KR20170081024A - Vertical orentation type liquid display device having an improved reliable property and improved contrast ratio and method for preparing the same - Google Patents

Vertical orentation type liquid display device having an improved reliable property and improved contrast ratio and method for preparing the same Download PDF

Info

Publication number
KR20170081024A
KR20170081024A KR1020150191701A KR20150191701A KR20170081024A KR 20170081024 A KR20170081024 A KR 20170081024A KR 1020150191701 A KR1020150191701 A KR 1020150191701A KR 20150191701 A KR20150191701 A KR 20150191701A KR 20170081024 A KR20170081024 A KR 20170081024A
Authority
KR
South Korea
Prior art keywords
polarizing plate
film
carbon atoms
protective film
cellulose ester
Prior art date
Application number
KR1020150191701A
Other languages
Korean (ko)
Other versions
KR101791320B1 (en
Inventor
김영수
김경수
김용원
이유미
이호준
강혁모
Original Assignee
주식회사 효성
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 효성 filed Critical 주식회사 효성
Priority to KR1020150191701A priority Critical patent/KR101791320B1/en
Publication of KR20170081024A publication Critical patent/KR20170081024A/en
Application granted granted Critical
Publication of KR101791320B1 publication Critical patent/KR101791320B1/en

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F2001/133742—

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention relates to a vertical alignment type liquid crystal display device having excellent reliability of a contrast ratio including an asymmetric ester compound containing an aromatic group represented by the following formula (1), and a polarizing plate protective film of a cellulose ester phase difference film produced by a solution casting method, And a method for manufacturing the same.
[Chemical Formula 1]
T + [D + P] n + D
T is a residue of a toluic acid or a benzenecarboxylic acid residue, D is a propyleneglycol having 2 to 8 carbon atoms, neopentylglycol, diethyleneglycol, dipropyleneglycol Triethylene glycol, an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, P is a phthalic acid having 2 to 10 carbon atoms Phthalic acid residue, an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms, or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.

Description

[0001] The present invention relates to a vertical alignment type liquid crystal display device having excellent reliability of a contrast ratio and a method of manufacturing the same,

The present invention relates to a vertical alignment type liquid crystal display device having excellent reliability of a contrast ratio and a manufacturing method thereof. More particularly, the present invention relates to a cellulose ester phase retardation film produced by a solution casting method, which comprises a vertical alignment type liquid crystal display device having an excellent reliability of a contrast ratio including an asymmetric ester compound having an aromatic group represented by the following formula And a manufacturing method thereof.

 [Chemical Formula 1]

T + [D + P] n + D

T is a residue of a toluic acid or a benzenecarboxylic acid residue, D is a propyleneglycol having 2 to 8 carbon atoms, neopentylglycol, diethyleneglycol, dipropyleneglycol Triethylene glycol, an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, P is a phthalic acid having 2 to 10 carbon atoms Phthalic acid residue, an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms, or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.

In general, a liquid crystal display (hereinafter referred to as LCD) is advantageous in that it is thinner and lighter than a CRT (Cathode Ray Tube), can be driven at a low voltage, and consumes less power. Therefore, LCDs are used in various electronic devices such as televisions, notebook type personal computers (PCs), desktop type PCs, PDAs (portable terminals) and cellular phones.

In recent years, a vertical alignment type LCD (also referred to as a VA (Vertical Alignment) type) LCD using vertical alignment type liquid crystal (liquid crystal having a negative dielectric anisotropy) has a viewing angle characteristic It is widely used, in terms of superiority.

However, in this VA-LCD, the demand for power saving is further increased, and the light shielding part is minimized and the color filter on array (COA) is increasingly becoming more and more widely used. A method of increasing the transmittance of the polarizing plate as a power saving means has been proposed. However, when the transmittance of the polarizing plate is increased only, the degree of polarization decreases and the front contrast ratio (contrast) is lowered.

In order to solve this problem, a method of suppressing the depolarization caused by a polarizing film and a film (protective film) disposed between the polarizing film and the liquid crystal cell, such as a retardation film and a viewing angle enlarging film, is used.

Patent Document 1 and Non-Patent Document 1 below disclose that the front contrast ratio is increased by the constitution of the retardation film. These methods suggest a possibility that the front contrast ratio can be maintained even if the transmittance of the polarizing plate is increased. However, as a means of improving the front contrast ratio by these methods, the color shift becomes very large. Originally, a vertical alignment type liquid crystal display device has a small color shift, but this configuration is a method of eliminating the inherent advantages of a vertical alignment type liquid crystal display device.

In addition, the LCD manufactured using the conventional retardation film is resistant to high temperature and high humidity environments, and the contrast ratio of the LCD is also deteriorated when exposed to a high temperature and high humidity reliability environment.

(Patent Literature): Japanese Laid-Open Patent Publication No. 2010-54736

(Non-Patent Document): SID 2010 Digest of Technical Papers 55.1

Accordingly, it is an object of the present invention to provide a vertical alignment type liquid crystal display device and a method of manufacturing the same, which are excellent in reliability without lowering the contrast ratio even when exposed to a high temperature and high humidity environment.

According to an embodiment of the present invention, there is provided a vertical alignment type liquid crystal display device having excellent reliability of a contrast ratio,

A total cellulose acylate phase difference film having a total degree of substitution of acyl groups of 2.10 to 2.70 between the vertically aligned panel and the upper and lower polarizing plates, wherein the total sum of phase retardation values (Ro total ) 2, and the mixture was allowed to stand in a high-temperature and high-humidity chamber at a temperature of 60 ° C and a RH of 90% RH for 500 hours, the variation range of CR (Contrast Ratio) Wherein the cellulose ester phase difference film produced by the casting method comprises an asymmetric ester compound having an aromatic group represented by the following formula (1).

[Equation 1]

Ro total = R - C + R LC

&Quot; (2) "

40 nm < Rt total < 190 nm

In the formulas (1) and (2), R- C is the total retardation value in the plane direction of the negative C-plate satisfying the following equation (3)

&Quot; (3) &quot;

R- C = (plane retardation value of the polarizing plate inner cellulose ester film) + (plane retardation value of the biaxial A plate) + (plane retardation value of the negative C plate)

R LC is the retardation value in the plane direction of the liquid crystal of the vertically oriented panel, and Ro total is the sum of R LC and R C.

&Quot; (4) &quot;

? CR = {CR? Reliability? CR? Reliability?} / (CR? Reliability x 100 (%

Where CR is the white luminance / black luminance, which is the contrast ratio of the luminance when the LCD is in the black state and the luminance state is white.

[Chemical Formula 1]

T + [D + P] n + D

T is a residue of a toluic acid or a benzenecarboxylic acid residue, D is a propyleneglycol having 2 to 8 carbon atoms, neopentylglycol, diethyleneglycol, dipropyleneglycol Triethylene glycol, an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, P is a phthalic acid having 2 to 10 carbon atoms Phthalic acid residue, an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms, or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.

The vertical bend-type liquid crystal display device according to the present invention includes an aromatic asymmetric ester compound represented by the above formula (1) so as to improve the high temperature and high humidity reliability of the cellulose ester phase difference film, The contrast ratio is not deteriorated and the reliability is excellent.

1 is an exploded perspective view of polarizer lamination.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 illustrates an exploded perspective view of a polarizing plate lamination. A vertical alignment type liquid crystal display (hereinafter referred to as VA-LCD) according to an embodiment of the present invention includes polarizing plates 110 and 120, An adhesive is coated on the surface of the film B (113, 121), and the upper and lower polarizers 110, 120 are attached so that the polarizer protective films B (113, 121) face the vertical alignment panel. For example, the polarizing plate protective films A 111 and 123 and the polarizing plate protective films B 113 and 121 are laminated with the polarizers 112 and 122, respectively, and they are attached to the upper and lower surfaces of the vertically aligned liquid crystal panel 100, respectively.

In FIG. 1, reference symbol a denotes an absorption axis of the polarizing plate, and b denotes an optical axis of the A-plate.

The cellulose-based polarizing plate according to one embodiment of the present invention comprises a polarizing plate protective film A (111, 123) having a film thickness of 20 to 100 μm containing a cellulose ester and a polarizing plate protective film B (113, 121) ; PVA film).

More specifically, the polarizing plate according to the present invention comprises a polarizing plate protective film A having a film thickness of 20 to 100 占 퐉 containing a cellulose ester,

The polarizing plate protective film B also serving as a retardation film having a film thickness of 20 to 60 탆 and containing cellulose ester having an acyl group total substitution degree of 2.1 to 2.7 has a thickness of 60 to 160 탆 sandwiching the polarizer.

In the present invention, the cellulose ester polarizing plate protective film A is preferably cellulose triacetate having an acetyl group total degree of substitution of 2.7 or more, and the polarizer preferably has polyvinyl alcohol and has a film thickness of 3 to 30 μm, The protective film B includes an asymmetric ester-based compound having an aromatic group represented by the following formula (1).

 [Chemical Formula 1]

T + [D + P] n + D

T is a residue of a toluic acid or a benzenecarboxylic acid residue, D is a propyleneglycol having 2 to 8 carbon atoms, neopentylglycol, diethyleneglycol, dipropyleneglycol Triethylene glycol, an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, P is a phthalic acid having 2 to 10 carbon atoms Phthalic acid residue, an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms, or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.

The method for producing the polarizing plate according to one embodiment of the present invention is not particularly limited, and can be manufactured by a general method. It is preferable that the back side of the cellulose ester film of the present invention is subjected to alkali saponification treatment and the treated cellulose ester film is immersed and stretched in an iodine solution to be bonded to at least one side of the polarizing film using a fully saponified polyvinyl alcohol aqueous solution . The cellulose ester film of the present invention may also be used on the other side, and another polarizing plate protective film may be used.

A polarizing film as a main component of the polarizing plate is an element that allows only light of a polarization plane in a certain direction to pass therethrough. A typical polarizing film currently known is a polyvinyl alcohol (PVA) polarizing film. This is a method of dyeing a polyvinyl alcohol film with iodine And dyed dichromatic dyes. The polarizing film is obtained by forming a film of a polyvinyl alcohol aqueous solution, uniaxially stretching the film, dyeing or dyeing it, uniaxially stretching it, and then durably treating it with a boron compound. The film thickness of such a polarizing film is 3 to 30 탆. A polarizing plate can be formed by bonding one side of the cellulose ester film of the present invention to the surface of the polarizing film. Preferably, it can be bonded by an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

The cellulose ester film of the polarizing plate protective film A is preferably cellulose triacetate having an acetyl group total degree of substitution of 2.7 or more. The cellulose ester film may be a cellulose solution containing triacetyl cellulose as a basic component, a UV absorber solution, The solution is mixed to prepare a casting stock solution, which is extruded, drawn and dried in the form of a sheet to form a film having a thickness of 20 to 100 탆.

More specifically, the cellulose solution is prepared by mixing 10 to 20 parts by weight of triacetylcellulose, 80 to 90 parts by weight of a mixed solvent obtained by mixing methylene chloride and methanol in a weight ratio of 9: 1, adding triphenylphosphate (TPP) and ethylphthalylethyl And 1 to 3 parts by weight of a plasticizer mixed with glycerol (EPEG) in a weight ratio of 3: 1. The ultraviolet absorber solution can be prepared, for example, by mixing Tinuvin 328 (manufactured by Ciba Specialty Chemicals) and Tinuvin 326 6 to 9 parts by weight of a mixed ultraviolet ray absorbent mixed in a ratio of 4: 1 in weight ratio and 90 to 95 parts by weight of a mixed solvent obtained by mixing methylene chloride and methanol in a weight ratio of 9: 1 . Further, in a dilute cellulose agarose solution containing the metal oxide is 9 for the cellulose solution of 25 to 35 parts by weight of silica (SiO 2) 1 to 2 parts by weight of methylene chloride and methanol in a weight ratio: a mixture solvent mixed with 160 To 80 parts by weight may be mixed to prepare a dilute cellulose solution containing silica (metal oxide).

A method for producing the cellulose ester film of the polarizing plate protective film A is as follows. 85 to 95 parts by weight of the cellulose solution, 3 to 5 parts by weight of a dilute cellulose solution containing the metal oxide and 2 to 5 parts by weight of the ultraviolet absorber solution are mixed to prepare a casting solution, In the form of extrusion. Next, the solvent of the casting stock solution is evaporated, followed by stretching and drying to form a cellulose film having a thickness in the range of 20 to 100 mu m.

The cellulose ester film of the polarizing plate protective film B according to one embodiment of the present invention is a cellulose ester film comprising 10 to 30 parts by weight of a cellulose ester having an acyl group total substitution degree of 2.10 to 2.70 and an asymmetric ester 2 to 8 parts by weight of a plasticizer, 70 to 90 parts by weight of a mixed solvent of methylene chloride and methanol in a weight ratio of 9: 1 are mixed to prepare a dilute cellulose solution containing silica as a metal oxide.

Next, 2 to 10 parts by weight of the particulate additive liquid is added to 100 parts by weight of the main dope solution, and then the mixture is uniformly softened on a support by using a belt softener, and the solvent is evaporated, followed by stretching and drying. Can be prepared.

For example, the entire process for producing such a cellulose ester-based film is performed by extruding the main dope liquid onto the surface of the belt through a die and applying it in a sheet form, evaporating the solvent present in the dope liquid, (MD) and the transverse direction (TD) in the tenter (first drying section), evaporation of the residual solvent in the second drying section, and then the film is obtained through the winding process in the winder have.

Here, the die may be a normal T-die, and the belt is preferably a stainless steel conveyor belt, for example, a high-temperature band support which forms a film by drying while transferring the dope liquid. The thickness of such a cellulose ester film (for example, the final thickness after stretching and drying) can be appropriately adjusted as necessary, but according to the present invention, it is preferably in the range of 20 to 60 탆.

The polarizing plate protective film B produced by the above method also serves as a retarder, and has in-plane retardation Ro of 40 to 60 nm and retardation Rth in the thickness direction of 110 to 140 nm.

Ro = (nx-ny) xd

Rth = ((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, nx &gt; = ny, , And d represents the thickness (nm) of the film. The retardation values Ro and Rt were measured at 590 nm under the environment of 23 ° C and 55% RH using an AxoScan (OPMF-1, Axometrics) optical measuring instrument.

The cellulose esters can be generally used alone or in combination with cellulose esters synthesized from cellulose ester synthesized from linter pulp, wood pulp and kenaf pulp, and other raw materials.

According to the present invention, the cellulose ester optical film may contain a specific plasticizer, and the plasticizer is an asymmetric ester plasticizer containing an aromatic group represented by the general formula (1). The cellulose ester film may be a barrier film of a cellulose ester film before / And is particularly preferable in setting the characteristics to a predetermined range.

Specific compounds of the aromatic-containing asymmetric ester compound according to the present invention are as follows, but the present invention is not limited thereto.

(2)

Mw = 400.4

Figure pat00001

(3)

Mw = 456.5

Figure pat00002

[Chemical Formula 4]

Mw = 460.5

Figure pat00003

[Chemical Formula 5]

Mw = 516.6

Figure pat00004

[Chemical Formula 6]

Mw = 548.6

Figure pat00005

(7)

Mw = 606.6

Figure pat00006

[Chemical Formula 8]

Mw = 690.8

Figure pat00007

[Chemical Formula 9]

Mw = 696.7

Figure pat00008

[Chemical formula 10]

Mw = 780.9

Figure pat00009

(11)

Mw = 828.9

Figure pat00010

According to the present invention, the polarizing plate can be produced by the following method. The polarizer 112 and the polarizer 112 and the cellulose ester film as the polarizer protective film B 113 and 121 and the cellulose ester film as the polarizer protective film A 111 and 123 on the back side are combined with the polarizer and the cellulose ester film As a polarizing plate protective film can be produced.

More specifically, a step of obtaining a saponified cellulose ester film on the side bonded to the polarizer (first step); Immersing the polarizing film in a polyvinyl alcohol adhesive tank (second step); A step of lightly wiping off excess adhesive adhered to the polarizing film in the step 2, placing the cellulose ester film on the cellulose ester film treated in the step 1 (third step); Joining the cellulose ester film A 123, the polarizer 121 and the back side cellulose ester film B 121 laminated in the step 3 under a constant pressure (fourth step); And a sample obtained by bonding the polarizer 122, the cellulose ester film A (123) and the back side cellulose ester film B (121) prepared in the step 4 to a polarizing plate can be manufactured by drying.

1, polarizer protective film B (113, 121) is coated with a pressure-sensitive adhesive and laminated on a glass substrate.

In the cellulose ester polarizing plate protective film of the present invention, especially when the polarizing plate protective film B contains the plasticizer proposed in the present invention and is within the range of the thickness and degree of substitution of the cellulose ester film, the reliability of the polarizing plate before and after the reliability treatment of the polarizing plate is excellent Able to know.

In the VA-LCD according to the embodiment of the present invention, the polarizer protective film B is coated with a pressure-sensitive adhesive on the polarizing plate protective film B as described above, And then attaching an up / down polarizer. That is, the polarizing plate protective films A 111 and 123 and the polarizing plate protective films B 113 and 121 are bonded to the polarizers 112 and 122 and are attached to the upper and lower surfaces of the vertically aligned liquid crystal panel 100, respectively.

In the polarizing plate according to the present invention, VA-LCD satisfies the above-mentioned conditions (1) and (2) and the total sum Ro (Ro total ) of the retardation values in the plane direction satisfies the above- After being left for a period of time, the variation range of the contrast ratio can satisfy the condition of the expression (4).

[Equation 1]

Ro total = R - C + R LC

&Quot; (2) &quot;

40 nm < Rt total < 190 nm

In the formulas (1) and (2), R- C is the total retardation value in the plane direction of the negative C-plate satisfying the following equation (3)

&Quot; (3) &quot;

R- C = (plane retardation value of the polarizing plate inner cellulose ester film) + (plane retardation value of the biaxial A plate) + (plane retardation value of the negative C plate)

R LC is the retardation value in the plane direction of the liquid crystal of the vertically oriented panel, and Ro total is the sum of R LC and R C.

&Quot; (4) &quot;

? CR = {CR? Reliability? CR? Reliability?} / (CR? Reliability x 100 (%

Where CR is the white luminance / black luminance, which is the contrast ratio of the luminance when the LCD is in the black state and the luminance state is white.

When the VA-LCD is manufactured using the cellulose ester film containing the plasticizer proposed in the present invention in the constitution of the cellulose ester polarizing plate protective film of the present invention, particularly in the polarizing plate protective film B, the reliability of the contrast ratio before and after the reliability processing of the LCD great.

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are for illustrative purposes only and the present invention is not limited thereto.

Example 1

Preparation of Polarizer Protective Film A-Cellulose Ester Film

(1) Preparation of cellulose solution

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.

(2) Preparation of ultraviolet absorber solution

7.5 parts by weight of a mixed ultraviolet light absorber obtained by mixing Tinuvin 328 (manufactured by Ciba Specialty) and Tinuvin 326 (manufactured by Ciba Specialty) 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.

(3) Preparation of Diluted Cellulose Solution Containing Metal Oxide

The cellulose solution of 28.5 parts by weight of silica (SiO 2) 1.5 parts by weight of methylene chloride and methanol 9: Preparation of diluted cellulose solution by mixing 1 (weight ratio) parts of a mixed solvent of 70 parts by weight mixed with comprises silica (metal oxide) Respectively.

(4) Production of film of cellulose

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.

Preparation of Polarizer Protective Film B-Cellulose Ester Film

( 1) Preparation of cellulose solution (initiator solution)

For the cellulose ester, acetyl group of 2.1, butyryl group of 0.2 and total degree of substitution of 2.3 was used, and as a plasticizer, 2 parts by weight of a terminal asymmetric plasticizer having the following chemical formula 2 was used.

(2)

Figure pat00011

(2) Preparation of Dilute Solution Containing Metal Oxide

20.0 parts by weight of the cellulose solution, 1.5 parts by weight of silica (SiO 2 ), and 78.5 parts by weight of a mixed solvent obtained by mixing methylene chloride and methanol in a weight ratio of 9: 1 were mixed to prepare a dilute cellulose solution containing silica (metal oxide) Respectively.

(3) Production of film of cellulose

100 parts by mass of the main doping liquid and 5 parts by mass of the fine particulate addition liquid were added, sufficiently mixed (Doped A) by an inline mixer, and then uniformly plied to a stainless steel band support of 2000 mm in width using a belt smoothing device. The solvent was evaporated on the stainless steel band support and peeled off from the stainless band support. Then, both ends of the web were held with a tenter and stretched so that the draw ratio in the (TD) direction was 1.3 times in a temperature environment of 170 ° C. After the stretching, the stretching was maintained for a few seconds, the tensile force in the width direction was relaxed, the stretching was performed in the width direction, the stretching was continued for 35 minutes in the drying section set at 110 DEG C, A cellulose ester film having a thickness of 40 탆 and a polarizing plate protective film B having a knurling width of 10 mm and a height of 8 탆 was prepared.

The cellulose ester film thus obtained was a retardation film having an in-plane retardation value Ro of 40 to 60 nm and a retardation value Rth in the thickness direction of 110 to 140 nm according to the following measurement.

&Quot; (5) &quot;

Ro = (nx-ny) xd

Rth = ((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, nx &gt; = ny, , And d represents the thickness (nm) of the film. The retardation values Ro and Rth were measured at 590 nm under the environment of 23 ° C and 55% RH using an AxoScan (OPMF-1, Axometrics) optical measuring instrument.

Production of Polarizer

First, a polarizer was produced using the following PVA film.

(1) Polarizer: Production of PVA film

The polyvinyl alcohol film having a thickness of 120 占 퐉 was uniaxially stretched (temperature: 110 占 폚, stretching magnification: 5 times). This was immersed in an aqueous solution containing 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds and then immersed in an aqueous solution at 68 DEG C containing 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizer (PF-1).

(2) Production of Polarizer

Next, according to the following steps 1 to 5, the polarizer and the cellulose ester film as the polarizing plate protective film B and the cellulose ester as the polarizing plate protective film A were bonded to the back side as a polarizing plate protective film according to the following process To prepare a polarizing plate.

And immersed in a 2 mol / L sodium hydroxide solution at 60 DEG C for 90 seconds, followed by washing with water and drying to obtain a cellulose ester film in which the side bonded to the polarizer was saponified (Step 1).

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 2).

In step 2, the excess adhesive adhered to the polarizing film was lightly wiped off and placed on the cellulose ester film treated in step 1 (step 3).

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 a conveying speed of about 2 m / min (Step 4).

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

The prepared polarizer was coated with a pressure-sensitive adhesive on the B-side of the polarizing plate protective film, and then laminated on a glass substrate (100 in Fig. 1) 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 an environment of 23 ° C and 55% RH.

The polarizing plate laminated on the glass substrate 100 was allowed to stand for 500 hours in a reliable environment of 60 DEG C and 90% RH using a high temperature and high humidity chamber, taken out from the high temperature and high humidity chamber again, , And the change in polarization degree before and after the reliability environmental treatment was observed. As shown in Table 6, when the cellulose ester polarizing plate protective film of the present example contains the plasticizer proposed in the present invention, particularly in the polarizing plate protective film B and is within the range of the thickness and degree of substitution of the cellulose ester film, It was found that the reliability of the polarization degree before and after the treatment was excellent.

Manufacturing of VA-LCD

(1) A pressure-sensitive adhesive was coated on the polarizing plate protective film B side of the prepared polarizing plate (Pol-1), and then an upper / lower polarizing plate was attached so that the polarizing plate protective film B was directed toward the vertically- To produce a VA-LCD. The polarizer protective films A 111 and 123 and the polarizer protective films B 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 100, 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 100 is filled with a vertically aligned liquid crystal having negative dielectric anisotropy Δ∈ = -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. In this state, the luminance was measured in a black state and a white state using a BM-7 luminance meter under an environment of 23 ° C and 55% RH.

In the same manner, a vertical alignment -LCD was manufactured using a polarizing plate (Pol-2), and the luminance was measured using the same equipment under the same conditions.

The prepared VA-LCD was allowed to stand in a reliable environment at 60 ° C and 90% RH for 500 hours using a high temperature and high humidity chamber, and then taken out from the high temperature and high humidity chamber and subjected to the same equipment under conditions of 23 ° C. and 55% RH The brightness of the black and white states was measured to observe the change of the contrast ratio before and after the reliability environmental treatment. As shown in the results of Table 7, when the VA-LCD is manufactured using the cellulose ester film containing the plasticizer proposed in the present invention in the constitution of the cellulose ester polarizing plate protective film of the present invention, particularly in the polarizing plate protective film B, The reliability of the contrast ratio before and after the reliability process is excellent.

Examples 2 to 15

A cellulose ester film A was prepared in the same manner as in Example 1 except that the cellulose ester, the plasticizer, and the dope solution as shown in the following Tables 1 to 4 were used. Cellulose films (TF-40-1 and TF-60-1) having thicknesses of 40 and 60 mu m were formed by changing the thickness as shown in Table 5 in the same manner as in Example 1. 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. Further, the cellulose ester film B having the film thicknesses of 30, 40 and 50 탆 was prepared after the main dopes (B to E) were prepared as shown in Tables 1 to 4 below, and the properties of the polarizer thus produced were measured Was measured in the same manner as in Example 1 above.

The polarizers were prepared in the same manner as in Example 1 using the PVA film as shown in Table 5 below, and the reliability of the prepared polarizer was measured. The results are shown in Table 6 below.

The VA-LCD was manufactured in the same manner as in Example 1, and the results are shown in Table 7.

Dope Cellulose ester Plasticizer A A * A ** B B * A ** C C * A ** D D * A ** E E * A ** F A * B ** G E * B ** H A * C ** I E * C **

* See Table 2, ** See Table 3

Cellulose ester Acetyl group Propionyl group Butyryl group Total degree of substitution A 2.1 0 0.2 2.3 B 2.1 0 0.5 2.6 C 1.7 0 0.5 2.2 D 1.7 0 0.8 2.5 E 1.8 0.5 0 2.3

Plasticizer Type Compound structure A (terminal asymmetric plasticizer 1)

Figure pat00012
B (terminal symmetric plasticizer 1)
Figure pat00013
 C (end symmetric plasticizer 2)
Figure pat00014

Dof Cellulose ester Plasticizer A A (100 kg) A (10 kg) B B (100 kg) A (10 kg) C C (100 kg) A (10 kg) D D (100 kg) A (10 kg) E E (100 kg) A (10 kg) F A (100 kg) B (10kg) G E (100 kg) B (10kg) H A (100 kg) C (10 kg) I E (100 kg) C (10 kg)

division Polarizing plate protective film B
Cellulose ester film No. Dof Film thickness (占 퐉) Example 1 CF-40-1 A 40 Example 2 CF-40-2 B 40 Example 3 CF-40-3 C 40 Example 4 CF-40-4 D 40 Example 5 CF-40-5 E 40 Comparative Example 1 CF-40-6 F 40 Comparative Example 2 CF-40-7 G 40 Comparative Example 3 CF-40-8 H 40 Comparative Example 4 CF-40-9 I 40 Example 6 CF-30-1 A 30 Example 7 CF-30-2 B 30 Example 8 CF-30-3 C 30 Example 9 CF-30-4 D 30 Example 10 CF-30-5 E 30 Comparative Example 5 CF-30-6 F 30 Comparative Example 6 CF-30-7 H 30 Example 11 CF-50-1 A 50 Example 12 CF-50-2 B 50 Example 13 CF-50-3 C 50 Example 14 CF-50-4 D 50 Example 15 CF-50-5 E 50 Comparative Example 7 CF-50-6 G 50 Comparative Example 8 CF-50-7 I 50

Figure pat00015

Figure pat00016

Comparative Examples 1 to 8

A cellulose ester film A was prepared in the same manner as in Example 1 except that the cellulose ester, the plasticizer, and the dope solution as shown in Tables 1 to 4 were used. Cellulose films (TF-40-1 and TF-60-1) having thicknesses of 40 and 60 占 퐉 were prepared in the same manner as in Example 1 except that the thickness was changed as shown in Table 5. 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. The cellulose ester film B was prepared in the same manner as in Example 1, except that the main dope liquids (F to I) were prepared as shown in Tables 1 to 4, and then the cellulose ester film B was prepared.

The polarizers were prepared in the same manner as in Example 1 using the PVA film in the same manner as in Table 5, and the reliability of the prepared polarizer was measured. The results are shown in Table 6 above.

The VA-LCD was manufactured in the same manner as in Example 1, and the results are shown in Table 7.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined in the appended claims. There will be.

100: transparent glass substrate
110, 120: polarizer
111, 123: protective film A
113,121: Protective film B
112, 122: Polarizer

Claims (9)

A polarizing plate having a cellulose ester polarizing plate protective film (A) and a cellulose ester polarizing plate protective film (B) laminated on a polarizer is attached to the upper surface and the lower surface of the vertically aligned liquid crystal panel,
And a cellulose ester polarizing plate protective film (B) having a total degree of substitution of acyl groups of 2.10 to 2.70 between the vertically aligned liquid crystal panel and polarizing plates of the upper and lower sides, wherein the total sum (Ro total ) Satisfying the conditions of equations (1) and (2) and allowing the high-temperature and high-humidity chamber to stand in a reliability environment of 60 ° C and 90% RH for 500 hours, the variation range of the contrast ratio satisfies the following formula (4) Wherein the cellulose ester polarizing plate protective film (B) comprises an asymmetric ester compound having an aromatic group represented by the following formula (1).
[Equation 1]
Ro total = R - C + R LC
&Quot; (2) &quot;
40 nm < Rt total &lt; 190 nm
In the formulas (1) and (2), R- C is the total retardation value in the plane direction of the negative C-plate satisfying the following equation (3)
&Quot; (3) &quot;
R- C = (plane retardation value of the polarizing plate inner cellulose ester film) + (plane retardation value of the biaxial A plate) + (plane retardation value of the negative C plate)
R LC is the retardation value in the plane direction of the liquid crystal of the vertically oriented panel, and Ro total is the sum of R LC and R C.
&Quot; (4) &quot;
? CR = {CR? Reliability? CR? Reliability?} / (CR? Reliability x 100 (%
Where CR is the white luminance / black luminance, which is the contrast ratio of the luminance when the LCD is in the black state and the luminance state is white.
[Chemical Formula 1]
T + [D + P] n + D
T is a residue of a toluic acid or a benzenecarboxylic acid residue, D is a propyleneglycol having 2 to 8 carbon atoms, neopentylglycol, diethyleneglycol, dipropyleneglycol Triethylene glycol, an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, P is a phthalic acid having 2 to 10 carbon atoms Phthalic acid residue, an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms, or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more. The cellulose ester polarizing plate protective film according to claim 1, wherein the cellulose ester polarizing plate protective film A is cellulose triacetate having an acetyl group total degree of substitution of 2.7 or more, and the polarizer has polyvinyl alcohol and a film thickness of 3 to 30 탆. Type liquid crystal display device. The cellulose ester polarizing plate protective film B according to claim 1, wherein the in-plane retardation Ro and the thickness direction retardation Rth of the cellulose ester polarizing plate protective film B are respectively 40 to 60 nm and 110 to 140 nm, Display device.
&Quot; (5) &quot;
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 and is 23 DEG C and 55% RH, respectively, where d is the film thickness (nm), nx is the maximum refractive index in the horizontal direction in the film plane, Under the environment of 550 nm. A method for manufacturing a vertical alignment type liquid crystal display device by coating an adhesive on a polarizing plate protective film B side of a polarizing plate and attaching a polarizing plate so that the polarizing plate protective film B faces the vertical alignment panel,
Preparing a cellulose film of a polarizing plate protective film A having a thickness of 20 to 100 mu m by a conventional method;
A cellulose ester having an acyl group with a total substitution degree of 2.10 to 2.70, an asymmetric ester plasticizer containing an aromatic group represented by the following formula (1), a mixed solvent of methylene chloride and methanol, a dilute cellulose solution containing silica as a metal oxide Preparing a cellulose ester film of the polarizing plate protective film B by evaporating, stretching and drying the solvent;
Bonding the polarizing plate protective film A and the polarizing plate protective film B to one side of the polarizer of the polyvinyl alcohol polarizing film under a constant pressure; And
Wherein the polarizing plate protective film (A) and the polarizing plate protective film (B) are bonded to the upper and lower surfaces of the vertically aligned liquid crystal panel, respectively.
[Chemical Formula 1]
T + [D + P] n + D
T is a residue of a toluic acid or a benzenecarboxylic acid residue, D is a propyleneglycol having 2 to 8 carbon atoms, neopentylglycol, diethyleneglycol, dipropyleneglycol Triethylene glycol, an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, P is a phthalic acid having 2 to 10 carbon atoms Phthalic acid residue, an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms, or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more. 5. The method according to claim 4, wherein the cellulose solution comprises 10 to 30 parts by weight of a cellulose ester, 2 to 8 parts by weight of an asymmetric ester plasticizer containing an aromatic group represented by the general formula (1), methylene chloride and methanol at a weight ratio of 9: Wherein 2 to 10 parts by weight of silica is contained as a metal oxide with respect to 100 parts by weight of the main dope liquid mixed with 70 to 90 parts by weight of the mixed solvent. 5. The method of claim 4, wherein the polarizing plate protective film (B) has a thickness of 20 to 60 mu m. The polarizing plate protective film B according to claim 4, wherein the polarizing plate protective film B is a film also serving as a retardation plate having an in-plane retardation Ro of 40 to 60 nm and a thickness direction retardation Rth of 110 to 140 nm defined by the following equation A method of manufacturing a vertical alignment type liquid crystal display device.
&Quot; (5) &quot;
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 and is 23 DEG C and 55% RH, respectively, where d is the film thickness (nm), nx is the maximum refractive index in the horizontal direction in the film plane, Under the environment of 550 nm. The method according to claim 4, wherein the plasticizer is at least one of an asymmetric ester plasticizer having an aromatic structure represented by the following general formulas (2) to (11).
(2)
Figure pat00017
,
(3)
Figure pat00018
,
[Chemical Formula 4]
Figure pat00019
,
[Chemical Formula 5]
Figure pat00020
,
[Chemical Formula 6]
Figure pat00021
,
(7)
Figure pat00022
,
[Chemical Formula 8]
Figure pat00023
,
[Chemical Formula 9]
Figure pat00024
,
[Chemical formula 10]
Figure pat00025
,
(11)
Figure pat00026
. The liquid crystal display device according to claim 4, wherein the total liquid crystal display device satisfies the following conditions (1) and (2): Ro total of surface direction retardation values satisfies the following expressions Wherein the variation range of the contrast ratio satisfies the condition of the following expression (4).
[Equation 1]
Ro total = R - C + R LC
&Quot; (2) &quot;
40 nm < Rt total &lt; 190 nm
In the formulas (1) and (2), R- C is the total retardation value in the plane direction of the negative C-plate satisfying the following equation (3)
&Quot; (3) &quot;
R- C = (plane retardation value of the polarizing plate inner cellulose ester film) + (plane retardation value of the biaxial A plate) + (plane retardation value of the negative C plate)
R LC is the retardation value in the plane direction of the liquid crystal of the vertically oriented panel, and Ro total is the sum of R LC and R C.
&Quot; (4) &quot;
? CR = {CR? Reliability? CR? Reliability?} / (CR? Reliability x 100 (%
Where CR is the white luminance / black luminance, which is the contrast ratio of the luminance when the LCD is in the black state and the luminance state is white.
KR1020150191701A 2015-12-31 2015-12-31 Vertical orentation type liquid display device having an improved reliable property and improved contrast ratio and method for preparing the same KR101791320B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020150191701A KR101791320B1 (en) 2015-12-31 2015-12-31 Vertical orentation type liquid display device having an improved reliable property and improved contrast ratio and method for preparing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020150191701A KR101791320B1 (en) 2015-12-31 2015-12-31 Vertical orentation type liquid display device having an improved reliable property and improved contrast ratio and method for preparing the same

Publications (2)

Publication Number Publication Date
KR20170081024A true KR20170081024A (en) 2017-07-11
KR101791320B1 KR101791320B1 (en) 2017-10-30

Family

ID=59355076

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020150191701A KR101791320B1 (en) 2015-12-31 2015-12-31 Vertical orentation type liquid display device having an improved reliable property and improved contrast ratio and method for preparing the same

Country Status (1)

Country Link
KR (1) KR101791320B1 (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5140520B2 (en) 2008-08-27 2013-02-06 富士フイルム株式会社 Method for producing cellulose ester film, retardation film, polarizing plate using the same, and liquid crystal display device
JP6015469B2 (en) 2013-01-31 2016-10-26 コニカミノルタ株式会社 Optical film roll, polarizing plate, and liquid crystal display device
WO2014132691A1 (en) 2013-02-26 2014-09-04 コニカミノルタ株式会社 Polarizing sheet, polarizing sheet production method and liquid crystal display device

Also Published As

Publication number Publication date
KR101791320B1 (en) 2017-10-30

Similar Documents

Publication Publication Date Title
JP5720687B2 (en) Retardation film, polarizing plate using the same, and liquid crystal display device
TWI474078B (en) Liquid crystal display and method of manufacturing polarizer plate
KR101793793B1 (en) Polarizing plate having an improved reliable property and high degree of polarization and method for preparing the same
KR101791320B1 (en) Vertical orentation type liquid display device having an improved reliable property and improved contrast ratio and method for preparing the same
KR101793348B1 (en) Vertical orentation type liquid display device having an improved reliable property and improved contrast ratio and method for preparing the same
KR101791321B1 (en) Vertical orentation type liquid display device having an improved reliable property and improved contrast ratio and method for preparing the same
KR20180071440A (en) Cellulose ester film, polarizing plate and liquid crystal display using the same
KR101878776B1 (en) Liquid crystal display including cellulose ester phase difference film
KR101665285B1 (en) An optical film having improved optical reliability
KR101793794B1 (en) Polarizing plate having an improved reliable property and high degree of polarization at high temperature/humidity condition and method for preparing the same
KR101807375B1 (en) Polarizing plate having an improved reliable property and high degree of polarization at high temperature/humidity condition and method for preparing the same
KR101807385B1 (en) An polarizer having improved optical reliability
KR101793795B1 (en) Polarizing plate having an improved reliable property and high degree of polarization at high temperature/humidity condition and method for preparing the same
KR101742422B1 (en) Polarizing plate protective film and the polarizing plate using the same
KR101791327B1 (en) LCD having excellent reliability at high-temperature, high-humidity
JPWO2012008242A1 (en) Liquid crystal display
KR101828365B1 (en) Polarization plate including cellulose ester phase difference film
KR101684810B1 (en) Cellulose ester film having an improved barrier property at high temperature/humidity condition and method for preparing the same
KR101684809B1 (en) Cellulose ester film having an improved reliable property at high temperature/humidity condition and method for preparing the same
KR101716117B1 (en) Cellulose ester phase difference film
JP5692237B2 (en) Retardation film, polarizing plate using the same, and liquid crystal display device
KR101787482B1 (en) Cellulose ester film for liquid crystal phase difference substrate film
KR101716123B1 (en) Cellulose ester phase difference film
KR20170009618A (en) In-plane switching liquid crystal display including cellulose ester phase difference film
KR20170009623A (en) In-plane switching liquid crystal display including cellulose ester phase difference film

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant