and the JP-A-2001-296401.
In addition, the preferred use by the colloidal metal oxide that hydrolytic condensation obtained of metal alkoxide and the curable layer that obtains by metal alkoxide compositions.For the details of these materials, can be referring to JP-A-2001-293818.
The refractive index of high refractive index layer is preferably 1.70-2.20.The thickness of high refractive index layer is preferably 5nm-10 μ m, more preferably 10nm-1 μ m.
The refractive index of index layer in the adjustment so that its drop between the refractive index of the refractive index of low-index layer and high refractive index layer.The refractive index of middle index layer is preferably 1.50-1.70.The thickness of high refractive index layer is preferably 5nm-10 μ m, more preferably 10nm-1 μ m.
(low-index layer)
Low-index layer is laminated on high refractive index layer.The refractive index of low-index layer is preferably 1.20-1.55, more preferably 1.30-1.50.
Preferably low-index layer is designed to have the outermost layer of scratch-resistant and resistance to soiling.In order greatly to improve the scratch-resistant of low-index layer, can on the surface of low-index layer, form the thin layer that surface smoothness is provided effectively by in it, introducing known silicon or fluorine.
As fluorochemicals, the preferred crosslinkable that uses amount with 35-80 quality % to contain to have fluorine atom or the compound of polymerizable functional group.
Such examples for compounds comprises and is disclosed in JP-A-9-222503, [0018]-[0026] section, and JP-A-11-38202, [0019]-[0030] section, those among the JP-A-20011-40284, [0027]-[0028] section and JP-A-2000-284102.
The refractive index of fluorochemicals is preferably 1.35-1.50, more preferably 1.36-1.47.
As silicon compound, preferred here the compound that uses with polysiloxane structure, wherein curable functional group or polymerizable functional group are bonded to and form bridging structure in the main polymer chain in films.Such examples for compounds comprises reactive silicon compound (for example, SILAPLANE is produced by CHISSO CORPORATION) and has the polysiloxane (being disclosed in JP-A-11-258403) of silanol group at its two ends.
For one of at least crosslinked or polyreaction in fluoropolymer with crosslinkable or polymerizable groups and the siloxane polymer, preferably contain polymerization initiator in coating, sensitizer etc. be used to form outermost coating composition the time or afterwards, form low-index layer with optical radiation or heating.
In addition, preferably use in the presence of catalyzer by solidifying for example silane coupling agent and contain the sol-gel cured film that the silane coupling agent of special hydrofluorocarbons group obtains of organometallics.
The example of such sol-gel cured film comprises and contains poly-fluoroalkyl silane compound and its partial hydrolysis condensation product (being disclosed in the compound among JP-A-58-142958, JP-A-58-147483, JP-A-58-147484, P-A-9-157582 and the JP-A-11-106704), with have poly-(perfluoroalkyl ethers) base as silyl compound of fluorine-containing long-chain (for example, be disclosed among JP-A-2000-117902, JP-A-2001-48590, the JP-A-2002-53804 compound).
The filler that this low-index layer can comprise the adjuvant of conduct incorporated therein except above-mentioned adjuvant (for example, primary average particle size is low-refraction mineral compound for example particulate silica (tripoli) and the particle fluorine material (magnesium fluoride of 1-150nm, calcium fluoride, barium fluoride), is disclosed in JP-A-11-3820, the organic granular material in [0020]-[0038] section), silane coupling agent, lubricant, surfactant, etc.
Under the situation below low-index layer is set at outermost layer, this low-index layer can pass through gas phase process (vacuum evaporating method, sputtering method, ion plating, plasma CVD method etc.) and form.Coating process wishes that this is because it can be with this low-index layer of low-cost production.
The thickness of low-index layer is preferably 30nm-200nm, more preferably 50nm-150nm, most preferably 60nm-120nm.
(hard conating)
Hard conating is provided in the diaphragm physical strength that gives to have on it anti-reflection layer on the surface of diaphragm usually.Particularly, preferably this hard conating is provided between transparent support thing and the above-mentioned high refractive index layer.This hard conating preferably cross-linking reaction by light solidity and/or heat-curable compounds or polyreaction forms.Curable functional group in the curable compound is photopolymerizable functional group preferably.In addition, organometallics or the organoalkoxysilane based compound that contains hydrolyzable functional group is desirable.
The instantiation of these compounds comprises the identical compound that is exemplified with high refractive index layer.The instantiation that constitutes the composition of hard conating comprises and is described in JP-A-2002-144913, those in JP-A-2000-9908 and the WO00/46617 pamphlet.
High refractive index layer can also be as hard conating.In this case, can with identical mode described in the high refractive index layer, particle be scattered in finely form high refractive index layer in the hard conating.
This hard conating can comprise that the mean grain size that is attached in it is used as providing the antiglare layer of anti-dazzle performance for the particle of 0.2 μ m-10 μ m.
Can suitably design the thickness of this hard conating according to purpose, the thickness one of this hard conating is preferably 0.2 μ m-10 μ m, more preferably 0.5 μ m-7 μ m.
Preferably be not less than H by intensity, more preferably be not less than 2H, most preferably be not less than 3H according to the definite anti-reflection layer of JIS K5400.When carrying out the tapering test according to JIS K5400 when, the wearing and tearing of preferred test sample are as far as possible little.
(other layer in the anti-reflection layer)
In addition, can provide the forescatering layer, prime coat, antistatic layer, undercoat, protective seam etc.
(antistatic layer)
This antistatic layer, if be provided with, preferably provide calculate according to specific insulation 10
-8(Ω cm
-3) or littler conductivity.The use of the surfactant of hygroscopic material, water-soluble inorganic salt, particular types, cationic polymer, anionic polymer, colloidal silica etc. makes it might provide 10
-8(Ω cm
-3) specific insulation.Yet therefore these materials have very big dependence for temperature and humidity can not provide enough conductances under low humidity.Therefore, as conductive layer, preferably use metal oxide here.There are some burning compounds that color is arranged.Use such metal oxide that has color to cause unfriendly that as the material of conductive layer whole film is colored.The example that forms the metal of colourless metallic oxide comprises Zn, Ti, Sn, Al, In, Si, Mg, Ba, Mo, W, and V.The preferred metal oxide that mainly constitutes that uses by these metals.The instantiation of these metal oxides comprises ZnO, TiO
2, SnO
2, Al
2O
3, In
2O
3, SiO
2, MgO, BaO, MoO
3, WO
3, V
2O
5And their composition.In these metal oxides, particularly preferably be ZnO, TiO
2And SnO
2About the combination of variety classes atom, effectively with Al, In etc. join ZnO
2In.Sb, Nb, halogen atoms etc. are joined SnO effectively
2In.Nb, Ta etc. are joined TiO effectively
2In.In addition, as disclosed among the JP-B-59-6235, can use attached to the material that comprises above-mentioned metal oxide on other crystal metal particle or the fibrous material (for example, titanium dioxide).Specific insulation is different physical values with surface resistivity, therefore can not contrast mutually simply.Yet, for provide calculate according to specific insulation 10
-8(Ω cm
-3) or littler conductivity, if this conductive layer has according to 10 of surface resistivity calculating
-10(Ω/) or still less, and preferred 10
-8(Ω/) or resistivity still less are then just enough.When conductive layer is provided with as outermost layer, be necessary to measure the surface resistivity of conductive layer.Carry out in the step of the measurement of surface resistivity in can the process of described in this article formation laminate film.
＜liquid crystal indicator 〉
Polarizer of the present invention can advantageously be used in the liquid crystal indicator.Polarizer of the present invention can be used in the liquid crystal cell of various display modes.For example TN (twisted-nematic) of various display modes has been proposed, IPS (face internal conversion), FLC (ferroelectric liquid crystals), AFLC (anti ferroelectric liquid crystal), OCB (optical compensation curved), STN (top twisted-nematic), VA (homeotropic alignment) and HAN (mix and arrange) to row.In these display modes, VA pattern preferably.
In VA mode liquid crystal element, when not applying voltage, the rod shaped liquid crystal molecule vertical orientation.
The VA liquid crystal cell comprises that (1) rod shaped liquid crystal molecule when not applying voltage is almost vertical orientated, but when applying voltage the sense stricto VA mode liquid crystal element (being disclosed in JP-A-2-176625) of horizontal alignment almost.Except VA mode liquid crystal element (1), provide (2) (to be disclosed in SID 97 here by the VA mode liquid crystal element (MVA pattern) of multidomain expanded field of vision angle, Digest ofTech.Papers (preprint) 28 (1997), 845), (3) rod shaped liquid crystal molecule perpendicular state is arranged when not applying voltage, but when applying voltage with liquid crystal cell (the n-ASM pattern of distortion multidomain pattern orientation, the CPA pattern) (is disclosed in Preprints of Forum on Liquid Crystal SocietyNos.58-59,1998) and (4) SURVIVAL mode liquid crystal element (being reported in LCDInternational 98).
As the VA mode LCD, can use two Polarizers that comprise liquid crystal cell (VA pattern) and be positioned at this each side of liquid crystal cell here.This liquid crystal cell has the liquid crystal that is arranged between the electrode matrix of both sides.
Fig. 9 and each self-described of Figure 10 the example of structure of liquid crystal indicator of the present invention.
In Fig. 9, diaphragm 72 and 73 is set on each face of polarizer 71.At least a in the diaphragm 72 and 73 has optical resin film of the present invention.Optical resin film of the present invention preferably is set on the liquid crystal cell side of polarizer 71.Functional membrane 81 is provided on the diaphragm 72 (observer's side).Polarizer 70 is adhered to the glass 92 that is used for liquid crystal cell with marginal adhesive phase 74.Liquid crystal cell 90 comprises the liquid crystal layer 91 between the glass sheet 92 and 93 that is used for liquid crystal cell.In light source side with marginal adhesive phase 74 ' with Polarizer 70 ' the adhere to glass 93 that is used for liquid crystal.The diaphragm 72 that Polarizer 70 ' comprise is arranged on polarizer 71 ' each side ' and 73 '.In the present invention, can have optical resin film of the present invention on Polarizer 70 and the 70 ' one or both sides.
Figure 10 has described liquid crystal indicator of the present invention in further detail.In Figure 10, liquid crystal indicator have comprise liquid crystal layer 107 and last matrix 106 and lower substrate 108 wherein liquid crystal layer 107 between they liquid crystal cells between the two.Make matrix 106 and lower substrate 108 through directional process at its liquid crystal side.Light polarizing film 101 and 201 has been set makes liquid crystal cell between between them.Made transmission shaft 102 on the light polarizing film 101 and 201 mutually vertical separately with 202 and with the orientation direction 45 setting of the liquid crystal layer in the liquid crystal cell 107.Be arranged at light polarizing film 101 and 201 and liquid crystal cell between be respectively resin molding 103a of the present invention and 203a and optical anisotropic layer 105 and 109.
Under the situation of using the diaphragm except optical resin film of the present invention, can use any common acylated cellulose.Such cellulose acylate film comprise the commercially available prod for example KC4UX2M (by Konica Minolta Opto Products Co., Ltd produces; 40 μ m), (by Konica Minolta Opto Products Co., Ltd produces KC5UX; 60 μ m), (by Konica Minolta Opto Products Co., Ltd produces KC80UVSFD; 80 μ m), (by Fuji Photo Film Co., Ltd. produces TD80U; 80 μ m), and TF80U (by FujiPhoto Film Co., Ltd. production; 80 μ m).Yet, the invention is not restricted to these products.
[embodiment]
Present invention will be further described in the following embodiments, but the present invention is not limited to this.
Embodiment 1
(preparation of cellulose acylate film)
Will by stir equably cellulose that 100 mass parts make by linter pulp and based on cellulosic quality be potpourri that 100 mass parts glacial acetic acids obtain join in the reaction vessel by 245 mass parts acetic anhydrides; in the potpourri that 365 mass parts acetate and 15 mass parts sulfuric acid constitute, make them then here 47 ℃ of following acetylations 60 minutes as the cooling of catalyzer.In the process that acetylization reaction finishes, in reaction mixture, add 45.5 mass parts and be used for the magnesium acetate aqueous solution (30 quality %) of hydrolysis and neutralization so that make excessive acetic anhydride and sulfuric acid pass through hydrolysis and neutralization respectively.After this, adding about 12.8 mass parts magnesium acetate aqueous solution (30 quality %) in reaction solution is used for slaking and is heated 60 ℃ simultaneously.After this, in this reaction solution, add entry.Make this solution descend the process slaking reactions 40 minutes then at 70 ℃.After slaking reaction finishes, in this reaction solution, add about 20 mass parts magnesium acetate aqueous solution (30 quality %) and come complete neutralisation of sulphuric acid and finish this reaction.After this reaction finished, precipitation reaction product and it is cleaned with excessive water made its drying then.
Following ingredients is poured in the mixing channel at their places, prepared triacetyl cellulose (triacetyl cellulose: TAC) solution while stir then to heat so that they dissolve.Simultaneously; in 100 mass parts acylated celluloses, add 0.05 mass parts matting agent (AEROSILR972; by NIPPON AEROSIL CO.; LTD. produce) as particulate material, the preparation that ultraviolet light absorber 1 below 0.3 mass parts and the ultraviolet light absorber 2 below 0.7 mass parts are finished dope.
Postpone to increase reagent
Ultraviolet light absorber 1
Ultraviolet light absorber 2
(curtain coating)
The dope temperature be 30 ℃ at width be the width of 1.6m with above-mentioned dope curtain coating on stainless steel band.The dope that makes such curtain coating is by contacting on the stainless steel band of controlling temperature dry 1 minute with its back side with 25 ℃ of warm water, overleaf with stainless steel band that 15 ℃ cold water contact on reservation 15 seconds, then it is stripped down from stainless steel band.
Next, use the single shaft stenter, clamp (steps A), at step B, with the horizontal distance that changes between two clips of the draw speed of 250%/min with the blank two ends that shelf will be peeled off like this.In this program, the environment temperature of film is that 120 ℃ and draw ratio are 1.3.
Next, at step C, when clamping, transport this film with clip.At step C, lax this film makes that this film is 98% among the step B.Next, wherein environment temperature is pre-determined at dry this film of step D1 and be 100 ℃ and obtain cellulose acylate film 1.
In above-mentioned film forming procedure, draft temperature pre-determined be (Tg+30 ℃), wherein Tg is the glass transition temperature of film.
Adjust drying condition in addition and make that be 3.1 in the average rate of drying that clamps step and stretching step with ratio in the average rate of drying of relaxation step.
Then, to twist in the fuse diameter with the length of the width of 1m and 100m be that the glass resin of 200mm strengthens and prepares the film volume on the resin core to the cellulose acylate film that will obtain like this by the diagonal tension method.In this program, be that 250 ℃ embossment ring is pressed on the edge of film so that film becomes and prevented bonding between film and the film afterwards with temperature.
Measure the Re and the Rth that roll up the cellulose acylate film that unclamps from the film of such acquisition then.The results are shown in the table 1.All these films have the thickness of 80 μ m.
(film No.2 and 3 preparation)
Except draft temperature and ultraviolet light absorber change, prepare film with optical property listed in the table 1 in the mode identical with film No.1.
All films that obtained in this embodiment show the turbidity of 0.1-0.9, the mass change of 0.1 μ m or the secondary mean grain size of matting agent still less and the 0%-3% that reservation formed later in 48 hours under 80 ℃-90%RH.
[preparation of Polarizer 1-3]
Making thickness with 30 ℃ warm water is that the 75 μ m and the degree of polymerization are 2,400 polyvinyl alcohol (PVA) (PVA) film swelling 40 seconds, it is impregnated in 30 ℃ the 6 quality % potassium iodide aqueous solutions 60 seconds so that it is colored, and is that 4 quality % and potassium iodide concentration are that it carries out longitudinal stretching with 5.0 factor pair in 60 seconds in 40 ℃ of aqueous solution of 3 quality % immersing boric acid concentration then.After this make this polyvinyl alcohol film obtain polarizer down in dry 4 minutes at 50 ℃.
The cellulose acylate film No.1-3 that has prepared is immersed in 55 ℃ the 1.5mol/l sodium hydrate aqueous solution, water cleans up hill and dale and removes NaOH then.After this, it is in 35 ℃ the 0.05mol/l Dilution of sulphuric acid aqueous solution 1 minute that this cellulose acylate film is immersed temperature, it is immersed in the water so that dilute sulfuric acid aqueous solution is rinsed then.At last, make this sample finish-drying at 120 ℃.
With polyvinyl alcohol-based adhesives that among the cellulose acylate film 1-3 of such saponification each is bonding mutually with " TD80U " (by Fuji Photo Film Co., Ltd. produce), wherein above-mentioned polarizer film is between between them.Then should laminated thing be heated to 70 ℃ 30 minutes.After this, be 1 thereby laterally modify this film preparation effective width with 3cm on the both sides of film, 000m and length are the rolled-up Polarizer 1-3 of 50m.
[coating of adhesive phase]
(preparation of acrylic acid polymer solution)
With 75 mass parts n-butyl acrylates (n-BA), 20 mass parts methyl acrylates (MA), 5 mass parts acrylic acid 2-hydroxy esters (2-HEA), 100 mass parts ethyl acrylates and 0.2 mass parts azoisobutyronitrile (AIBN) are poured in the reaction vessel that the air in it replaced by nitrogen.Stirring on one side this reaction mixture then in nitrogen atmosphere is heated to reaction vessel 60 ℃ on one side and makes reaction mixture reaction 4 hours.After 4 hours, in this reaction mixture, add 100 mass parts toluene, 5 mass parts α-Jia Jibenyixi and 2 mass parts AIBN.This reaction mixture is heated to 90 ℃ of reactions 4 hours.After reaction, obtaining solid content with ethyl acetate diluting reaction product is 20% acrylic polymers solution.In the polymer solution of 100 mass parts solid contents, add 1.0 mass parts isocyanates based cross-linkers (trade name: Colonate L, by NIPPON POLYURETHANE INDUSTRY CO., LTD. produces) then.Fully stir this potpourri then and obtain adhesive composition.
(preparation has the Polarizer 1-3 of bonding agent)
The Polarizer 1-3 for preparing above is coated with applies bonding agent.
The above-mentioned adhesive composition that contains acrylic polymers solution is coated on the polyester film through discharge handling forms the adhesive phase that thickness is 25 μ m thereon.The adhesive phase that will form is like this transferred to (on the film film of component side) on the Polarizer then, makes its slaking under the humidity of 23 ℃ temperature and 65% prepare the Polarizer 1-3 with bonding agent over 7 days then.Then diffusion barrier is adhered on the adhesive phase.Diaphragm is adhered on the diaphragm of the Polarizer side opposite with element.
[the humidity conditioning of Polarizer]
The Polarizer with bonding agent that obtains is like this cut into the size (being arranged in parallel) of 41cm * 30cm according to the absorption axes of Polarizer and a side.Peel off this diaphragm from Polarizer then.In the atmosphere of 25 ℃ and 60%RH, this Polarizer carried out 48 hours humidity conditioning.
[being installed on the panel]
(being installed on the VA panel)
From VA mode liquid crystal TV (LC-20C5 is produced by SHARP CORPORATION) both sides, Polarizer and retardation plate are stripped down.Use laminated roller, with preparation and in the above-described embodiments the Polarizer 1-3 that nursed one's health of humidity adhere to respectively on the dorsal part of this liquid crystal TV.Use laminated roller, the commercially available Polarizer that does not have the field-of-view angle compensating plate is adhered on the front side of this liquid crystal TV.Like this, just prepared liquid crystal panel.
In this program, to arrange the feasible absorption axes of the Polarizer of side of watching and be parallel to the panel setting, the absorption axes of the Polarizer of backlight side is provided with perpendicular to this panel, and adhesive surface is arranged on the liquid crystal cell side.
Use the liquid crystal panel that has adhered to Polarizer to assemble liquid crystal TV then.Open the backlight of this liquid crystal TV then.Determined that the position angle is 0 °, polar angle is 60 ° of aberration Δ x that locate with the place ahead.On this screen, measure 10 points.Average then these measured values provide Δ x.The result is set forth in the following table 1.
Aberration: at the position angle be 0 ° Δ Cu ' v ' (u ' v ': the chromaticity coordinate in CIELAB space): u ' v ' (60 ° of polar angles)-u ' v ' (0 ° of polar angle) and be Δ Cu ' v ' of 180 ° at the position angle: the summation of u ' v ' (60 ° of polar angles)-u ' v ' (0 ° of polar angle)
In table 1, as can be seen, comprise that the liquid crystal indicator of the film with optical property of the present invention advantageously demonstrates very little aberration.
Embodiment 2
Except changing drying condition and change as shown in Figure 2 the distribution of Re and Rth in the face, prepare film in the mode identical with embodiment 1.Then with embodiment 1 in identical mode, estimate the aberration of the film of preparation like this.The result is set forth in the table 2.
As can be seen, the distribution of Re and Rth is pre-determined in institute of the present invention restricted portion in the superincumbent table 2, might obtain to have the display device of very little aberration.
Embodiment 3
With the potassium hydroxide solution of 1.0N (solvent: water/isopropyl alcohol/propylene glycol=69.2 mass parts/15 mass parts/15.8 mass parts) in the belt side with 10cc/m
2Speed be coated in embodiment 1 on the film of preparation.Coated film was kept 30 seconds down at about 40 ℃.Wipe alkaline solution from this coated film.Wash this coated film with pure water.Leave water droplet on the coated film with the air of air doctor then.After this, this coated film is following dry 15 seconds at 100 ℃.Measure the film of processing like this and the contact angle of pure water then.The result is 42 °.
(preparation of alignment film)
Use #16 line rod spreader, with 28ml/m
2The speed alignment film coating solution that will have a following prescription be coated among the film No.1-3 each.Then with each coated film of hot-air dry of 60 ℃ 60 seconds then with 90 ℃ hot-air to preparing alignment film in its dry 150 seconds.
Modified polyvinylalcohol
Gan Zao alignment film has the thickness of 1.1 μ m like this.Measure the surfaceness of the alignment film that forms so then by atomic force microscope (AFM:Atomic Force Microscope, SPI3800N are produced by Seiko Instruments Inc.).The result is 1.147nm.
(formation of optical anisotropic layer)
Use the #2.8 line rod of the direction identical, will contain on the film that the speed with 20m/min that coating solution that discotic mesogenic has following prescription is coated in the alignment film side continuously transports with 391rpm rotation with the carriage direction of film.
Disc liquid-crystal compounds
Be heated to 100 ℃ step continuously from room temperature, dry this film desolvates to remove.After this in 130 ℃ dry section, be that the mode of 2.5m/sec heats this film and made the disc liquid-crystal compounds orientation in 90 seconds with the wind speed on the disc liquid-crystal compounds laminar surface.Next (uviol lamp: output: 120W/cm) this film of Fa She ultraviolet radiation made the surface temperature of film be about 130 ℃ in 4 seconds simultaneously and makes crosslinked carrying out, thereby the disc liquid-crystal compounds orientation is fixed to use actinolyte.After this, with this film cool to room temperature, and it is rolled into cylindricality forms volume.The optical compensation films that like this, has just prepared rolling.
The angle on the disk-like surface of disc liquid-crystal compounds and transparent polymeric film surface is 0 degree.
Measure by film No.1 the film No.33 of 2 and 3 preparations, 35 and 31 optical property then respectively.The results are shown in the table 3.
This Polarizer is placed in the Nicol crossed, observes the homogeneity of the optical compensation films that obtains like this.The result is, and is inhomogeneous when not finding from the front and these optical compensation films of direction observation of 60 ° of tilted off surface normal the time.
In the mode identical, in these films each is installed in estimates aberration in the liquid crystal indicator with embodiment 1.The result is presented in the following table 3.
Effect of the present invention can be brought into play significantly having on the film of optical anisotropic layer.
Embodiment 4
[preparation (film 25)] with diaphragm of antireflection property
(preparation of light scattering layer coating solution)
Potpourri (PETA, by NIPPON KAYAKU CO., LTD. produces) with 38.5g dilution with toluene 50g three acrylic acid pentaerythrites and tetraacrylate and pentaerythrite.In addition, heating 2g polymerization initiator (Irgacure 184, and by Ciba Specialty ChemicalsCo., Ltd. produces) in this solution.Stir this potpourri then.The solution that coating obtains like this, carrying out ultraviolet curing then, to obtain refractive index be 1.51 coating.
Then, adding 1.7g in this solution is the particle crosslinked polystyrene (refractive index: 1.60 of 3.5 μ m by mean grain size; SX-350 is by Soken Chemical﹠amp; Engineering Co., Ltd. production) process polytron dispersion machine is with 10,000rpm disperse 20 minutes formed 30% toluene suspension and 13.3g by mean grain size be 3.5 μ m particle crosslink propylene styrene (refractive index: 1.55, by Soken Chemical﹠amp; Engineering Co., Ltd. produces) 30% toluene suspension.At last, in this potpourri, add the solution that fluorine-based surface modifier of 0.75g (FP-1) and 10g silane coupling agent (KBM-5103, by Shin-Etsu Chemical Co., Ltd produces) obtain to finish.
Be that the polypropylene filter of 30 μ m filters said mixture and prepares the light scattering layer coating solution by the aperture then.
(preparation of low-index layer coating solution)
Prepare colloidal sol at first, in the following manner.Specifically, with 120 parts of methyl ethyl ketones, 100 parts of acryloyl-oxy propyl trimethoxy silicane (KBM-5103, by Shin-Etsu ChemicalCo., Ltd produces) and 3 parts of oacetic acid diisopropoxy aluminium pour in the reaction vessel that stirrer and reflux condensing tube have been installed and prepare potpourri.In this potpourri, add 30 parts of deionized waters then.This potpourri was reacted 4 hours down at 60 ℃, make its cool to room temperature obtain colloidal sol a then.The matter average molecular weight of this colloidal sol is 1,600.Molecular weight is 1,000-20, and the ratio of 000 composition in the oligomer composition is 100%.The gas chromatography demonstration of this colloidal sol does not stay raw material propylene acyl-oxygen propyl trimethoxy silicane.
By stirring, making the 13g refractive index is 1.42 hot crosslinkable fluoropolymer (JN-7228, solid content: 6%, by JSR Co., Ltd. produces), the 1.3g silica sol (silicon dioxide with the particle diameter that is different from MEK-ST; Mean grain size: 45nm; Solid content: 30%, by NISSAN CHEMICAL INDUSTRIES, LTD. produces), 0.6g is the colloidal sol of preparation like this, and 5g methyl ethyl ketone and 0.6g cyclohexanone mix.Be that the polypropylene filter of 1 μ m filters this solution and prepares the low-index layer coating solution by the aperture then.
(preparation) with transparent protective film of anti-reflection layer
Using the diameter with 180 line/inches is nick version print roller and the scraper of 40 μ m as the 50mm and the degree of depth, and it is that 30rpm and travelling speed are that the thickness that the roller of 30m/min unclamps is the tri acetyl cellulose membrane of 80 μ m that the above-mentioned coating solution that is used for functional layer (light scattering layer) is coated in from the intaglio printing rotational speed.With this coated film 60 ℃ dry 150 seconds down, air by the atmosphere of nitrogen purge in, using from output rating is that the air cool metal halide lamp (by EYE GRAPHICS CO., LTD. produces) of 160W/cm is with 400mW/cm
2Illuminance and 250mJ/cm
2The ultraviolet ray that dosage is emitted is carried out radiation to it, and making coating be cured and forming thickness is the functional membrane of 6 μ m.Then this film is rolled.
Using the diameter with 180 line/inches is nick version print roller and the scraper of 40 μ m as the 50mm and the degree of depth, and it is that 30rpm and travelling speed are the tri acetyl cellulose membrane with this functional layer (diffusion layer) that the roller of 15m/min unclamps that the coating solution that is used for low-index layer of preparation like this is coated in from the intaglio printing rotational speed.With this coated film 120 ℃ dry 150 seconds down, then 140 ℃ dry 8 minutes down.Air by the atmosphere of nitrogen purge in, using from output rating is that the air cool metal halide lamp (by EYE GRAPHICSCO., LTD. produce) of 240W/cm is with 400mW/cm
2Illuminance and 900mJ/cm
2The ultraviolet ray that dosage is emitted is carried out radiation to this film, forms the low-index layer that thickness is 100nm.Then this film is rolled and prepare diaphragm (film 25) with antireflection property.
[diaphragm 26] with antireflection property
(preparation of hard coating solution)
To 750.0 mass parts trimethylolpropane triacrylate (TMPTA, by NIPPONKAYAKU CO., LTD. adding 270.0 mass parts matter average molecular weights production) is 3,000-7,000 poly-(glycidyl methacrylate), 730.0g methyl ethyl ketone, 500.0g cyclohexanone and 50.0g Photoepolymerizationinitiater initiater (Irgacure 184, produced by Ciba Geigy Japan Inc.).Stir this potpourri.Be that the polypropylene filter of 0.4 μ m filters this potpourri and prepares hard coating solution with the aperture then.
(preparation of particulate titanium dioxide suspending liquid)
As particulate titanium dioxide, the particulate titanium dioxide (MPT-129, by ISHIHARA SANGYOKAISHA, LTD. produces) that is contained cobalt by aluminium hydroxide and zirconium hydroxide surface-treated that here uses.
In the 27.1g particulate titanium dioxide, add spreading agent and 704.3g cyclohexanone below the 38.6g then.Use dinomill to disperse this potpourri to prepare the suspending liquid of the equal particle diameter of matter then as the titanium dioxide granule of 70nm.
(preparation of middle index layer coating solution)
In the above-mentioned titanium dioxide granule suspending liquid of 88.9g, the potpourri (DPHA) that adds 58.4g five acrylic acid dipentaerythritol ester and six acrylic acid dipentaerythritol ester, 3.1g Photoepolymerizationinitiater initiater (Irgacure 907), 1.1g photosensitizer (Kayacure DETX, by NIPPONKAYAKU CO., LTD. produce), 482.4g methyl ethyl ketone and 1,869.8g cyclohexanone.Stir this potpourri then.Fully stir this potpourri, then with the aperture be the polypropylene filter of 0.4 μ m filter this potpourri prepare in the index layer coating solution.
(preparation of high refractive index layer coating solution)
In the above-mentioned titanium dioxide granule suspending liquid of 586.8g, the potpourri (DPHA) that adds 47.9g five acrylic acid dipentaerythritol ester and six acrylic acid dipentaerythritol ester, 4.0g Photoepolymerizationinitiater initiater (Irgacure 907), 1.3g photosensitizer (Kayacure DETX, by NIPPONKAYAKU CO., LTD. produce), 455.8g methyl ethyl ketone and 1,427.8g cyclohexanone.Stir this potpourri then.Fully stirring this potpourri, is that the polypropylene filter of 0.4 μ m filters this potpourri and prepares the high refractive index layer coating solution with the aperture then.
(preparation of low-index layer coating solution)
The multipolymer (P-1) that will have following array structure is dissolved in the methyl isobutyl ketone, makes its concentration reach 7 quality %.Then respectively with amount based on solid content 3 quality % and 5 quality %, in this solution, add the silicones X-22-164C of methacrylate end-blocking (by Shin-EtsuChemical Co., Ltd. produce) and optical free radical generation body Irgacure 907 (trade names), prepare low-index layer.
Multipolymer (P-1)
(ratio 50: 50th is in mol's)
(preparation) with transparent protective film of anti-reflection layer
Use nick version printing spreader, hard coating solution is coated in (Fujitack TD80U, by Fuji Photo Film Co., Ltd. produces) on the tri acetyl cellulose membrane that thickness is 80 μ m.With this coated film 100 ℃ down dry, reached by nitrogen purge in the atmosphere of oxygen content of 1.0vol% at air then, using from output rating is that the air cool metal halide lamp (by EYE GRAPHICS CO., LTD. produces) of 160W/cm is with 400mW/cm
2Illuminance and 300mJ/cm
2The ultraviolet ray that dosage is emitted is carried out radiation to it, and making coating be cured and forming thickness is the hard conating of 8 μ m.
Use has the intaglio printing spreader of three coating stations continuously with middle index layer coating solution, and high refractive index layer coating solution and low-index layer coating solution are coated on this hard conating.
The drying condition of middle index layer is 100 ℃ and 2 minutes.About the ultraviolet curing condition, make oxygen concentration reach 1.0vol% with the air in this atmosphere of nitrogen purge.In this atmosphere, ultraviolet ray is to be that the air cool metal halide lamp (by EYEGRAPHICS CO., LTD. produce) of 180W/cm is with 400mW/cm by output rating
2Illuminance and 300mJ/cm
2Dosage is emitted.The middle index layer of Gu Huaing has 1.630 refractive index and the thickness of 67nm like this.
Next the drying condition of high refractive index layer and low-index layer is 90 ℃ and 1 minute is 100 ℃ and 1 minute.About the ultraviolet curing condition, make oxygen concentration reach 1.0vol% with the air in this atmosphere of nitrogen purge.In this atmosphere, ultraviolet ray is to be that the air cool metal halide lamp (by EYE GRAPHICS CO., LTD. produce) of 240W/cm is with 600mW/cm by output rating
2Illuminance and 600mJ/cm
2Dosage is emitted.
The high refractive index layer of Gu Huaing has the thickness of 1.905 refractive index and 107nm and the low-index layer that solidifies like this has 1.440 refractive index and the thickness of 85nm like this.Like this, just prepared transparent protective film (film 26) with anti-reflection layer.
Except replace TD80U with above-mentioned film 25 and 26, carry out the Polarizer preparation method of embodiment 1.Estimate in these samples the aberration of each then in the mode identical with embodiment 1.
Even on diaphragm, also can bring into play effect of the present invention significantly with hard conating and anti-reflection layer.
(formation of cellulose acylate film)
(1) acylated cellulose
In as the cellulose of raw material, add sulfuric acid as catalyzer.In this potpourri, add carboxylic acid anhydrides then and cause acetylization reaction as the starting material of acyl substituent.After this, this reaction product is neutralized, saponification and slaking prepare acylated cellulose.In this program, suitably adjust the amount of catalyzer, the kind of carboxylic acid anhydrides and amount, the addition of neutralization reagent, the addition of water, temperature of reaction and curing temperature prepare and have different types of acyl group, degree of substitution, the acylated cellulose of the bulk specific gravity and the degree of polymerization.
In the acylated cellulose of like this preparation, degree of substitution be 2.79 and DS6/ (DS2+DS3+DS6) be 0.332 those be used to prepare dope with following prescription.
(2) preparation of dope
＜1-1〉the acylated cellobiose cellulose solution
Following ingredients being poured in the mixing channel, there they are stirred then and prepared the solution that is heated to 90 ℃ in 10 minutes, is that the filter paper of 34 μ m and sintered metal filter that average pore size is 10 μ m come they are filtered with average pore size then.
＜1-2〉matting agent suspending liquid
Next, the following composition that contains the acylated cellobiose cellulose solution of preparation is like this poured into and prepared matting agent suspending liquid in the decollator.
＜1-3〉delay developping agent (retardation developer) solution
Next, the following composition that contains the acylated cellobiose cellulose solution of preparation is in the above poured in the mixing channel, heated the solution for preparing as postponing the developping agent solution A here while stir then.
With the above-mentioned acylated cellobiose cellulose solution of 100 mass parts, 1.35 mass parts matting agent suspending liquid and the amount of the feasible developping agent A of delay in this cellulose acylate film are that the delay developping agent solution of the amount of 4.5 mass parts mixes, and prepare the film forming dope.
Postpone developping agent A
(curtain coating)
Use the glass sheet casting device to come the above-mentioned dope of curtain coating.Be the dope 6 minutes of 70 ℃ the such curtain coating of hot-air dry with temperature, then it peeled off from glass sheet.The film that will form like this is fixed on the frame then.With temperature is this film of hot-air dry 10 minutes of 100 ℃, is that 140 ℃ hot-air dry prepared the cellulose acylate film that thickness is 100 μ m in 20 minutes with temperature then.
Then in table 5 under the listed condition on its four limits by biaxial stretch-formed device (by ToyoSeiki Seisaku-Sho, Ltd. produces) when clamping, make the film of such acquisition stretched and shrink.Stretching and contraction are under general condition carried out.Specifically, before these steps in each embodiment this film of preheating 2 minutes under the air supply temperature of appointment.After this, under identical air supply temperature at stretch this film and of TD direction at lax this film of MD direction.After these steps finish, when this film is clamped by clip, come its cooling 5 minutes with moving air.MD in the table shows the curtain coating direction in the process of curtain coating on glass sheet.TD represents the horizontal direction perpendicular to MD.The film that obtains like this is used separately as film 51-55.
＜wavelength is at 450nm, the Re and the Rth of 550nm and 650nm place film 〉
Use KOBRA 21ADH (by Ouji ScientificInstruments Co., Ltd. produces) by method described above, at 450nm, the Re and the Rth of each film in these films measure in the wavelength place of 550nm and 650nm.
The results are shown in the table 4.Can from following table 4, find out, by the preparation method who comprises stretching step and collapse step can realize Re variation factor of the present invention be 5% or still less and the Rth variation factor be 10% or still less cellulose acylate film.In addition clearly, be the relational expression (A) of requirement of the present invention-(D) be satisfied.
Table 4
| Film No. | The % draw ratio | The % contraction factor | The S/S temperature *1 | The acetyl degree of substitution | The propionyl degree of substitution | The butyryl degree of substitution | Rc (450) | Re (550) | Re (650) | Rth (450) | Rth (550) | Rth (650) |
| 51 | 33 | 10 | 175 | 2.83 | 0 | 0 | 29 | 45 | 61 | 177 | 165 | 158 |
| 52 | 33 | - | 175 | 2.83 | 0 | 0 | 40 | 44 | 50 | 168 | 160 | 157 |
| 53 | - | 10 | 175 | 2.83 | 0 | 0 | 38 | 40 | 42 | 164 | 159 | 153 |
| 54 | 33 | 10 | 165 | 1.9 | 0.8 | 0 | 34 | 50 | 64 | 180 | 170 | 160 |
| 55 | 33 | 10 | 145 | 2 | 0 | 0.7 | 36 | 51 | 67 | 183 | 172 | 162 |
*1: contraction/shrinkage temperature
*The 2:Re variation factor
*The 3:Rth variation factor
(continuing)
| Film No. | (A) | (B) | (C) | (D) | Re v.c. *2 | Rth v.c. *3 | Remarks |
| 51 | 0.64 | 1.36 | 0.60 | 1.42 | 3.8 | 7.6 | Invention |
| 52 | 0.91 | 1.14 | 0.87 | 1.16 | 6.3 | 14.5 | Contrast |
| 53 | 0.95 | 1.05 | 0.92 | 1.09 | 7.8 | 13.5 | Contrast |
| 54 | 0.68 | 1.28 | 0.64 | 1.36 | 3.5 | 5.5 | Invention |
| 55 | 0.71 | 1.31 | 0.66 | 1.39 | 3.6 | 5.7 | Invention |
Embodiment 6
With 10cc/m
2Speed with the potassium hydroxide solution of 1.0N (solvent: water/isopropyl alcohol/propylene glycol=69.2 mass parts/15 mass parts/15.8 mass parts) be coated on the cellulose acylate film 51-55 of preparation in embodiment 5, then it kept 30 seconds down at about 40 ℃.After this, wipe alkaline solution from this coated film.Wash this coated film with pure water.Blow away water droplet on the coated film with the air of air doctor then.After this, this coated film is following dry 18 seconds at 100 ℃.
Measure this film then by the contact angle of the surface of alkali treatment and pure water.The result is 40 °.
(preparation of alignment film)
Use #16 line rod spreader, with 28ml/m
2The speed alignment film coating solution that will have a following prescription be coated in this film by on the surface of alkali treatment.Use this coated film of hot-air dry 60 seconds of 60 ℃ then, then with 90 ℃ hot-air to forming alignment film in its dry 150 seconds.
Modified polyvinylalcohol
(friction)
In order to the friction roller of 650rpm rotation (diameter: 300mm) transport with the speed of 20m/min in, the alignment film surface of the transparent support thing that formed alignment film on it is rubbed.Friction roller is arranged feasible friction to carry out to depart from the y direction 45.The contact length of friction roller and transparent support thing is 18mm.
(formation of optical anisotropic layer)
Make the disc liquid-crystal compounds below the 35.03kg, 4.35kg the trimethylolpropane acrylates (V#360 of oxirane modification, produce by OSAKA ORGANIC CHEMICALINDUSTRY LTD.), 0.35kg cellulose acetate-butyrate (CAB531-1, by Eastman Chemical Co., Ltd.), 1.31kg (Irgacure 907 for Photoepolymerizationinitiater initiater, produce by Ciba Geigy Inc.) and 0.47kg sensitizer (Kayacure DETX, by NIPPONKAYAKU CO., LTD. produces) be dissolved in the 102kg methyl ethyl ketone.(Megafac F780 by DAINIPPONINK AND CHEMICALS, INCORPORATED) prepares coating solution to add the fluorine-containing aliphatic group multipolymer of 0.1kg in the solution of such preparation.Use the #3.2 line rod of the direction identical, the coating solution for preparing like this is coated on the film alignment film film surface of transporting with the speed of 20m/min continuously with the 391rpm rotation with the carriage direction of film.
Disc liquid-crystal compounds
This film is heated to 100 ℃ so that solvent is removed fully continuously from room temperature.After this, dry this film is 90 seconds in 130 ℃ dry section, makes wind speed on the disc liquid-crystal compounds laminar surface reach 2.5m/sec and makes this disc liquid-crystal compounds orientation.Next, this film is transported to uses ultraviolet radiator (uviol lamp: output: 160W/cm in 80 ℃ the dry section then there; Emission wavelength: 1.6m) Fa She illuminance is that this film of 600Mwd ultraviolet ray irradiation makes the surface temperature of this film be maintained at about 100 ℃, so that carry out cross-linking reaction the disc liquid-crystal compounds orientation is fixed.After this, with this film cool to room temperature and it is rolled form volume there cylindrically.The optical compensation films that like this, has just prepared rolling.
Under 127 ℃ film surface temperature, measure the viscosity of this optical anisotropic layer then.The result is 695cp.For the measurement of the viscosity of optical anisotropic layer, measure the liquid crystal layer (not comprising solvent) that has same recipe with optical anisotropic layer by the E type viscosity apparatus of heating.
The optical compensation films of rolling of preparation so partly cut prepare the sample that is used to measure optical property.The length of delay of the optical anisotropic layer of measuring at the wavelength place of 546nm is 35nm.The angle on the surface of the disk-like surface of disc liquid-crystal compounds and stilt (pitch angle) has shown 28 ° of continuous variation on this layer depth direction and average out in optical anisotropic layer.In addition, from this sample, only this optical anisotropic layer is stripped down.Measure the mean direction of the molecule axis of symmetry of the optical anisotropic layer of peeling off so then.The result is that the mean direction of molecule axis of symmetry vertically is 45 ° with respect to this optical compensation films.
(the installation evaluation on the OCB panel)
In the mode identical these cellulose acylate film samples are processed into Polarizer with embodiment 1.
Installation evaluation on the＜liquid crystal indicator 〉
(preparation of the liquid crystal cell of bend alignment)
Polyimide is provided in to have on the glass basis of ITO electrode as alignment film.This alignment film is rubbed.With two glass basiss that obtain like this so that the arrangement that this frictional direction of two is parallel to each other is laminated mutually.It is 4.7 μ m that the element gap is pre-determined.In this element gap, inject Δ n then and be the liquid crystal cell that 0.1396 liquid-crystal compounds " ZLI1132 " (by Melc Co., Ltd. produces) prepares bend alignment.
With two in the above the preparation Polarizers laminated mutually, wherein with above-mentioned bend alignment element between between them.Arrange and make that the film that forms like this is opposite with element body, and make the frictional direction of liquid crystal cell and be not parallel to each other with respect to the frictional direction of other optical anisotropic layer of this liquid crystal cell.
This liquid crystal cell is applied the rectangular voltage of 55Hz.This liquid crystal cell has by dialogue demonstration 2V with to the black white mode that shows the routine that 5V reached.By apply make before the voltage of transmission minimum, for example, black voltage has been determined the observed in front color of showing, and on the polar angle direction of 0 °-90 ° position angle and 60 ° with the observed aberration Δ x that shows of field-of-view angle.The results are shown in the following table 5.These results represent according to following grade.Aberration (Δ x :) in black procedure for displaying azimuthal maximal value of 0 °-90 °
E: be less than 0.02
G：0.02-0.04
F：0.04-0.06
P:0.06 or more
As can be seen, the use of film of the present invention makes to obtain the having high fidelity liquid crystal indicator that little aberration changes in Fig. 5.
The present invention is based on that inventor's the knowledge that further investigation obtained makes.In the present invention, suitably select material and production method to control the interior delay of face of optical resin film and the wavelength dispersion of thickness direction retardation independently of each other.Can determine the best optical value of optical resin film like this, allow the field-of-view angle compensation under black state in whole wavelength coverage of liquid crystal cell, especially VA pattern.The result is that liquid crystal indicator of the present invention is subjected to the influence of light leak at vergence direction in black procedure for displaying, thereby has shown the field-of-view angle contrast that significantly improves.In addition, liquid crystal indicator of the present invention can suppress the light leak on the black procedure for displaying medium dip direction basically in visible wavelength range, thereby show the very big reduction that depends on the aberration of field-of-view angle in black procedure for displaying, this is a problem to be solved up to now.Correspondingly, the present invention can be provided at the optical resin film that shows high-contrast on the wide region and can suppress aberration, and the Polarizer and the liquid crystal indicator that comprise this optical resin film.
At this, with having required whole disclosures of each foreign patent application of external right of priority to be incorporated herein by reference in this application, just as it is set forth in full at this.
Claims (8)
1, a kind of optical resin film, it has and satisfy to postpone requires (A)-(D)
Re (λ) And Rth (λ), and have 5% or face insied width direction still less postpone (Re) variation factor and 10% or thickness direction retardation still less (Rth) variation factor:
(A)0.1＜Re(450)/Re(550)＜0.95
(B)1.03＜Re(650)/Re(550)＜1.93
(C)0.4＜(Re/Rth(450))/(Re/Rth(550))＜0.95
(D)1.05＜(Re/Rth(650))/(Re/Rth(550))＜1.9
Wherein, Re (λ) expression is the light of λ nm for wavelength, the face insied width length of delay of this optical resin film;
Rth (λ) expression is the light of λ nm for wavelength, the length of delay of this optical resin film thickness direction; And
Re/Rth (λ) expression is the light of λ nm for wavelength, the face insied width length of delay of this optical resin film and the ratio of thickness direction retardation value.
2, optical resin film according to claim 1, it comprises cellulose acylate film.
3, optical resin film according to claim 1, it comprises and is selected from by plastifier, ultraviolet light absorber, peels off at least a in the group that promoter, dyestuff and matting agent form.
4, optical resin film according to claim 1, it comprises at least a delay developping agent that comprises bar-shaped compound or discotic compound.
5, a kind of Polarizer, it comprises:
Polarizer with polyvinyl alcohol (PVA); With
Be provided on these polarizer both sides
At least two diaphragms,
Wherein at least one is an optical resin film according to claim 1 in these at least two diaphragms.
6, Polarizer according to claim 5, it further comprises and is provided in described two diaphragms lip-deep at least one layer that is selected from the group that is made of hard conating, antiglare layer and anti-reflection layer of film at least.
7, Polarizer according to claim 5, it further comprises and is provided in the optical anisotropic layer at least one film in described at least two diaphragms.
8, a kind of liquid crystal indicator that comprises Polarizer according to claim 5.
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|---|---|---|---|
| JP236753/2005 | 2005-08-17 | ||
| JP2005236753 | 2005-08-17 | ||
| JP066459/2006 | 2006-03-10 |
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| CN100590458C true CN100590458C (en) | 2010-02-17 |
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| JP4888853B2 (en) | 2009-11-12 | 2012-02-29 | 学校法人慶應義塾 | Method for improving visibility of liquid crystal display device, and liquid crystal display device using the same |
| CN102906604B (en) * | 2010-05-28 | 2016-04-27 | 3M创新有限公司 | Light-redirecting film and the display system comprising light-redirecting film |
| US9798189B2 (en) * | 2010-06-22 | 2017-10-24 | Toyobo Co., Ltd. | Liquid crystal display device, polarizer and protective film |
| JP5879157B2 (en) * | 2011-03-07 | 2016-03-08 | 富士フイルム株式会社 | Optical film, laminate, retardation film, polarizing plate and optical film manufacturing method |
| TWI542907B (en) | 2011-05-18 | 2016-07-21 | 東洋紡績股份有限公司 | Liquid crystal device, polarizing plate and polarizer protection film |
| US10175494B2 (en) | 2011-05-18 | 2019-01-08 | Toyobo Co., Ltd. | Polarizing plate suitable for liquid crystal display device capable of displaying three-dimensional images, and liquid crystal display device |
| CN108845451B (en) * | 2012-07-30 | 2021-12-10 | 东洋纺株式会社 | Liquid crystal display device, polarizing plate and polarizer protective film |
| JP6076035B2 (en) * | 2012-10-26 | 2017-02-08 | 住友化学株式会社 | Method for producing polarizing laminated film and method for producing polarizing plate |
| WO2014175312A1 (en) * | 2013-04-26 | 2014-10-30 | 富士フイルム株式会社 | Transfer material, substrate with transfer layer, touch panel, manufacturing methods therefor, and information display device |
| CN112484905B (en) * | 2020-12-04 | 2022-03-29 | 中国航空工业集团公司北京长城计量测试技术研究所 | High-precision pressure optical measurement method in variable temperature environment |
| CN114648532B (en) * | 2022-05-23 | 2022-08-23 | 河南银金达新材料股份有限公司 | Polyester film mechanical property detection device based on optical recognition |
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