KR101716122B1

KR101716122B1 - Cellulose ester phase difference film

Info

Publication number: KR101716122B1
Application number: KR1020150102128A
Authority: KR
Inventors: 김영수; 김경수; 김용원; 하선영; 이유미; 이호준; 강혁모
Original assignee: 주식회사 효성
Priority date: 2015-07-20
Filing date: 2015-07-20
Publication date: 2017-03-14
Also published as: KR20170010462A

Abstract

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

Description

Cellulose ester phase difference film < RTI ID = 0.0 >

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

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

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

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

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

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

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

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

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

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

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

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a cellulose ester phase difference film capable of improving reliability quality in the production of a polarizing plate by including a resin and additives capable of improving high- .

In order to achieve the above object, the present invention provides a cellulose ester having an acetyl group substitution degree of 2.70 to 2.95; And an asymmetric ester compound having an aromatic group represented by the following formula (1).

[Chemical Formula 1]

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

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

M _A is an aryl having a carbon number of 6 or more monocarboxylic acid residue, D _O represents an alkylene glycol residue, D _A is an aryl dicarboxylic acid residue as a compound having a carbon number of 6 ~ 2, n represents an integer of 1 or more.

At this time, the cellulose ester phase difference film preferably has an effective retardation value Reff of 30 to 30 nm, which is defined by the following formula (1) measured under conditions of 23 ° C and 55% RH.

[Equation 1]

Reff = (nx'- ny ') xd

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

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

The present invention having such a constitution can improve the reliability quality of the cellulose ester phase difference film of the present invention when the polarizing plate is manufactured by including the resin and the additive which can improve the high temperature and high humidity reliability.

Fig. 1 is a view showing an effective surface direction formed from nx, ny and nz when measuring Reff according to the present invention.

Hereinafter, the present invention will be described.

The cellulose ester phase difference film according to the present invention is a cellulose ester having an acetyl group substitution degree of 2.70 to 2.95; And an asymmetric ester compound containing an aromatic group represented by the following formula (1).

[Chemical Formula 1]

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

At this time, the cellulose ester phase difference film of the present invention is a plasticizer and includes an asymmetric ester-based compound having an aromatic group represented by the general formula (1). It is particularly preferable that the optical reliability properties of the cellulose ester film before and after the reliability treatment are set within a predetermined range by including the asymmetric ester compound containing the aromatic group.

Specific examples of such aromatic-containing asymmetric ester compounds include, but are not limited to, the following formulas (2) to (4).

(2)

(3)

[Chemical Formula 4]

Meanwhile, the cellulose ester phase difference film according to the present invention can be produced by solution casting method. In the solution film forming method, the cellulose ester is dissolved in an additive such as a plasticizer, a UV absorber, a matting agent, etc. and a mixed solvent such as methylene chloride and methanol to prepare a dope, which can be filtered using a filtration apparatus.

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

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

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

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

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

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

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

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

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

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

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

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

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

[Equation 1]

Reff = (nx'- ny ') xd

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

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

Example One

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

For cellulose esters, triacetylcellulose having an average degree of acetyl substitution (DS) of 2.86 was used, and a cellulose as a plasticizer was prepared using a terminal asymmetric plasticizer A represented by the following formula as a plasticizer.

<Step 2> Preparation of Dilute Solution Containing Metal Oxide

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

&Lt; Step 3 > Preparation of cellulose ester film

100 parts by mass of the initiator solution and 5 parts by mass of the fine particle additive solution were added, and sufficiently mixed with an inline mixer to prepare a dope. At this time, the composition of the dope was 72 wt% of methylene chloride, 8 wt% of methanol, 17.95 wt% of cellulose ester, 2 wt% of plasticizer and 0.05 wt% of silica. Thereafter, the belt was softened uniformly on a stainless steel band support having a width of 2000 mm by using a flexible machine. Then, the solvent was evaporated on the stainless band support to peel off from the stainless band support. Then, both ends of the web were gripped with a tenter and stretched so that the stretching magnification in the (TD) direction in the temperature environment of 170 ° C was 1.1 times. Thereafter, the stretching was maintained for a few seconds while maintaining the width, , And the film was transported for 35 minutes in a drying zone set at 110 캜 for drying for 35 minutes to produce a cellulose ester film having a thickness of 20 탆 and a knurling width of 1900 mm and a width of 10 mm and a height of 8 탆 at the end.

Example 2

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

Example 3

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

Example 4

A cellulose ester film was prepared in the same manner as in Example 1, except that the plasticizer was changed to 10 parts by weight instead of 5 parts by weight in the preparation of the cellulose ester film.

Example 5

A cellulose ester film was prepared in the same manner as in Example 2, except that the plasticizer was changed to 10 parts by weight instead of 5 parts by weight in the preparation of the cellulose ester film.

Example 6

A cellulose ester film was prepared in the same manner as in Example 3, except that the plasticizer was changed to 10 parts by weight in place of 5 parts by weight in the preparation of the cellulose ester film.

Example 7

A cellulose ester film was prepared in the same manner as in Example 1 except that the plasticizer was changed to 10 parts by weight instead of 5 parts by weight and the film thickness was changed to 25 占 퐉 in the preparation of the cellulose ester film.

Comparative Example One

A cellulose ester film was produced in the same manner as in Example 1, except that the terminal symmetric plasticizer B represented by the following formula was used as a plasticizer.

Comparative Example 2

A cellulose ester film was prepared in the same manner as in Example 1, except that a terminal symmetric plasticizer C represented by the following formula was used as a plasticizer.

Comparative Example 3

A cellulose ester film was prepared in the same manner as in Example 1 except that a terminal symmetric plasticizer D represented by the following formula was used as a plasticizer.

Experimental Example One

The optical properties of the cellulose ester films prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.

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

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

Cellulose ester Plasticizer Type Film thickness
(um) Reliability Before / After Reff (nm) Kinds Addition amount
(kg) Kinds Additive amount (kg) Before processing After processing Variation Example 1 TAC 100 A 5 20 13.2 11.7 -1.5 Example 2 TAC 100 A 5 30 22.5 16.4 -6.1 Example 3 TAC 100 A 5 40 27.4 23.8 -3.6 Example 4 TAC 100 A 10 20 12.9 8.5 -4.4 Example 5 TAC 100 A 10 30 18.4 16.4 -2 Example 6 TAC 100 A 10 40 28.2 20.9 -7.3 Example 7 TAC 100 A 10 25 15.8 12.7 -3.1 Comparative Example 1 TAC 100 B 10 40 38.9 26.1 -12.8 Comparative Example 2 TAC 100 C 10 40 28.6 14.3 -14.3 Comparative Example 3 TAC 100 D 10 40 27.3 11.7 -15.6

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

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

Claims

A cellulose ester having an acetyl group substitution degree of 2.70 to 2.95; And
1. A cellulose ester phase difference film comprising an asymmetric ester compound having an aromatic group represented by the following formula (1), wherein the cellulose ester phase difference film has a film thickness of 20 to 40 탆 and measured under conditions of 23 캜 and 55% RH The retardation value Reff defined by the formula (1) is 12.9 to 28.2 nm, and the Reff variation amount? Reff before and after the storage is maintained at 60 占 폚 and 90% RH for 500 hours is -1.5 to -7.3 lt; RTI ID = 0.0 > nm. < / RTI >

[Chemical Formula 1]
_{M A - [D O -D A} ] nD O
In Formula _{1, M A: R 1 -COOH} , D O: HO-R 2 -OH, D A: HOOC-R 1 is -COOH, M _A is a carbon number of 6 or more aryl monocarboxylic acid residues, D _O Represents an alkylene glycol residue, D _A represents an aryldicarboxylic acid residue, and n represents an integer of 1 or more.
[Equation 1]
Reff = (nx'- ny ') xd
In the above formula (1), d is the thickness (nm) of the film, and nx 'and ny' are formed from nx, ny and nz when observed at the positions of? = 45 ° and? Is an effective surface refractive index value.

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