KR20170009623A

KR20170009623A - In-plane switching liquid crystal display including cellulose ester phase difference film

Info

Publication number: KR20170009623A
Application number: KR1020150101950A
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: 2017-01-25

Abstract

The present invention relates to a liquid crystal display device including a cellulose ester film, and more particularly, to an IPS liquid crystal display device 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 an IPS liquid crystal display device including a cellulose ester film,

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 _υθ) 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 The present invention has been made in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide an IPS liquid crystal display device having reliability and improved quality by including a resin and additives 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; And a polarizer disposed on a rear surface and a front surface of the liquid crystal panel and converting an incident light axis, wherein the polarizer plate has a cellulose ester having an acetyl group substitution degree of 2.70 to 2.95; And a first protective film which is a cellulose ester film comprising an asymmetric ester compound containing an aromatic group represented by the following formula (1) and a terminal symmetric aliphatic compound represented by the following formula (2); A polarizer formed on the first protective film; And a second protective film formed on the polarizer and being a triacetylcellulose film.

[Chemical Formula 1]

_{M A - [D O -D A} ] nD O

In the formula 1, M _A : R ₁ -COOH, D ₂ _O : HO-R ₂ -OH, D _A : HOOC-R ₁ -COOH,

R ₁ is an aryl dicarboxylic acid residue having 6 or more carbon atoms, R ₂ is a compound having 2 to 6 carbon atoms as a propylene glycol residue, and n is an integer of 1 or more.

(2)

I - (T) n - I

In Formula 2, I represents an ester group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a hydroxyl group, T is 2,2,4-trimethyl-1,3-pentanylene group, or a divalent saturated bridging group having 0 to 40 carbon atoms and 0 to 20 carbon atoms, and the number of atoms 0 means that the groups at both ends of the linkage form a single bond directly. N is an integer greater than or equal to 1.

In this case, the first protective film preferably has an effective retardation value Reff of 30 to 30 nm, which is defined by the following formula (1) measured under conditions of 23 ° C and 55% RH.

[Equation 1]

Reff = (nx'- ny ') xd

In the above formula (1), d is the thickness (nm) of the film, and nx 'and ny' are formed from nx, ny and nz when observed at the positions of? = 45 ° and? Is an effective surface refractive index value.

It is also preferable that the first protective film has a Reff change amount? Reff of 10 to 10 nm after being left for 500 hours in an environment of 60 deg. C and 90% RH.

In addition, it is preferable that the polarizing plate has a degree of polarization of 99.95% or more after being allowed to stand in an environment of 60 ° C and 90% RH for 500 hours.

&Quot; (2) "

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

In the above formula (2), Tp is the transmittance of the polarizing plate to the visible light transmittance band of 400 to 700 nm under an environment of 23 ° C and 55% RH in a state where the transmission axes are parallel to each other and Tc is orthogonal.

Further, it is preferable that the IPS liquid crystal display device has a CR (Contrast Ration) fluctuation range before and after being allowed to stand for 500 hours in an environment of 60 ° C and 90% RH satisfies the following condition (3).

&Quot; (3) "

ΔCR (= after leaving CR_-before leaving CR_ / before leaving CR_ × 100 (%)) <± 15%

In Equation (3), CR is the white luminance / black luminance, and the contrast ratio of the luminance in the state where the LCD is in the black state and the luminance is white.

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.

Fig. 1 is a view showing an effective surface direction formed from nx, ny and nz when measuring Reff according to the present invention.
2 is a schematic view showing a process for producing a cellulose ester film according to the present invention.
3 is a view schematically showing a polarizing plate according to the present invention.
4 is a view schematically showing an IPS liquid crystal display device according to the present invention.

Hereinafter, the present invention will be described.

An IPS liquid crystal display device according to the present invention includes: a liquid crystal panel having a plurality of pixel cells and displaying an image; And a polarizing plate having an elongated PVA and at least one TAC, disposed on the back and front surfaces of the liquid crystal panel, for converting an advancing axis of incident light.

Here, the polarizing plate may be a cellulose ester having an acetyl group substitution degree of 2.70 to 2.95; And a first protective film which is a cellulose ester film comprising an asymmetric ester compound containing an aromatic group represented by the following formula (1) and a terminal symmetric aliphatic compound represented by the following formula (2); A polarizer formed on the first protective film; And a second protective film formed on the polarizer and being a triacetylcellulose film.

[Chemical Formula 1]

_{M A - [D O -D A} ] nD O

(2)

I - (T) n - I

Meanwhile, the cellulose ester phase difference film as the first protective film of the present invention is a plasticizer and includes an asymmetric ester compound having an aromatic group represented by the formula (1) and a terminal symmetric aliphatic compound represented by the formula (2). By including the above plasticizer, it is particularly preferable to set the optical reliability characteristics of the cellulose ester film before and after the reliability treatment to a predetermined range.

Specific examples of the asymmetric ester compound containing an aromatic group are shown in the following general formulas (2) to (4), but the present invention is not limited thereto.

(2)

(3)

[Chemical Formula 4]

Further, specific compounds of the terminal symmetric aliphatic compound are represented by the following general formula (5), but are not limited thereto.

[Chemical Formula 5]

Meanwhile, the cellulose ester phase difference film according to the present invention can be produced by solution casting method. 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.

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.

The cellulose ester phase difference film preferably has an effective retardation value Reff of 30 to 30 nm defined by the following formula (1) measured under the conditions of 23 deg. C and 55% RH.

[Equation 1]

Reff = (nx'- ny ') xd

Further, the cellulose ester phase difference film is characterized in that the Reff change amount? Reff after being left in an environment of 60 ° C and 90% RH for 500 hours and before and after being left is 10 to 10 nm.

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.

The second protective film is preferably formed of triacetyl cellulose having a total degree of substitution of acetyl groups of 2.7 or more on the polarizer. 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 produced as described above has a polarization degree of 99.95% or more of the polarizing plate expressed by the following formula (2) after being left at 60 ° C and 90% RH for 500 hours.

&Quot; (2) "

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 cellulosic solution was prepared by using triacetyl cellulose having an average acetyl substitution degree (DS) of 2.86 and a terminal asymmetric aromatic plasticizer A represented by the following formula as a plasticizer and a terminal symmetric aliphatic plasticizer B as the plasticizer for the cellulose ester.

<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 in the temperature environment of 170 ° C was 1.1 times. Thereafter, the stretching was maintained for a few seconds while maintaining the width, , And the film was transported for 35 minutes in a drying zone set at 110 캜 for drying for 35 minutes to produce a cellulose ester film having a thickness of 20 탆 and a knurling width of 1900 mm and a width of 10 mm and a height of 8 탆 at the end.

Manufacturing example 1-2: Preparation of first protective film

A cellulose ester film was produced in the same manner as in Production Example 1-1, except that the film thickness was changed to 25 탆.

Manufacturing example 1-3: Preparation of first protective film

A cellulose ester film was produced in the same manner as in Production Example 1-1, except that the film thickness was changed to 30 탆.

Manufacturing example 1-4: Preparation of first protective film

A cellulose ester film was produced in the same manner as in Production Example 1-1, except that the film thickness was changed to 40 탆.

Comparative Manufacturing Example 1-1

A cellulose ester film was prepared in the same manner as in Production Example 1-4, except that a terminal symmetrical aliphatic plasticizer B and a terminal symmetrical aromatic plasticizer C represented by the following chemical formula were used as plasticizers.

Comparative Manufacturing Example 1-2

A cellulose ester film was produced in the same manner as in Production Example 1-4, except that the terminal symmetric aliphatic plasticizer B and the terminal symmetrical aromatic plasticizer D represented by the following formulas were used as plasticizers.

Experimental Example One

The optical properties of the cellulose ester films prepared in Production Examples 1-1 to 1-4 and Comparative Production Examples 1-1 to 1-2 were measured by the following methods, and the results are shown in Table 1 below.

The cellulose ester film was irradiated with a wavelength of 590 nm as a reference wavelength under an environment of 23 ° C. and 55% RH using an optical measuring instrument of AxoScan (OPMF-1, Axometrics), and was effective at positions θ = 45 ° and Φ = 45 ° Plane direction retardation value Reff was measured.

In addition, the cellulose ester film was subjected to a reliability treatment for 500 hours at 60 ° C and 90% RH using a high temperature and high humidity chamber, and the Reff after the reliability treatment was measured using the same measuring equipment.

Cellulose ester Plasticizer Type Film thickness
(um) Reliability Before / After Reff (nm) Kinds Addition amount
(kg) Kinds Additive amount (kg) Before processing After processing Variation Production Example 1-1 TAC 100 A + B 5 + 5 20 2.4 0.7 -1.7 Production Example 1-2 TAC 100 A + B 5 + 5 25 3.2 1.4 -1.8 Production Example 1-3 TAC 100 A + B 5 + 5 30 4.5 1.8 -2.7 Production Example 1-4 TAC 100 A + B 5 + 5 40 5.4 0.5 -4.9 Comparative Production Example 1-1 TAC 100 B + C 5 + 5 40 15.8 2.4 -13.4 Comparative Production Example 1-2 TAC 100 B + D 5 + 5 40 12.7 0.9 -11.8

As can be seen from the above Table 1, when the plasticizer (asymmetric ester compound including an aromatic group) shown in the present invention is included, the ΔReff characteristic of the cellulose ester film before and after the reliability treatment is excellent, I was able to see that it was excellent.

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 mu m 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 3-1 to 3-4: 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 (tank) 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 3-1 to 3-2: 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 3-1 in the combination of Table 2 below.

Experimental Example 2

The polarizing plate protective films (first protective films) were coated with a pressure-sensitive adhesive on the polarizing plates prepared in Production Examples 3-1 to 3-4 and Comparative Production Examples 3-1 to 3-2, respectively, Lamination on. 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, and 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 Polarization degree (%) Appearance (optical stain) The first protective film The second protective film Film thickness
(um) Before reliability After reliability Before reliability After reliability Production example 3-1 Production Example 1-1 TF-40-1 PF-1 100 99.9831 99.9742 none none Production example 3-2 Production Example 1-2 TF-40-1 PF-1 100 99.9821 99.9672 none none Production Example 3-3 Production Example 1-3 TF-40-1 PF-1 100 99.9843 99.9731 none none Production example 3-4 Production Example 1-4 TF-40-1 PF-1 100 99.9815 99.9701 none none Comparative Production Example 3-1 Comparative Production Example 1-1 TF-40-1 PF-1 100 99.9831 99.9337 none With partial staining Comparative Production Example 3-2 Comparative Production Example 1-2 TF-40-1 PF-1 100 99.9828 99.9401 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.

Example 1 to 4: IPS Manufacturing of Liquid Crystal Display

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) according to the combination of Table 3 below, and then the polarizing plate protective film B was applied to the horizontal alignment panel And a horizontal 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 surface and the lower surface of the horizontally aligned liquid crystal panel 10 respectively. In Fig. 4, a indicates the absorption axis of the polarizing plate, and b indicates the slow axis of the retardation film.

The liquid crystal panel 10 includes a thin film transistor (TFT) formed in each pixel cell defined by a plurality of gate lines and a plurality of data lines, and a liquid crystal capacitor connected to the TFT. The liquid crystal capacitor is composed of a pixel electrode connected to the TFT, and a common electrode facing the pixel electrode and the liquid crystal. The TFT supplies a data signal from each data line to the pixel electrode in response to a scan pulse from each gate line. The liquid crystal capacitor charges the difference voltage between the data signal supplied to the pixel electrode and the common voltage supplied to the common electrode, adjusts the arrangement of the liquid crystal molecules according to the difference voltage, and adjusts the light transmittance to realize the gradation. The storage capacitor is connected to the liquid crystal capacitor in parallel so that the voltage charged in the liquid crystal capacitor is maintained until the next data signal is supplied. The storage capacitor is formed such that the pixel electrode overlaps the storage line with the insulating film interposed therebetween. In other words, the liquid crystal panel 10 has a storage capacitor formed in parallel with the liquid crystal capacitor, that is, a storage on command structure in which a storage capacitor is formed between the pixel electrode and the storage line.

Comparative Example 1 to 2: IPS Manufacturing of Liquid Crystal Display

A liquid crystal display device was prepared according to the procedure of Example 1 with the combination of Table 3 below.

Experimental Example 3

The IPS liquid crystal display devices manufactured in Examples 1 to 4 and Comparative Examples 1 and 2 were allowed to stand in a high-temperature and high-humidity chamber for 500 hours under conditions of a reliable environment of 60 ° C and 90% RH, And the brightness was measured in the black and white state using the same equipment under the environment of 23 ° C and 55% RH to observe the change in the contrast ratio before and after the reliability environmental treatment. The results are shown in Table 3 below.

LCD Horizontally oriented LCD structure Contrast Ratio The upper polarizer plate VA panel The lower polarizer plate Before reliability processing After reliability processing ? CR (%) Example 1 Production example 3-1 In the liquid crystal panel 10, Production example 3-1 5657 5184 -8.4 Example 2 Production example 3-2 In the liquid crystal panel 10, Production example 3-2 5645 5191 -8.0 Example 3 Production Example 3-3 In the liquid crystal panel 10, Production Example 3-3 5662 5175 -8.6 Example 4 Production example 3-4 In the liquid crystal panel 10, Production example 3-4 5228 4794 -8.3 Comparative Example 1 Comparative Production Example 3-1 In the liquid crystal panel 10, Comparative Production Example 3-1 5628 4394 -21.9 Comparative Example 2 Comparative Production Example 3-2 In the liquid crystal panel 10, Comparative Production Example 3-2 5638 4568 -19.0

As can be seen from the above Table 3, the cellulose ester polarizing plate protective film of the present invention, particularly the polarizing plate protective film B (first protective film), was prepared by using the cellulose ester film containing the plasticizer When the horizontal alignment-LCD was fabricated, it was found that the reliability of the contrast ratio before and after the reliability process of the LCD was 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, IPS 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; And
And a polarizing plate disposed on a front surface and a front surface of the liquid crystal panel for converting an incident light axis,
Wherein the polarizer comprises a cellulose ester having an acetyl group substitution degree of 2.70 to 2.95; And a first protective film which is a cellulose ester film comprising an asymmetric ester compound containing an aromatic group represented by the following formula (1) and a terminal symmetric aliphatic compound represented by the following formula (2);
A polarizer formed on the first protective film; And
And a second protective film formed on the polarizer and being a triacetylcellulose film.
[Chemical Formula 1]
_{M A - [D O -D A} ] nD O
In the formula 1, M _A : R ₁ -COOH, D ₂ _O : HO-R ₂ -OH, D _A : HOOC-R ₁ -COOH,
R ₁ is an aryl dicarboxylic acid residue having 6 or more carbon atoms, R ₂ is a compound having 2 to 6 carbon atoms as a propylene glycol residue, and n is an integer of 1 or more.
(2)
I - (T) n - I
In Formula 2, I represents an ester group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a hydroxyl group, T is 2,2,4-trimethyl-1,3-pentanylene group, or a divalent saturated bridging group having 0 to 40 carbon atoms and 0 to 20 carbon atoms, and the number of atoms 0 means that the groups at both ends of the linkage form a single bond directly. N is an integer greater than or equal to 1.

The method according to claim 1,
Wherein the first protective film has an effective retardation value Reff of 30 to 30 nm, which is defined by the following formula (1) measured under conditions of 23 deg. C and 55% RH.
[Equation 1]
Reff = (nx'- ny ') xd
In the above formula (1), d is the thickness (nm) of the film, and nx 'and ny' are formed from nx, ny and nz when observed at the positions of? = 45 ° and? Is an effective surface refractive index value.

The method according to claim 1,
Wherein the first protective film has a Reff change amount? Reff of 10 to 10 nm after being left in an environment of 60 占 폚 and 90% RH for 500 hours and before and after being left standing.

The method according to claim 1,
Wherein the polarizing plate has a degree of polarization of 99.95% or more after being allowed to stand in an environment of 60 DEG C and 90% RH for 500 hours, and a polarizing plate represented by the following formula (2).
&Quot; (2) "
Polarization degree (PE,%) = [(Tp-Tc) / (Tp + Tc)] ^1/2 x 100
In the above formula (2), Tp is the transmittance of the polarizing plate to the visible light transmittance band of 400 to 700 nm under an environment of 23 ° C and 55% RH in a state where the transmission axes are parallel to each other and Tc is orthogonal.

The method according to claim 1,
Wherein the IPS liquid crystal display device has a CR (Contrast Ration) fluctuation range before and after being allowed to stand for 500 hours in an environment of 60 deg. C and 90% RH satisfies the condition of the following formula (3).
&Quot; (3) "
ΔCR (= after leaving CR_-before leaving CR_ / before leaving CR_ × 100 (%)) <± 15%
In Equation (3), CR is the white luminance / black luminance, and the contrast ratio of the luminance in the state where the LCD is in the black state and the luminance is white.