KR101791321B1 - 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

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KR101791321B1
KR101791321B1 KR1020150191710A KR20150191710A KR101791321B1 KR 101791321 B1 KR101791321 B1 KR 101791321B1 KR 1020150191710 A KR1020150191710 A KR 1020150191710A KR 20150191710 A KR20150191710 A KR 20150191710A KR 101791321 B1 KR101791321 B1 KR 101791321B1
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polarizing plate
film
protective film
quot
cellulose ester
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KR20170081027A (en
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김영수
김경수
김용원
하선영
이유미
이호준
강혁모
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주식회사 효성
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    • 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—

Abstract

The present invention relates to a cellulose ester phase retardation film produced by solution casting comprising a low molecular weight asymmetric ester compound having an aromatic group represented by the following formula (1) and a low molecular weight symmetrical ester compound containing an aromatic group represented by the following formula And a method of manufacturing the liquid crystal display device.
[Chemical Formula 1]
T + [D] n
(2)
T + [D] n + T
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, 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 specifically, the present invention relates to a cellulose ester phase retardation film produced by a solution casting method, wherein the cellulose ester phase difference film comprises a low molecular weight asymmetric ester compound having an aromatic group represented by the following formula (1) and a low molecular weight symmetrical ester The present invention relates to a vertical alignment type liquid crystal display device having excellent reliability of a contrast ratio including a compound, and a method of manufacturing the same.

[Chemical Formula 1]

T + [D] n

(2)

T + [D] n + T

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, 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 (also referred to as a VA (Vertical Alignment) type) LCD using vertical alignment type liquid crystal (liquid crystal having a negative dielectric anisotropy) has superior viewing angle characteristics In point, it is widely used.

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 described below disclose that the front contrast ratio is increased by the configuration 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.

Japanese Laid-Open Patent Publication No. 2010-54736

 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) Characterized in that the cellulose ester phase difference film produced by the casting method comprises a low molecular weight asymmetric ester compound having an aromatic group represented by the following formula 1 and a low molecular weight symmetrical ester compound containing an aromatic group represented by the formula 2 The liquid crystal display device is a vertical alignment type liquid crystal display device.

[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_Receive-CR_reliability transfer} / CR_reliability transfer x 100 (%)) <± 20%

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] n

(2)

T + [D] n + T

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, and n represents an integer of 1 or more .

In order to improve the high temperature and high humidity reliability of the cellulose ester phase difference film, the vertical alignment type liquid crystal display device according to the present invention comprises a low molecular weight asymmetric ester compound having an aromatic group represented by Formula 1 and an aromatic group represented by Formula 2 , The contrast ratio is not lowered even when exposed to a high temperature and high humidity environment, 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 a low molecular weight asymmetric ester compound having an aromatic group represented by the following formula (1) and a low molecular weight symmetrical ester compound having an aromatic group represented by the following formula (2).

[Chemical Formula 1]

T + [D] n

(2)

T + [D] n + T

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, 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 a low molecular weight 2 to 8 parts by weight of a plasticizer containing an asymmetric ester compound and a low molecular weight symmetrical ester compound containing an aromatic group represented by the general formula (2), 70 to 90 parts by weight of a mixed solvent in which methylene chloride and methanol are mixed at a weight ratio of 9: 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 Rth 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, which is obtained by reacting a low molecular weight asymmetric ester compound containing an aromatic group represented by the above formula (1) and a low molecular substance containing an aromatic group represented by the formula Based symmetrical ester compound and is particularly preferable in setting the barrier properties of the cellulose ester film before and after the reliability treatment to a predetermined range.

The present invention relates to a low molecular weight asymmetric ester compound containing an aromatic group of the present invention and a low molecular weight symmetrical ester compound of the following general formula (8) to (12) But is not limited thereto.

(3)

Mw = 194.2

Figure 112015129521257-pat00001

[Chemical Formula 4]

Mw = 222.3

Figure 112015129521257-pat00002

[Chemical Formula 5]

Mw = 224.3

Figure 112015129521257-pat00003

[Chemical Formula 6]

Mw = 252.4

Figure 112015129521257-pat00004

(7)

Mw = 268.3

Figure 112015129521257-pat00005

[Chemical Formula 8]

Mw = 312.3

Figure 112015129521257-pat00006

[Chemical Formula 9]

Mw = 340.4

Figure 112015129521257-pat00007

[Chemical formula 10]

Mw = 342.4

Figure 112015129521257-pat00008

(11)

Mw = 370.5

Figure 112015129521257-pat00009

[Chemical Formula 12]

Mw = 386.5

Figure 112015129521257-pat00010

According to the present invention, the polarizing plate can be produced by the following method. The polarizer 122 and the cellulose ester film as the polarizing plate protective film B (113 and 121) and the cellulose ester as the polarizing plate 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 attached to the upper and lower surfaces of the vertically aligned liquid crystal panel 10, 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

&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  One

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)

As 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 formulas 3 and 8 was used.

(3)

Figure 112015129521257-pat00011

[Chemical Formula 8]

Figure 112015129521257-pat00012

(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 obtained cellulose ester film was a retardation film having an in-plane retardation value R o of 40 to 60 nm and a retardation value R t in the thickness direction of 110 to 140 nm according to the following measurement.

&Quot; (5) &quot;

R o = (n x -n y ) x d

R t = ((n x + n y ) / 2 - n z ) x d

Wherein n x , n y and n z represent refractive indices of principal axes x, y and z of the refractive index ellipsoid respectively, n x and n y represent refractive indices in the in-plane direction of the film and n z represent refractive indices N x? N y , and d represents the thickness (nm) of the film. The retardation values R o and R t were measured at a wavelength of 590 nm under an 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

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

And 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 cellulose ester film which was saponified at the side bonded to the polarizer (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 10 is packed 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.

Example  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 Tables 1 to 3 were used. Cellulose films (TF-40-1 and TF-60-1) having thicknesses of 40 and 60 탆 were formed by the same method as in Example 1 except that the thickness was changed as shown in Table 4. 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. In addition, the cellulose ester film B having the film thicknesses of 30, 40 and 50 탆 was prepared after the main dope liquids (B to E) were prepared as shown in Tables 1 to 3, and the properties of the polarizer plate 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 4 below, and the reliability of the prepared polarizer was measured. The results are shown in Table 5 below.

The VA-LCD was manufactured in the same manner as in Example 1, and the results are shown in Table 6. &lt; tb &gt; &lt; TABLE &gt;

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

* 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 low molecular weight plasticizer 1)

Figure 112015129521257-pat00013
B (terminal asymmetric low molecular weight plasticizer 1)
Figure 112015129521257-pat00014
 C (terminal symmetric plasticizer 1)
Figure 112015129521257-pat00015
 D (terminal symmetric plasticizer 2)
Figure 112015129521257-pat00016

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 112015129521257-pat00017

Figure 112015129521257-pat00018

Comparative Example  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 3, and then the cellulose ester film B was prepared.

A polarizing plate was produced in the same manner as in Example 1 using the PVA film in the same manner as in Table 4, and the reliability of the prepared polarizing plate was measured. The results are shown in Table 5 above.

The VA-LCD was manufactured in the same manner as in Example 1, and the results are shown in Table 6. &lt; tb &gt; &lt; TABLE &gt;

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: vertically aligned liquid crystal panel substrate 110: lower polarizer plate
120: upper polarizer 111, 123: polarizer protective film A
112, 122: Polarizer 113, 121: Polarizing plate protective film B
a - Absorption axis of the polarizer b - S-axis of the A-plate

Claims (9)

A polarizing plate in which a cellulose ester polarizing plate protective film (A) and a cellulose ester polarizing plate protective film (B) are laminated around a polarizer is attached to the upper surface and the lower surface of the vertically aligned liquid crystal panel,
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 panel and the upper and lower polarizing plates, wherein the total sum (Ro total ) of the retardation values in the plane direction satisfies the following formula 1 and 2, and allowed to stand for 500 hours in a high-temperature and high-humidity chamber at a temperature of 60 ° C and a 90% RH reliability, 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 at least one of the following formulas 3 to 7 and a symmetrical ester compound having an aromatic group represented by at least one of the following formulas 8 to 12 Wherein the liquid crystal display device is a vertical alignment type liquid crystal display device.
[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.
(3)
Figure 112017054793101-pat00030
,
[Chemical Formula 4]
Figure 112017054793101-pat00031
,
[Chemical Formula 5]
Figure 112017054793101-pat00032
,
[Chemical Formula 6]
Figure 112017054793101-pat00033
,
(7)
Figure 112017054793101-pat00034
,
[Chemical Formula 8]
Figure 112017054793101-pat00035
,
[Chemical Formula 9]
Figure 112017054793101-pat00036
,
[Chemical formula 10]
Figure 112017054793101-pat00037
,
(11)
Figure 112017054793101-pat00038
,
[Chemical Formula 12]
Figure 112017054793101-pat00039
. 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 R o of the cellulose ester polarizer protective film B is 40 to 60 nm and the thickness direction retardation R t is 110 to 140 nm, Type liquid crystal display device.
&Quot; (5) &quot;
Ro = (nx-ny) xd
Rt = ((nx + ny) / 2-nz) xd
Herein, nx, ny and nz represent refractive indices of principal axes x, y and z of the refractive index ellipsoid, 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, , d represents the thickness (nm) of the film, and is a value measured at a wavelength of 550 nm under an environment of 23 deg. C and 55% RH. A method for manufacturing a vertical alignment type liquid crystal display device by coating a polarizer protective film B side with a pressure sensitive adhesive on a polarizing plate and then 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 in the range of 20 to 100 mu m;
A cellulose ester having a total degree of substitution of an acyl group of 2.10 to 2.70, an asymmetric ester compound containing an aromatic group represented by at least one of the following formulas (3) to (7) and a symmetrical ester containing an aromatic group represented by at least one of The cellulose ester film of the polarizing plate protective film B is produced through the process of softening from a dilute cellulose solution containing silica as a mixed solvent of methylene chloride and methanol as a metal oxide, silica, evaporating, stretching and drying the solvent step;
Bonding the polarizing plate protective film A and the other surface of the polarizing plate protective film B to one side of the polarizer 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.
(3)
Figure 112017054793101-pat00040
,
[Chemical Formula 4]
Figure 112017054793101-pat00041
,
[Chemical Formula 5]
Figure 112017054793101-pat00042
,
[Chemical Formula 6]
Figure 112017054793101-pat00043
,
(7)
Figure 112017054793101-pat00044
,
[Chemical Formula 8]
Figure 112017054793101-pat00045
,
[Chemical Formula 9]
Figure 112017054793101-pat00046
,
[Chemical formula 10]
Figure 112017054793101-pat00047
,
(11)
Figure 112017054793101-pat00048
,
[Chemical Formula 12]
Figure 112017054793101-pat00049
. The cellulose solution according to claim 4, wherein the cellulose solution contains 10 to 30 parts by weight of a cellulose ester, an asymmetric ester compound having an aromatic group represented by at least one of the above formulas 3 to 7 and an aromatic group represented by at least one of formulas 8 to 12 , 2 to 8 parts by weight of a plasticizer containing a symmetrical ester compound, and 70 to 90 parts by weight of a mixed solvent of methylene chloride and methanol mixed at a weight ratio of 9: 1 were mixed with 100 parts by weight of the main dope, 2 to 10 parts by weight based on 100 parts by weight of the liquid crystal composition. 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 R o of 40 to 60 nm and a retardation R th in the thickness direction of 110 to 140 nm defined by the following equation Wherein the liquid crystal display device is a vertical alignment type liquid crystal display device.
&Quot; (5) &quot;
R o = (n x -n y ) x d
R t = ((n x + n y ) / 2 - n z ) x d
Herein, nx, ny and nz represent refractive indices of principal axes x, y and z of the refractive index ellipsoid, 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, , d represents the thickness (nm) of the film, and is a value measured at a wavelength of 550 nm under an environment of 23 deg. C and 55% RH.
delete 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.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010054736A (en) 2008-08-27 2010-03-11 Fujifilm Corp Retardation film and polarizing plate using the same, liquid crystal display device
JP2014149325A (en) 2013-01-31 2014-08-21 Konica Minolta Inc Method for manufacturing optical film, method for manufacturing polarizing plate and method for manufacturing 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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010054736A (en) 2008-08-27 2010-03-11 Fujifilm Corp Retardation film and polarizing plate using the same, liquid crystal display device
JP2014149325A (en) 2013-01-31 2014-08-21 Konica Minolta Inc Method for manufacturing optical film, method for manufacturing polarizing plate and method for manufacturing 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

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