KR101878776B1

KR101878776B1 - Liquid crystal display including cellulose ester phase difference film

Info

Publication number: KR101878776B1
Application number: KR1020150101941A
Authority: KR
Inventors: 김영수; 김경수; 김용원; 하선영; 이유미; 이호준; 강혁모
Original assignee: 주식회사 효성
Priority date: 2015-07-17
Filing date: 2015-07-17
Publication date: 2018-07-16
Also published as: KR20170009614A

Abstract

The present invention relates to a polarizing plate comprising a cellulose ester film, and more particularly, to a polarizing plate having improved reliability by including a resin capable of improving high temperature and high humidity reliability and an additive.

Description

[0001] The present invention relates to a liquid crystal display device including a cellulose ester film,

The present invention relates to a liquid crystal display device including a cellulose ester film, and more particularly, to a vertically aligned liquid crystal display device having improved reliability by including a resin capable of improving high temperature and high humidity reliability and an additive.

In recent years, the development of thin and lightweight notebook computers is under way. Accordingly, a protective film of a polarizing plate used in a display device such as a liquid crystal display device has been increasingly demanded for further thinning and higher performance. Since a liquid crystal display device displays a display by polarization control by a liquid crystal, a polarizing plate is required, and a polarizing plate in which a PVA film containing iodine is stretched is usually used. Since the polarizing plate is fragile, a polarizing plate protective film is used to protect the polarizing plate. In general, triacetylcellulose film is widely used for a polarizing plate protective film. In addition to these polarizing plate protective films, a retardation film is also used to control the retardation of the polarized light. These used a retardation film in a liquid crystal display device or the like may be used in order to solve the problems such as color compensation and wide viewing angle by using the phase difference (R _τη) in the thickness direction by the use in combination with a polarizing plate, and the phase difference in-plane direction (R _ο) May have a function of converting linearly polarized light into circularly polarized light with respect to the wavelength of the visible light region or conversely converting circularly polarized light into linearly polarized light.

The polarizing plate protective film is intended to protect the polarizing plate and it is most preferable to use a film made of cellulose acetate in order to protect the polarizing plate made of PVA containing moisture, considering the production process of the polarizing plate. On the other hand, as a retardation film, materials other than cellulose acetate have been used to exhibit optical performance. That is, conventionally, as a material of the retardation film, for example, there are polycarbonate, polysulfone, polyethersulfone, amorphous polyolefin and the like. These polymer films have such characteristics that the longer the wavelength is, the smaller the retardation, and it is difficult to impart an ideal retardation property to the entire wavelength of the visible light region.

In the case where linearly polarized light is converted into circularly polarized light with respect to the wavelength of the visible light region or conversely circularly polarized light is converted into linearly polarized light, in order to obtain the above effect with one piece of retardation film, the retardation in the wavelength? 4 < / RTI > Such a retardation film can be obtained by using, for example, a retardation film having a phase difference of? / 4 and only one polarizing plate for a reflective liquid crystal display device having a back electrode as a reflective electrode, thereby obtaining a reflective display device having excellent image quality . Further, with respect to the observer of the guest-host type liquid crystal layer, the retardation film is used on the back side, or the circularly polarized light of the reflection type polarizing plate composed of cholesteric liquid crystal or the like that reflects only one of the left and right circularly polarized light is converted into linearly polarized light It is also used as an element.

Further, the retardation film has a function of converting linearly polarized light into elliptically polarized light or circularly polarized light, or converting linearly polarized light in a certain direction into another direction, and therefore, the viewing angle, contrast, etc. of the liquid crystal display device can be improved .

Generally, a retardation film is attached to a pair of polarizing plates, respectively. At present, N-TAC of Konica Minolta Holdings, Inc. of Japan is generally used as a phase difference film for a VA mode liquid crystal display. The NTAC phase difference film was a cellulose acetate propionylate (CAP) having a retardation in the plane of 50 nm (in terms of retardation (R ₀ , λ = 550 nm) and a retardation in the thickness direction (R _υθ , ) Film.

In order to improve the viewing angle characteristics (black display state (black characteristic), etc.) of the liquid crystal display device, wavelength dispersion and control techniques are required. In general, the N-TAC film exhibits an inverse wavelength dispersion characteristic in which the retardation value increases with increasing wavelength, and exhibits an excellent viewing angle characteristic improvement effect as compared with the retardation film having a regular wavelength dispersion characteristic in which the retardation value decreases with increasing wavelength. Further, in order to improve a liquid crystal display device, a retardation film having a specific retardation value and a combination thereof are used.

Conventional retardation films (PC, PSu, PA, etc.) have such characteristics that the longer the wavelength is, the smaller the retardation. It is difficult to impart an ideal retardation characteristic to the entire wavelength of the visible light region. So that necessary performance is obtained. Order in one piece of the retardation film to obtain the same performance as that, at a wavelength (λ) incident on the retardation film in-plane retardation (R _ο) is preferably a λ / 4 but, for him and the characteristics of the opposite The longer the wavelength, the more the in-plane directional phase difference (R _ο ) becomes larger. In the film made of cellulose acetate, if such a retardation property can be given, the polarizing plate protective film and the retardation film can be used together, the retardation film composed of a plurality of retardation films can be omitted, It is possible to improve the total light transmittance.

With respect to this problem, Japanese Patent Laid-Open No. 2000-137116 proposes to use an oriented film of cellulose acetate having a degree of substitution (acetylation degree) of 2.5 to 2.8 as a retardation film. According to this method, the longer the wavelength, the larger the phase difference, and the ideal phase difference characteristic is obtained with respect to the entire wavelength of the visible light region. That is, the above-mentioned patent discloses a phase difference plate in which the phase difference becomes smaller as the measurement wavelength becomes shorter with one film. A retardation film comprising a polymeric orientation film having a longer birefringence (? N) at a wavelength of 400 to 700 nm, wherein the polymeric orientation film is an orientation film of a polymeric film having an average refractive index at the above- And the like. As a means for solving this problem, a technique of orienting cellulose acetate having an acetylation degree of 2.5 to 2.8 by stretching is disclosed.

In the embodiment of the above-mentioned patent, 100 parts by weight of cellulose triacetate having an intrinsic viscosity [?] = 1.335 and an acetylation degree of 2.917 obtained from Wako Junyaku Kogyo Co., Ltd. was dissolved in 500 parts by weight of methylene chloride, Hydrolysis of cellulose triacetate with acetic acid and water at 70 DEG C for 100 minutes while removing methylene chloride by depressurization and the reaction product was precipitated with a large amount of water and washed and dried , And a cellulose acetate having an acetylation degree of 2.661 was obtained. Then, a film was prepared from a solution prepared by dissolving 100 parts by weight of this polymer and 3 parts by weight of dibutyl phthalate as a plasticizer in 700 parts by weight of a mixed solvent of methylene chloride / methanol (weight ratio 9/1) by solvent casting method, And uniaxially stretched at a temperature of 170 캜 at 1.5 times. That is, in Embodiment 1 of the patent, the retardation film having the same wavelength characteristics (wavelength dispersion characteristics) as the latter is obtained by stretching. It is also disclosed that by adjusting the retardation value, it is possible to use? / 4 or another retardation film. In Example 4 of the aforementioned patent, cellulose acetate having an acetylation degree of 2.421 was obtained. When the retardation property of the film using the film is measured, the retardation is insufficient when the film thickness is about 100 mu m (50 to 150 mu m) and when the film thickness is preferable as the self-supporting film. When the thickness of the film is as large as about 200 mu m, a preferable retardation of about 80 to 150 nm is provided. In this case, the thickness direction retardation ( _Rv [ _theta] ) is excessively larger than 350 nm, It did not function as an enlarged film and was not sufficient. Furthermore, the molecular weight distribution of the obtained cellulose acetate is not described, and the control of the retardation characteristics by controlling the molecular weight distribution is not described or suggested.

On the other hand, although the protective film of the polarizer PVA layer of the polarizing plate was produced by using materials such as TAC and acrylic, the raw materials added to the CAP, COP, and TAC at the time of manufacturing the retardation film are expensive, .

In addition, the cellulose-based polarizing plate made of the conventional retardation film has a low resistance to high temperature and high humidity environment, and the water resistance property of the film is deteriorated when exposed to a high temperature and high humidity reliability environment, thereby deteriorating the reliability quality of the polarizing plate and LCD.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a vertically aligned liquid crystal display device having reliability and improved quality by including a resin and an additive capable of improving high temperature and high humidity reliability .

According to an aspect of the present invention, there is provided a liquid crystal display device including: a liquid crystal panel;

A first protective film formed on the liquid crystal panel; A polarizer formed on the first protective film; And an upper polarizer including a second protective film formed on the polarizer; And

A first protective film formed under the liquid crystal panel; A polarizer formed on the first protective film; And a lower protective film formed on the polarizer,

When the contrast ratio is measured after being left at 60 DEG C and 90% RH for 500 hours, the change value before and after the leaving is within 20%.

It is preferable that the first protective film is a cellulose ester film having a range of cellulose ester represented by the following formula (1) and average unmodified hydroxyl group of the saccharide compound represented by the following formula (2) satisfying the following formula (1).

[Chemical Formula 1]

In the above formula (1), R is substituted with an acyl group (acetyl group, propionyl group, butyryl group), and unsubstituted R is left as a hydroxyl group.

(2)

In the above formula (2), R is substituted with benzoic acid or acetate, and unsubstituted R remains as a hydroxyl group.

[Equation 1]

R _SOH + A _SOH? 1.5 * R _SOH? 0.4

In the above formula (1), R _SOH is the degree of substitution of R, which is unsubstituted in formula (1) and remains as a hydroxyl group, and A _SOH is the degree of substitution of R which is unsubstituted and remains as a hydroxyl group in formula (2).

It is also preferable that the first protective film has a variation range of -0.001 to 0.001 before and after the P value expressed by the following formula (2) after being left at 60 DEG C and 90% RH for 500 hours.

&Quot; (2) "

P value = 1 - sin 2 (2?) * Sin 2 (? /? * Ro) * 100

-0.5 <

In the above equation (2),? Is the optical axis of the first protective film,? Is 550 nm as the reference wavelength of the measurement light, and Ro is the retardation in the plane direction when measured with 550 nm light.

The first protective film has a film thickness of 20 to 60 탆 and an in-plane retardation Ro defined by the following formula (3): 30 to 100 nm under the conditions of 23 캜 and 55% RH, and a retardation Rth It is preferably 100 to 300 nm under the conditions of 23 deg. C and 55% RH.

&Quot; (3) "

Ro = (nx-ny) xd

Rth = {(nx + ny) / 2-nz} xd

Nx is the maximum refractive index in the vertical direction in the film plane, and nz is the maximum refractive index in the thickness direction of the film, and is 23 DEG C, 55 DEG C, respectively, % RH under a wavelength of 550 nm.

The second protective film preferably has a thickness of 20 to 100 占 퐉 and a thickness of 60 to 160 占 퐉 sandwiched between the polarizer and the second protective film.

The upper polarizer and the lower polarizer are preferably allowed to stand at 60 DEG C and 90% RH for 500 hours, and then the degree of polarization of the polarizer expressed by Equation (4) is 99.95% or more.

&Quot; (4) "

Polarization degree (PE,%) = [(Tp-Tc) / (Tp + Tc)] ^1/2 x 100

In Equation (4), Tp is the transmittance of the polarizing plate in a state where the transmission axes thereof are parallel to each other, and Tc is the transmittance of the visible light range of 400 to 700 nm in an environment of 23 DEG C and 55% RH in an orthogonal state.

The present invention having such a constitution can improve the reliability quality of the liquid crystal display device with the cellulose ester film of the present invention by including the resin and the additive which can improve the high temperature and high humidity reliability.

1 is a schematic view showing a process for producing a cellulose ester film according to the present invention.
2 is a view schematically showing a polarizing plate according to the present invention.
3 is a view schematically showing a vertical alignment liquid crystal display device according to the present invention.

Hereinafter, the present invention will be described.

A liquid crystal display device according to the present invention includes: a liquid crystal panel;

A first protective film formed under the liquid crystal panel; A polarizer formed on the first protective film; And a second protective film formed on the polarizer.

At this time, the liquid crystal display device is characterized in that when the contrast ratio is measured after being left at 60 DEG C and 90% RH for 500 hours, the change value before and after being left standing is within 20%.

It is preferable that the first protective film is a cellulose ester film having a range of cellulose ester represented by the following formula (1) and an average unsubstituted hydroxyl group of the saccharide compound represented by the following formula (2) But is not limited thereto.

[Chemical Formula 1]

(2)

[Equation 1]

R _SOH + A _SOH? 1.5

R _SOH? 0.4

On the other hand, the first protective film, which is the cellulose ester film, can be produced by solution casting. In the solution film forming method, the cellulose ester is dissolved in an additive such as a plasticizer, a UV absorber, a matting agent, etc. and a mixed solvent such as methylene chloride and methanol to prepare a dope, which can be filtered using a filtration apparatus.

In the present invention, the molecular weight range of the cellulose ester is not limited, but the weight average molecular weight is preferably in the range of 150,000 to 220,000.

By reducing the molecular weight to a certain level or more, the strength of the film can be effectively prevented from being lowered.

Further, by keeping the molecular weight at a certain level or less, the viscosity of the cellulose ester solution (dope) is maintained at a certain level or less, thereby facilitating film production by solution casting method.

The degree of molecular weight dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the cellulose ester is preferably in the range of 2.5 to 4.5.

When a film is produced by a solution film forming method (or a solvent casting method), an organic solvent is preferable as the solvent for preparing the cellulose ester composition (dope). As the organic solvent, it is preferable to use halogenated hydrocarbons, and halogenated hydrocarbons include chlorinated hydrocarbons, methylene chloride and chloroform, among which methylene chloride is most preferred.

If necessary, organic solvents other than halogenated hydrocarbons may be mixed and used. Organic solvents other than halogenated hydrocarbons include esters, ketones, ethers, alcohols and hydrocarbons. Examples of the ester include methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acylate, ethyl acylate, and pentaacetate. Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, di Isobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone and the like can be used. As the ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, Ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-butanol and the like can be used. Methyl-2-butanol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol and 2,2,3,3-tetrafluoro-1-propanol.

More preferably, methylene chloride may be used as the main solvent, and alcohol may be used as the minor solvent. Specifically, methylene chloride and alcohol may be mixed at a weight ratio of 80:20 to 95: 5.

The cellulose ester composition can be prepared by room temperature, high temperature or low temperature dissolution.

Next, the additives used in the production of the cellulose ester film will be explained. The cellulose ester solution (dope) used in the solution softening method may contain various additives depending on the application in each preparation step such as a plasticizer, a deterioration inhibitor, a matte fine particle, a stripper, a UV stabilizer, an ultraviolet absorber, An additive such as a dispersing agent, an optical anisotropy adjusting agent and the like may be added. The specific kind of such additives can be used without limitation as long as they are commonly used in the field, and the content thereof is preferably used within a range that does not deteriorate the physical properties of the film. The timing of adding the additives depends on the type of additive. A step of adding an additive to the end of the doping treatment may be performed.

In this case, it is preferable that the first protective film has a variation range of -0.001 to 0.001 before and after the P value expressed by the following formula (2) after being left at 60 DEG C and 90% RH for 500 hours.

&Quot; (2) "

P value = 1 - sin 2 (2?) * Sin 2 (? /? * Ro) * 100

-0.5 <

&Quot; (3) "

Ro = (nx-ny) xd

Rth = {(nx + ny) / 2-nz} xd

It is preferable that the first protective film has a film thickness of 60 to 160 μm sandwiched between polarizers, but the present invention is not limited thereto.

On the other hand, the cellulose ester film as the first protective film contains a plasticizer for improving mechanical strength, good castability, imparting water absorbency, and reducing water permeability. As the plasticizer, any conventionally used plasticizer can be used without limitation. For example, carboxylic acid esters selected from phosphoric acid esters, phthalic acid esters or citric acid esters and the like can be used. In the present invention, .

The cellulose ester solution thus obtained is cast on a support through a casting die to form a cellulose ester sheet.

The cellulose ester sheet thus formed is subjected to a stretching step in a tenter. In the preheating step, the glass transition temperature (Tg) of the cellulose ester flake is 185 to 200 ° C, the glass transition temperature (Tg) of the retardation film is 150 to 190 Lt; / RTI >

The cellulose ester film of the present invention may be completed in a drying process in a dryer after removing the left and right ends of a film whose surface is damaged by a clip or pin of a tenter after being subjected to a stretching step in a tenter under the above conditions.

On the other hand, the polarizer formed on the first protective film includes polyvinyl alcohol. The polyvinyl alcohol is preferably an iodine-impregnated body. It is preferable that the thickness of the polarizer is in the range of 3 to 30 占 퐉. When the thickness of the polarizer is in the above range, the polarizer can be efficiently used as a polarizing layer have.

In addition, the polarizing plate of the present invention comprises a second protective film.

It is preferable that the second protective film is formed on a polarizer and cellulose triacetate having a total degree of substitution of acetyl groups of 2.7 or more. At this time, the thickness of the second protective film is preferably 20 to 100 占 퐉, but is not limited thereto.

After the polarizer formed on the first protective film and the second protective film are disposed in contact with each other, a polarizing plate is completed. The polarizer may further include an adhesive layer between the polarizer and the second protective film to facilitate adhesion between the polarizer and the second protective film.

The polarizing plate of the present invention manufactured as described above has a polarization degree of 99.95% or more of the polarizing plate expressed by the following formula (4) after being left at 60 ° C and 90% RH for 500 hours.

&Quot; (4) "

Polarization degree (PE,%) = [(Tp-Tc) / (Tp + Tc)] ^1/2 x 100

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.

Manufacturing example 1-1: Preparation of first protective film

&Lt; Step 1 > Cellulose solution ( Lead juice )

A cellulose ester having an acetyl group degree of substitution of 2.03, a butyryl group degree of substitution of 0.25 and an acyl group total substitution degree of 2.28 and a degree of substitution (OH group) of 0.72 was used, and as a plasticizer, OH group, A _SOH ) was 0 was used to prepare a cellulose solution.

<Step 2> Preparation of Dilute Solution Containing Metal Oxide

20.0 parts by weight of the cellulose solution prepared in <Step 1>, 1.5 parts by weight of silica (SiO2), and 78.5 parts by weight of a mixed solvent obtained by mixing 9: 1 (by weight) of methylene chloride and methanol were added to a mixing tank, ) Was prepared. &Lt; tb > < TABLE >

&Lt; Step 3 > Preparation of cellulose ester film

100 parts by mass of the initiator solution and 5 parts by mass of the fine particle additive solution were added, and sufficiently mixed with an inline mixer to prepare a dope. At this time, the composition of the dope was 72 wt% of methylene chloride, 8 wt% of methanol, 17.95 wt% of cellulose ester, 2 wt% of plasticizer and 0.05 wt% of silica. Thereafter, the belt was softened uniformly on a stainless steel band support having a width of 2000 mm by using a flexible machine. Then, the solvent was evaporated on the stainless band support to peel off from the stainless band support. Then, both ends of the web were gripped with a tenter and stretched so that the stretching magnification in the (TD) direction was 1.3 times in the temperature environment of 170 DEG C, and then the stretching was maintained for a few seconds while maintaining the width, , And the film was transported for 35 minutes in a drying section set at 110 DEG C for drying for 35 minutes to produce a cellulose ester film having a thickness of 40 mu m and a knurling width of 1900 mm, a width of 10 mm at the end and a height of 8 mu m.

Manufacturing example 1-2: Preparation of first protective film

Except that a cellulose ester having an acetyl group degree of substitution of 2.03, a butyryl group degree of substitution of 0.51, an acyl group total degree of substitution of 2.54, and a degree of substitution (OH group) of 0.46 was used, To prepare a cellulose ester film.

Manufacturing example 1-3: Preparation of first protective film

Except that a cellulose ester having an acetyl group degree of substitution of 1.32, a butyryl group degree of substitution of 0.52, an acyl group total degree of substitution of 1.84, and a notch degree (OH group) of 1.16 was used, To prepare a cellulose ester film.

Manufacturing example 1-4: Preparation of first protective film

Was the same as that of Production Example 1-1, except that the acetyl group degree of substitution was 1.82, the propionyl group degree of substitution was 0.55, the acyl group total degree of substitution was 2.37, and the degree of substitution (OH group) was 0.63. Was carried out to prepare a cellulose ester film.

Manufacturing example 1-5: Preparation of first protective film

A cellulose ester film was produced in the same manner as in Preparation Example 1-1, except that a saccharide compound having a microchannel (OH group, A _SOH ) of 0.5 was used as a plasticizer.

Manufacturing example 1-6: Preparation of first protective film

A cellulose ester film was produced in the same manner as in Preparation Example 1-2, except that a saccharide compound having a microchannel (OH group, A _SOH ) of 0.5 was used as a plasticizer.

Manufacturing example 1-7: Preparation of first protective film

A cellulose ester film was produced in the same manner as in Preparation Example 1-4, except that a saccharide compound having a michiichi-turn degree (OH group, A _SOH ) of 0.5 was used as a plasticizer.

Manufacturing example 1-8: Preparation of first protective film

A cellulose ester film was produced in the same manner as in Preparation Example 1-2, except that a saccharide compound having a microchannel (OH group, A _SOH ) of 1.0 was used as a plasticizer.

Comparative Manufacturing Example 1-1

Was the same as that of Production Example 1-1, except that the acetyl group substitution degree was 2.61, the propionyl group substitution degree was 0.25, the acyl group total substitution degree was 2.86, and the degree of substitution (OH group) was 0.14 was used. Was carried out to prepare a cellulose ester film.

Comparative Manufacturing Example 1-2

A cellulose ester film was produced in the same manner as in Preparation Example 1-1, except that a saccharide compound having a michi-ring (OH group, A _SOH ) of 1.0 was used as a plasticizer.

Comparative Manufacturing Example 1-3

A cellulose ester film was produced in the same manner as in Preparation Example 1-3, except that a saccharide compound having a microchannel (OH group, A _SOH ) of 1.0 was used as a plasticizer.

Comparative Manufacturing Example 1-4

Was the same as that of Production Example 1-8, except that the acetyl group substitution degree was 2.61, the propionyl group substitution degree was 0.25, the acyl group total substitution degree was 2.86, and the degree of substitution (OH group) was 0.14 was used. Was carried out to prepare a cellulose ester film.

Experimental Example One

The optical characteristics of the cellulose ester films prepared in Production Examples 1-1 to 1-8 and Comparative Production Examples 1-1 to 1-4 were measured by the following methods, and the results are shown in Table 1 below.

Ro = (nx-ny) xd

Rt = ((nx + ny) / 2-nz) xd

Nx and ny represent refractive indices in the in-plane direction of the film, nz represent refractive indices in the thickness direction of the film, and nx, ny and nz represent refractive indices in the x, y and z directions of the refractive index ellipsoid, Gt; n, and d represents the thickness (nm) of the film.

The in-plane retardation value (Ro) and the retardation value (Rth) in the thickness direction were measured at 550 nm under an environment of 23 ° C and 55% RH using an optical measuring instrument of AxoScan (OPMF-1, Axometrics) The optical axis was measured with a measuring instrument.

The cellulose ester film prepared above was subjected to a reliability treatment for 500 hours in a high temperature and high humidity chamber under conditions of 60 ° C and 90% RH. Using the same measuring equipment, the retardation in the surface direction and the retardation in the thickness direction and the optical axis Respectively.

Dope type Before reliability After reliability P value fluctuation Total degree of substitution of cellulose ester Mitch's ratio of plasticizer Michihan Road
(OH group) Optical axis
(') Ro
(nm) Rth
(nm) P value Optical axis
(') Ro
(nm) Rth
(nm) P value Production Example 1-1 2.28 0.0 0.72 0.31 55.2 125.2 99.9989 0.37 52.1 137.2 99.9986 0.0003 Production Example 1-2 2.54 0.0 0.96 0.29 54.3 124.3 99.9990 0.39 52.2 136.3 99.9984 0.0006 Production Example 1-3 1.84 0.0 1.16 0.29 56.5 126.5 99.9990 0.39 54.1 138.5 99.9983 0.0007 Production Example 1-4 2.37 0.0 0.63 0.37 50.1 120.1 99.9987 0.45 47.2 132.1 99.9982 0.0004 Production Example 1-5 2.28 0.5 1.22 0.35 49.9 119.9 99.9988 0.42 47.7 131.9 99.9984 0.0004 Production Example 1-6 2.54 0.5 0.96 0.32 52.7 122.7 99.9989 0.42 50.4 134.7 99.9983 0.0006 Preparation Example 1-7 2.37 0.5 1.13 0.33 53.4 123.4 99.9988 0.43 50.2 135.4 99.9982 0.0006 Production Example 1-8 2.37 1.0 1.46 0.41 50.5 120.5 99.9983 0.48 48.1 132.5 99.9979 0.0004 Comparative Production Example 1-1 2.86 0.0 0.14 0.35 23.7 93.7 99.9997 0.49 19.8 110.7 99.9996 0.0001 Comparative Production Example 1-2 2.28 1.0 1.72 0.27 49.2 119.2 99.9993 0.54 42 136.2 99.9980 0.0013 Comparative Production Example 1-3 1.84 1.0 2.16 0.21 51.1 121.1 99.9996 0.49 42.9 138.1 99.9983 0.0013 Comparative Production Examples 1-4 2.86 1.0 1.14 0.41 24.6 94.6 99.9996 0.55 20.7 111.6 99.9995 0.0001

As can be seen from Table 1, when the plasticizer and the cellulose ester film proposed in the present invention were within the range of the degree of substitution of the unsubstituted OH group (Examples 1 to 8), the cellulose ester film before / after the reliability treatment of the cellulose ester film It was found that the P value variation characteristic of the film was excellent. In the case of Comparative Examples 1 and 4, the P value variation was excellent, but the retardation in the initial plane direction was 30 nm or less.

Manufacturing example 2: Preparation of second protective film

&Lt; Step 1 > Cellulose solution ( Lead juice )

16 parts by weight of triacetyl cellulose having an average degree of acetyl substitution (DS) of 2.86, 82 parts by weight of a mixed solvent obtained by mixing methylene chloride and methanol in a ratio of 9: 1 (weight ratio), triphenylphosphate (TPP) And 2 parts by weight of a plasticizer mixed with ethyl glycolate (EPEG) at a ratio of 3: 1 (weight ratio) were mixed to prepare a cellulose solution.

&Lt; Step 2 > Preparation of ultraviolet absorber solution

7.5 parts by weight of a mixed ultraviolet absorber obtained by mixing Tinuvin 328 (manufactured by Ciba Specialty Chemicals) and Tinuvin 326 (manufactured by Ciba Specialty Chemicals) in a ratio of 4: 1 (weight ratio), and 9 parts by weight of methylene chloride and methanol (Weight ratio) were mixed to prepare an ultraviolet absorber solution.

<Step 3> Preparation of Dilute Solution Containing Metal Oxide

28.5 parts by weight of the cellulose solution prepared in <Step 1>, 1.5 parts by weight of silica (SiO2), and 70 parts by weight of a mixed solvent of methylene chloride and methanol mixed at a weight ratio of 9: 1 were mixed to prepare silica (metal oxide) A dilute cellulose solution was prepared.

&Lt; Step 4 > Preparation of cellulose film

93 parts by weight of the cellulose solution, 4 parts by weight of the dilute cellulose solution containing the metal oxide and 3 parts by weight of the ultraviolet absorber solution were mixed to prepare a casting stock solution. Then, on the surface of the metal belt, a sheet having a thickness of 400 μm and a width of 1800 mm ). While the metal belt was being rotated, the solvent of the casting stock solution was evaporated, stretched and dried to form a cellulose film (TF-40-1) having a thickness of 40 占 퐉. The light transmittance T (380 nm) of the prepared cellulose film at 380 nm wavelength was 2.62%, the light transmittance T (620 nm) at 620 nm was 92.8%, and the b * value was 0.60 in the CIE colorimetric system. A cellulose film (TF-60-1) having a thickness of 60 탆 was formed by changing the thickness in the same manner. The light transmittance T (380 nm) of the prepared cellulose film at 380 nm wavelength was 2.56%, the light transmittance T (620 nm) at 620 nm was 92.7%, and the b * value was 0.59 in the CIE colorimetric system.

Manufacturing example 3: Preparation of polarizing plate

The polarizer, the cellulose ester film as the polarizing plate protective film (first protective film), and the cellulose ester as the polarizing plate protective film (second protective film) on the back side, according to the following steps 1 to 5, , A polarizing plate in which a polarizer and a cellulose ester film were bonded as a polarizing plate protective film was produced according to the following process.

Step 1: The film was immersed in a 2 mol / L sodium hydroxide solution at 60 占 폚 for 90 seconds, followed by washing with water and drying to obtain a saponified cellulose ester film bonded to the polarizer.

Step 2: The polarizing membrane was immersed in a polyvinyl alcohol adhesive tank (bath) having a solid content of 2 mass% for 1 to 3 seconds.

Step 3: In step 2, excess glue adhered to the polarizing film was lightly wiped off, and placed on a cellulose ester film treated in step 1.

Step 4: The cellulose ester film laminated in Step 3, the polarizer, and the back side cellulose ester film were bonded at a pressure of 20 to 30 N / cm 2 and at a conveying speed of about 2 m / min.

Step 5: A sample obtained by bonding the polarizer, the cellulose ester film, and the back side cellulose ester film prepared in Step 4 to a dryer at 80 캜 was dried for 2 minutes to prepare a polarizing plate.

Comparative Manufacturing Example 3: Preparation of polarizing plate

A polarizing plate in which a polarizer and a cellulose ester film were bonded as a polarizing plate protective film was prepared according to the process of Production Example 3 with the combination of Table 2 below.

Experimental Example 2

The polarizing plate protective film (first protective film) was coated with a pressure-sensitive adhesive on each of the polarizing plates prepared in Production Example 3 and Comparative Production Example 3, and laminated on a glass substrate having a thickness of 0.5 mm. In this state, the degree of polarization was measured using a spectrophotometer (Jasco, Model V7100) optical measuring instrument under the environment of 23 ° C and 55% RH. The results are shown in Table 2 below.

The polarizing plate laminated on the glass was allowed to stand for 500 hours in a reliable environment of 60 ° C. and 90% RH using a high temperature and high humidity chamber, and then taken out from the high temperature and high humidity chamber again. The polarization degree of use was measured, and the change in polarization degree before and after the reliability environmental treatment was observed. The results are shown in Table 2 below.

Polarizer Cellulose ester film No. Polarizer Polarizer
Film thickness
(um) Polarization degree (%) Appearance (optical stain) The first protective film The second protective film Before reliability After reliability Before reliability After reliability Production example 3-1 Production Example 1-1 TF-40-1 PF-1 100 99.9816 99.9749 none none Production example 3-2 Production Example 1-2 TF-40-1 PF-1 100 99.9823 99.9676 none none Production Example 3-3 Production Example 1-3 TF-40-1 PF-1 100 99.9863 99.9733 none none Production example 3-4 Production Example 1-4 TF-40-1 PF-1 100 99.9827 99.9704 none none Production Example 3-5 Production Example 1-5 TF-40-1 PF-1 100 99.9886 99.9600 none none Production Example 3-6 Production Example 1-6 TF-40-1 PF-1 100 99.9818 99.9661 none none Production Example 3-7 Preparation Example 1-7 TF-40-1 PF-1 100 99.9816 99.9607 none none Production Example 3-8 Production Example 1-8 TF-40-1 PF-1 100 99.9818 99.9721 none none Comparative Production Example 3-1 Comparative Production Example 1-1 TF-40-1 PF-1 100 99.9836 99.9340 none With partial staining Comparative Production Example 3-2 Comparative Production Example 1-2 TF-40-1 PF-1 100 99.9888 99.9411 none With partial staining Comparative Production Example 3-3 Comparative Production Example 1-3 TF-40-1 PF-1 100 99.9822 99.9351 none With partial staining Comparative Production Example 3-4 Comparative Production Examples 1-4 TF-40-1 PF-1 100 99.9860 99.9252 none With partial staining

As can be seen from the above Table 2, the cellulose ester polarizing plate protective film of the present invention, particularly the polarizing plate protective film (first protective film), contains the plasticizer as proposed in the present invention and substitutes the thickness of the cellulose ester film The reliability and appearance (optical unevenness) of the polarization degree before and after the reliability treatment of the polarizing plate were excellent.

Manufacturing example 4: Manufacture of vertical alignment liquid crystal display device

The polarizing plate prepared in Preparation Example 3 was coated with a pressure-sensitive adhesive on the surface of the polarizing plate protective film B (the first protective film) by the combination of Table 3 below, and then the polarizing plate protective film B was applied to the vertically- And a vertical alignment-LCD was manufactured by attaching an up / down polarizer. The second protective films 111 and 123 and the first protective films 113 and 121 are bonded to the polarizers 112 and 122 and attached to the upper and lower surfaces of the vertically aligned liquid crystal panel 10, respectively. In Fig. 1, a indicates the absorption axis of the polarizing plate, and b indicates the slow axis of the A-plate.

The vertically aligned liquid crystal panel 10 is packed with a vertically aligned liquid crystal having negative dielectric anisotropy Δε = -4.92 and birefringence Δn = 0.0971 in a VA cell having a cell gap of 3.5 μm and a pretilt angle of 89 °, and a retardation value Rt_VA (550 nm) was 307 nm, and the retardation value Ro_VA (550 nm) in the plane direction was 3 nm.

Comparative Manufacturing Example 4: Manufacture of vertical alignment liquid crystal display device

A liquid crystal display device was prepared according to the process of Production Example 4 with the combination of Table 3 below.

Experimental Example 3

The vertically aligned liquid crystal panel 10 produced in Production Example 4 and Comparative Production Example 4 had a 3.5 μm cell gap and a VA cell having a pretilt angle of 89 ° and a vertical direction having a negative dielectric anisotropy Δε = -4.92 and a birefringence Δn = 0.0971 The retardation value Rt_VA (550 nm) in the thickness direction was 307 nm and the retardation value Ro_VA (550 nm) in the plane direction was 3 nm.

In this state, the brightness was measured in a black state and a white state using a BM-7 luminance meter under conditions of 23 ° C and 55% RH, respectively. The results are shown in Table 3 below.

The thus prepared vertical alignment-LCD was allowed to stand for 500 hours in a reliable environment of 60 ° C and 90% RH using a high temperature and high humidity chamber, and then taken out from the high temperature and high humidity chamber again under the conditions of 23 ° C. and 55% And the contrast ratios before and after the reliability environmental treatment were observed. The results are shown in Table 3 below.

Vertically oriented LCD structure CR (contrast ratio) according to reliability processing Appearance (optical stain) The upper polarizer plate VA panel The lower polarizer plate I'm after ? CR (%) Before reliability After reliability Production Example 4-1 Production example 3-1 In the liquid crystal panel 10, Production example 3-1 6664 5799 -13.0 none none Production example 4-2 Production example 3-2 In the liquid crystal panel 10, Production example 3-2 6622 5794 -12.5 none none Production Example 4-3 Production Example 3-3 In the liquid crystal panel 10, Production Example 3-3 6660 5799 -12.9 none none Production Example 4-4 Production example 3-4 In the liquid crystal panel 10, Production example 3-4 6247 5798 -7.2 none none Production Example 4-5 Production Example 3-5 In the liquid crystal panel 10, Production Example 3-5 6519 5798 -11.1 none none Production Example 4-6 Production Example 3-6 In the liquid crystal panel 10, Production Example 3-6 6488 5799 -10.6 none none Production Example 4-7 Production Example 3-7 In the liquid crystal panel 10, Production Example 3-7 6583 5799 -11.9 none none Production Example 4-8 Production Example 3-8 In the liquid crystal panel 10, Production Example 3-8 6486 5794 -10.7 none none Comparative Production Example 4-1 Comparative Production Example 3-1 In the liquid crystal panel 10, Comparative Production Example 3-1 4200 3193 -24.0 none Partly smeary Comparative Production Example 4-2 Comparative Production Example 3-2 In the liquid crystal panel 10, Comparative Production Example 3-2 6275 4798 -23.5 none Partly smeary Comparative Production Example 4-3 Comparative Production Example 3-3 In the liquid crystal panel 10, Comparative Production Example 3-3 6690 4798 -28.3 none Partly smeary Comparative Production Example 4-4 Comparative Production Example 3-4 In the liquid crystal panel 10, Comparative Production Example 3-4 4095 3197 -21.9 none Partly smeary

As can be seen from the above Table 3, when the vertical orientation-LCD is produced using the plasticizer and the cellulose ester film proposed in the present invention in the protective film B of the cellulose ester polarizing plate of the present invention, It was found that the reliability of the contrast ratio before and after the reliability process of the LCD is excellent.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. It will be easy for anyone to know.

10: 0.5t transparent glass substrate, vertically aligned liquid crystal panel
a: absorption axis of the polarizer
b: Optical axis of the cellulose ester phase difference film
11: Lower polarizer plate
111: Polarizing plate protective film (second protective film)
112: Polarizer (PVA film)
113: Polarizing plate protective film (first protective film)
12: polarizer, upper polarizer
121: Polarizing plate protective film (first protective film)
122: Polarizer (PVA film)
123: Polarizing plate protective film (second protective film)

Claims

A liquid crystal panel;
An upper polarizer formed on the liquid crystal panel; And
And a lower polarizer formed on the lower surface of the liquid crystal panel,
Wherein each of the upper polarizer and the lower polarizer comprises a first protective film; A polarizer formed on the first protective film; And a second protective film formed on the polarizer,
When the contrast ratio of the liquid crystal display device was measured after being left at 60 ° C and 90% RH for 500 hours, the change value after pre-exposure was within 20%
Wherein the first protective films are a cellulose ester film satisfying the following formula (1) in the range of cellulose ester represented by the following formula (1) and average unmodified hydroxyl group of the saccharide compound represented by the following formula (2)
The first protective films are allowed to stand at 60 ° C and 90% RH for 500 hours, respectively. Thereafter, the variation range of P value before and after leaving is -0.001 to 0.001 expressed by the following formula (2) And the retardation Rth in the thickness direction is 100 to 300 nm under the conditions of 23 deg. C and 55% RH,
Wherein the upper polarizer and the lower polarizer are left at 60 ° C and 90% RH for 500 hours, respectively, and the degree of polarization of the polarizer represented by the following formula (4) is 99.95% or more.
[Chemical Formula 1]

In the above formula (1), R is substituted with an acyl group (acetyl group, propionyl group, butyryl group), and unsubstituted R is left as a hydroxyl group.
(2)

In the above formula (2), R is substituted with benzoic acid or acetate, and unsubstituted R remains as a hydroxyl group.
[Equation 1]
R _SOH + A _SOH? 1.5
R _SOH? 0.4
In the above formula (1), R _SOH is the degree of substitution of R, which is unsubstituted in formula (1) and remains as a hydroxyl group, and A _SOH is the degree of substitution of R which is unsubstituted and remains as a hydroxyl group in formula (2).
&Quot; (2) "
P value = 1 - sin 2 (2?) * Sin 2 (? /? * Ro) * 100
-0.5 <
In the above equation (2),? Is the optical axis of the first protective film,? Is 550 nm as the reference wavelength of the measurement light, and Ro is the retardation in the plane direction when measured with 550 nm light.
&Quot; (3) "
Ro = (nx-ny) xd
Rth = {(nx + ny) / 2-nz} xd
Ny is the maximum refractive index in the vertical direction in the film plane, and nz is the maximum refractive index in the thickness direction of the film. The refractive indices of the film are 23 deg. C, And a value measured at a wavelength of 550 nm under an environment of 55% RH.
&Quot; (4) "
Polarization degree (PE,%) = [(Tp-Tc) / (Tp + Tc)] ^1/2 x 100
In Equation (4), Tp is the transmittance of the polarizing plate in a state where the transmission axes thereof are parallel to each other, and Tc is the transmittance of the visible light range of 400 to 700 nm in an environment of 23 DEG C and 55% RH in an orthogonal state.

delete

The method according to claim 1,
Wherein the first protective films each have a thickness of 20 to 60 mu m.

The method according to claim 1,
Wherein the second protective films each have a thickness of 20 to 100 占 퐉 and a thickness of 60 to 160 占 퐉 sandwiched between the polarizers.

delete