WO2014104519A1 - Method for manufacturing polarizing plate, polarizing plate manufactured by same, and optical display device including same - Google Patents

Method for manufacturing polarizing plate, polarizing plate manufactured by same, and optical display device including same Download PDF

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Publication number
WO2014104519A1
WO2014104519A1 PCT/KR2013/006818 KR2013006818W WO2014104519A1 WO 2014104519 A1 WO2014104519 A1 WO 2014104519A1 KR 2013006818 W KR2013006818 W KR 2013006818W WO 2014104519 A1 WO2014104519 A1 WO 2014104519A1
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Prior art keywords
polarizing plate
film
polyvinyl alcohol
polarizer
organic acid
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PCT/KR2013/006818
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French (fr)
Korean (ko)
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신직수
김도원
김종훈
김진숙
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제일모직 주식회사
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Publication of WO2014104519A1 publication Critical patent/WO2014104519A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a method of manufacturing a polarizing plate, a polarizing plate manufactured therefrom, and an optical display device including the same.
  • the organic light emitting display device does not require a polarizing plate due to self emission.
  • a polarizing plate is included to compensate for the disadvantage that the luminance is reduced due to reflection of external light by the Al plate of the OLED driving panel.
  • the polarizing plate has a structure in which a protective film such as a triacetyl cellulose-based film is laminated on a polarizer with an aqueous adhesive made of a polyvinyl alcohol-based aqueous solution.
  • a polarizer a polarizer having a structure in which a polyvinyl alcohol-based molecular chain is aligned in a predetermined direction and includes an iodine compound or a dichroic polarizer is used.
  • the polarizer which has a polyene structure which has a polyvinylene structure by the dehydration reaction of a polyvinyl alcohol film is used.
  • a polarizer including an iodine compound or a dichroic polarizing material has a problem in that polarization performance is high but durability is low when the polarizer is a thin film.
  • Polyene type polarizer is excellent also in the case of a thin film.
  • the manufacturing process of a polyene polarizer includes the process of immersing and swelling a polyvinyl alcohol-type film in hydrochloric acid. Such acid treatment process is basically to be included for polyenization, there is a problem that the production process is complicated and the polarizer manufacturing cost increases.
  • Another object of the present invention is to provide a method for producing a polarizing plate including a polyene polarizer having a polarizing performance and excellent durability as a thin film form.
  • Still another object of the present invention is to provide a polarizing plate manufactured by the manufacturing method and an optical display device including the same.
  • a method of manufacturing a polarizing plate may include preparing a polyvinyl alcohol-based film including an organic acid, and dehydrating and dry stretching the polyvinyl alcohol-based film to prepare a polyene polarizer.
  • the polarizing plate which is another aspect of this invention can be manufactured by the said manufacturing method.
  • an optical display device may include the polarizing plate.
  • the present invention provides a method for producing a polarizing plate including a polyene polarizer which eliminates the need for an acid treatment step of a polyvinyl alcohol-based film.
  • the present invention provides a method of manufacturing a polarizing plate comprising a polyene polarizer having a polarizing performance in the form of a thin film.
  • FIG. 1 is a cross-sectional view of a polarizing plate of an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of an optical display device according to an exemplary embodiment of the present invention.
  • the method of manufacturing a polarizing plate according to an embodiment of the present invention may include preparing a polyvinyl alcohol-based film including an organic acid and dehydrating and dry stretching the polyvinyl alcohol-based film including an organic acid to prepare a polyene polarizer. Can be.
  • the organic acid may be included in the polyvinyl alcohol-based film and used as a dehydration accelerator in the dehydration reaction for polyenylation of polyvinyl alcohol. That is, since the polyvinyl alcohol-based film already contains an organic acid, a process of additionally acid-processing the polyvinyl alcohol-based film during the polyene polarizer manufacturing process is not required.
  • the organic acid is low in volatility, so that even with a small amount of organic acid, polyenylation can be sufficiently achieved, so that it is not necessary to remove the acid later in the polarizer and can be easily removed even if there is an acid.
  • an acid catalyst may be used as a dehydration accelerator for dehydration of polyvinyl alcohol to polyenize.
  • Hydrochloric acid has a problem that temperature and humidity control is necessary because of the instability of acid concentration in the film due to volatility, and when polyvinyl alcohol-based film has to be manufactured in a thin film, it is difficult to polyenize polyvinyl alcohol-based film in a general oven. There is this.
  • sulfuric acid may lower the transmittance of the final polarizer produced and difficult to remove acid may lower the heat resistance reliability of the polarizing plate.
  • phosphoric acid requires 20 parts by weight or more based on 100 parts by weight of polyvinyl alcohol-based resin in order to polyenize the polyvinyl alcohol, and there is a problem in that acid removal is difficult after polyenylation.
  • the production method according to an embodiment of the present invention used an organic acid as an acid catalyst.
  • the organic acid has a low volatility, so that the acid concentration in the polyvinyl alcohol-based film can be kept constant during the dehydration reaction, can be combined with a polyvinyl alcohol resin, and the acid can be easily removed after polyenylation.
  • the organic acid may be included in about 5% by weight or less, specifically about 0.5 to 5% by weight, more specifically about 4 to 4.9% by weight of the polyvinyl alcohol-based film. In the above range, the polyvinyl alcohol of the polyvinyl alcohol can be sufficient and can be easily removed from the final polarizer to prevent the acid left in the polarizer.
  • the organic acid may comprise sulfonic acids of aromatic hydrocarbons.
  • the sulfonic acid of the aromatic hydrocarbon has low volatility, so that the acid concentration may be maintained constant during the dehydration reaction, may be combined with a polyvinyl alcohol resin, and the acid may be easily removed after polyenylation.
  • the organic acid may be an aromatic hydrocarbon sulfonic acid having 6 to 20 carbon atoms, toluene sulfonic acid, for example, para toluene sulfonic acid or a mixture containing the same.
  • the polyvinyl alcohol-based film including an organic acid may be prepared using a polyvinyl alcohol-based resin solution and a polyvinyl alcohol-based resin solution containing an organic acid.
  • the degree of polymerization of the polyvinyl alcohol-based resin may be about 2000 or more, specifically about 2600 to 4000. In the above range, there may be no problem that the film breaks even in the wet stretching of the film.
  • the saponification degree of the polyvinyl alcohol-based resin may be about 99 mol% or more, specifically about 99 to 99.9 mol%. In the above range, there may be an effect capable of excellent durability and high stretching.
  • the organic acid may be included in about 5 parts by weight or less, specifically about 0.5 to 5 parts by weight, and more specifically about 4 to 5 parts by weight, based on 100 parts by weight of the polyvinyl alcohol-based resin. Within this range, the polyenylated polyvinyl alcohol can be made sufficiently and can be easily removed to prevent the acid from remaining in the polarizer.
  • the polyvinyl alcohol resin solution may further include a conventional solvent in addition to the polyvinyl alcohol resin and the organic acid.
  • a conventional solvent in addition to the polyvinyl alcohol resin and the organic acid.
  • it may include water, an organic solvent, and the like.
  • Polyvinyl alcohol-based film containing an organic acid can be produced by a conventional film production process using a polyvinyl alcohol-based resin solution.
  • the polyvinyl alcohol-based resin solution may be coated on a substrate to prepare the substrate as an integrated body.
  • a thin polyvinyl alcohol-based film can be produced, and the film can be prevented from breaking during subsequent stretching, and a thin polyvinyl alcohol-based film or a polyene polarizer can be produced.
  • the "substrate integrated type” may mean a state in which a polyvinyl alcohol-based film including a free acid is laminated on one or both surfaces of the base film.
  • the base film is a polyolefin-based, polyethylene-terephthalate or polyethylenenaphthalate, including polypropylene-based, cellulose-based, acrylic-based, cyclic polyolefin-based (COP) -based, polycarbonate-containing triacetylcellulose (TAC), etc.
  • the thickness of the film may be about 5 to 500 ⁇ m, and the base film may be removed after wet stretching, but a laminate of the base film and the polyene polarizer may be a polarizing plate without removing the base film after wet stretching.
  • the laminate of the substrate integrated may have a thickness of about 5 to 500 ⁇ m, specifically about 5 to 100 ⁇ m. Within this range, it is possible to prevent the break during stretching and to produce a thin polarizer.
  • the polyvinyl alcohol-based film including the organic acid may have a thickness of about 5 ⁇ m to 100 ⁇ m, specifically about 5 ⁇ m to 30 ⁇ m. In the above range, it can be used for the polarizing plate application, it is possible to prevent the break during stretching and to produce a thin polarizer.
  • the polyene polarizer may be prepared by dehydrating and dry stretching a polyvinyl alcohol-based film including an organic acid.
  • Dehydration may comprise polyenylating polyvinyl alcohol in the presence of an organic acid that is a dehydration catalyst.
  • Dehydration and dry stretching can be performed simultaneously. That is, dehydration process can be carried out while dry-stretching the polyvinyl alcohol-type film containing an organic acid. Through this, it is possible to obtain a stretching effect together with the polyenization effect by dehydration.
  • dehydration and dry stretching may comprise treating a polyvinyl alcohol-based film comprising an organic acid at about 100 ° C. or greater, specifically about 100 to 160 ° C. Within this range, sufficient dehydration effect can be obtained.
  • dehydration and dry stretching may comprise treating the polyvinyl alcohol-based film comprising organic acid for about 1 to 10 minutes. Within this range, sufficient dehydration effect can be obtained.
  • dry stretching can include stretching the polyvinyl alcohol-based film at a draw ratio of about 2 to 6 times. In the above range, there may be an effect of improving the orientation of the polyvinyl alcohol-based resin.
  • the method of manufacturing a polarizing plate according to an embodiment of the present invention may further include performing a wet stretching process of the dry stretched polyvinyl alcohol-based film after the dry stretching step. Wet stretching can fix the double bonds of the polyene and provide a crosslinking effect.
  • wet stretching can be performed in an aqueous boric acid solution.
  • the aqueous boric acid solution can be an aqueous solution of about 1 to 10 weight percent boric acid. In the above range, the double bond immobilization effect of the polyene may be good.
  • the stretching ratio may be about 1 times or more, specifically about 1 to 1.5 times, based on the polyvinyl alcohol-based film subjected to dry stretching. In the above range, there may be a stretching effect of the polyvinyl alcohol-based film.
  • the total draw ratio by dry stretching and wet drawing can be about 6 to 8 times that of the original polyvinyl alcohol-based film. In the above range, there may be an effect on the optical properties of the thin high performance polarizing film.
  • Wet stretching may include treating at about 60 ° C. or higher, specifically about 60 to 85 ° C. Within this range, the immobilization effect of the double bond can be obtained together with the stretching effect.
  • Polarizing plate manufacturing method may further comprise the step of removing the organic acid from the polyene polarizer. This is because when the organic acid remains in the polarizer, the polarization performance of the polarizer can be changed at high temperature.
  • the method may include immersing the polyene polarizer in an aqueous inorganic solution such as water, a weak alkaline water solution, and saline solution.
  • the polarizing plate manufacturing method according to an embodiment of the present invention may further include the step of drying the polyene polarizer.
  • the method may comprise treating the polyene polarizer at about 80 ° C. or higher, specifically 80 to 120 ° C. for about 1 to 10 minutes.
  • Polarizing plate manufacturing method may not include the step of dyeing the polyvinyl alcohol-based film with iodine or dichroic dye.
  • the polarizer may have polarization performance even if it does not contain iodine or dichroic dye.
  • the polarizing plate manufacturing method may further include removing the base film from the laminate of the wet stretched base film and the polyene polarizer.
  • the base film may be removed by attaching a release film to the opposite side of the base film and then removing both the base film and the release film.
  • the integrated film of the base film and the polyene polarizer can be used as a polarizing plate without removing the base film from the laminate of the finally stretched base film and the polyene polarizer.
  • the thickness of the polyene polarizer may be about 5 ⁇ m or less, specifically about 1 to 5 ⁇ m. In the above range, the polarizing plate can be used, and a thin effect can be obtained. In general, as the thickness of the polyene polarizer decreases, the degree of polarization decreases, but the polyene polarizer of the present invention can maintain high polarization degree even with a thin thickness.
  • the content of iodine or dichroic pigment in the polyene polarizer may be about 0.3% by weight or less, specifically about 0 to 0.3% by weight.
  • the polyene polarizer of this invention can fully implement a polarizing effect, even if it does not contain a dichroic dye. If the content of iodine or dichroic dye in the polyene polarizer exceeds 0.3% by weight, the transmittance of the polarizing plate may be reduced.
  • the content of the organic acid in the polyene polarizer may be about 0.001 wt% or less, specifically about 0 to 0.001 wt%. In the above range, it may not lower the polarization performance of the polyene polarizer.
  • Polarizing plate manufacturing method may further comprise the step of laminating an optical film on at least one surface of the polyene polarizer.
  • the optical film may include one or more of a protective film or a retardation film.
  • the optical film is a cellulose-based, tritere-based cellulose (TAC) or the like, polyester-based, such as polyethylene terephthalate (PET), acrylic, cyclic polyolefin (COP) -based, polycarbonate-based, polyether
  • TAC tritere-based cellulose
  • PET polyethylene terephthalate
  • COP cyclic polyolefin
  • polycarbonate-based polyether
  • the film may be made of at least one of sulfone, polysulfone, polyamide, polyimide, polyolefin, polyarylate, polyvinyl alcohol, polyvinyl chloride, and polyvinylidene chloride.
  • the thickness of the optical film may be about 20 to 100 ⁇ m. In the said range, it can use for a polarizing plate use.
  • the optical film may be laminated on the polyene polarizer by conventional methods.
  • the optical film may be laminated with a polarizing plate adhesive, for example, a polyvinyl alcohol-based water-based adhesive or a pressure-sensitive adhesive.
  • the adhesive layer may have a thickness of about 80 to 200 nm.
  • Another polarizing plate of the present invention is a polyene polarizer; And it may include an optical film or a base film formed on one side or both sides of the polarizer.
  • the optical film may include one or more of a conventional protective film or a retardation film, and the base film is a base film that has been used in manufacturing a polyene polarizer.
  • the polarizing plate 100 includes a polyene polarizer 10; A first optical film 20 formed on an upper surface of the polyene polarizer 10; And a second optical film 30 formed on the lower surface of the polyene polarizer 10.
  • the polarizing plate may have a change in polarization degree (PE) represented by Equation 1 below about 3%, specifically about 0.1 to 2.9%:
  • A is the initial degree of polarization of the polarizing plate
  • B is the polarization degree of the polarizing plate after leaving the polarizing plate for 500 hours at 80 °C and 90% relative humidity conditions).
  • the degree of polarization depends only on the polarizer and is hardly affected by the protective film.
  • the polarizing plate may have a transmittance of about 42.5% or more, specifically about 43 to 45%. Within this range, it is possible to use the optical display device with high transmittance.
  • the transmittance may be a value measured at a wavelength of 380 nm to 780 nm, but is not limited thereto.
  • the base film is used in the production of a polyene polarizer, and a polyolefin-based, polyethylene terephthalate or polyethylenenaphthalate, including polypropylene-based, and the like, and a cellulose-based triacetyl cellulose (TAC).
  • TAC cellulose-based triacetyl cellulose
  • the thickness of the base film may be controlled by stretching during the production of the polyene polarizer, the thickness may be about 20 to 200 ⁇ m. In the said range, it can use for a polarizing plate use.
  • an optical display device may include the polarizing plate.
  • the optical display device may include, but is not limited to, an organic light emitting diode (OLED) display device.
  • OLED organic light emitting diode
  • 2 is a cross-sectional view of an optical display device according to an exemplary embodiment of the present invention. Referring to FIG. 2, an optical display device includes an OLED panel 200; And a polarizer 110 formed on the OLED panel 200.
  • aqueous PVA resin solution containing 100 parts by weight of PVA (polyvinyl alcohol, polymerization degree 2600, saponification degree 99.9 mol%) resin and 5 parts by weight of organic acid (pTSA, p-toluenesulfonic acid) was coated on the A-PET base film to have a thickness of 15 ⁇ m.
  • the PVA film containing the organic acid of the substrate integrated type was produced.
  • the produced film was dry-stretched 4 times at hot air circulation type OVEN 140 degreeC. Subsequently, it was immersed in a 5 wt% aqueous solution of boric acid for 2 minutes, and 1.5-fold wet stretching was simultaneously performed at 85 ° C. After drying at 80 ° C. OVEN for 3 minutes, the substrate film was removed to prepare a polarizer having a polyene structure having a thickness of 5 ⁇ m (measured by Mitutoyo Micrometer).
  • a polarizer was prepared in the same manner as in Example 1, except that polymerization degree 3300 PVA resin was used instead of polymerization degree 2600 PVA resin.
  • a polarizer was prepared in the same manner as in Example 1 except that a polymerization degree of 4000 PVA resin was used instead of a polymerization degree of 2600 PVA resin.
  • a PVA resin aqueous solution containing 100 parts by weight of a PVA (polymerization degree 3300, saponification degree 99.9 mol%) resin was coated on an A-PET film to prepare a PVA film having a substrate integral type having a thickness of 15 ⁇ m.
  • the film thus prepared was immersed in an aqueous hydrochloric acid solution for 2 minutes, acid treated, 4 times dry stretched, and dehydrated for 2 minutes. 2 minutes immersion and 1.5 times wet drawing were performed simultaneously at 85 degreeC in 5 wt% boric-acid aqueous solution.
  • the polarizer which has a thickness of 5 micrometers polyene structure was produced by drying for 3 minutes at 80 degreeC OVEN.
  • a PVA resin aqueous solution containing 100 parts by weight of a PVA (polymerization degree 3300, saponification degree 99.9 mol%) resin was coated on an A-PET film to prepare a PVA film having a substrate integral type having a thickness of 15 ⁇ m.
  • the polarizer which has a 5-micrometer-thick polyene structure was obtained by dyeing the produced film to the iodine type compound, extending
  • a triacetyl cellulose film (Konica Co., Ltd. 40tac), which is a protective film, was attached to both surfaces of the polarizers prepared in Examples and Comparative Examples to prepare a polarizing plate. The following physical properties were evaluated about the manufactured polarizing plate.
  • Transmittance (%) and polarization degree (%) It measured using V-7100 (JASCO Corporation, Japan) about a polarizing plate.
  • the polarization degree was measured using V-7100 (JASCO, Japan). The initial polarization degree A of the polarizing plate was measured. After the polarizing plate was allowed to stand at 80 ° C. and 90% relative humidity (RH) for 500 hours, the polarization degree (B) was measured for the polarizing plate. Reliability was evaluated by the rate of change of polarization degree
  • the polarizing plate manufactured with the polarizer of the present invention had a good transmittance and polarization degree even with a thin film thickness polarizer, good reliability and good durability, and does not include an acid treatment step in the manufacturing method, so that the manufacturing process is It was simple.
  • the polarizing plate of Comparative Example 1 prepared by the conventional hydrochloric acid treatment process has a problem that the acid treatment process is required and cumbersome.
  • the polarizing plate of Comparative Example 2 including a polarizer dyed with conventional iodine was not good reliability and poor durability.

Abstract

The present invention relates to a method for manufacturing a polarizing plate including a step of manufacturing a polyvinyl alcohol-based film containing an organic acid and manufacturing a polyene polarizer by dehydrating and dry stretching the polyvinyl alcohol-based film. The present invention also relates to a polarizing plate manufactured by same and to an optical display device including same.

Description

편광판의 제조방법, 이로부터 제조된 편광판 및 이를 포함하는 광학표시장치Method for manufacturing polarizing plate, polarizing plate manufactured therefrom and optical display device comprising same
본 발명은 편광판의 제조 방법, 이로부터 제조된 편광판 및 이를 포함하는 광학표시장치에 관한 것이다.The present invention relates to a method of manufacturing a polarizing plate, a polarizing plate manufactured therefrom, and an optical display device including the same.
유기발광표시장치는 자체 발광으로 편광판을 필요로 하지 않는다. 그러나, OLED 구동 패널의 Al 판에 의해 외부광 반사로 휘도가 떨어지는 단점을 보완하기 위해 편광판을 포함한다. 편광판은 편광자에 트리아세틸셀룰로오스계 필름 등의 보호필름을 폴리비닐알콜계 수용액으로 이루어진 수계 접착제로 합지시킨 구조를 갖는다. 편광자로 폴리비닐알콜계 분자 사슬이 일정 방향으로 배향되고 요오드계 화합물 또는 이색성 편광물질을 포함하는 구조를 갖는 편광자가 사용된다. 또는 폴리비닐알콜 필름의 탈수 반응으로 폴리비닐렌 구조를 갖는 폴리엔(polyene) 구조를 갖는 편광자가 사용되고 있다.The organic light emitting display device does not require a polarizing plate due to self emission. However, a polarizing plate is included to compensate for the disadvantage that the luminance is reduced due to reflection of external light by the Al plate of the OLED driving panel. The polarizing plate has a structure in which a protective film such as a triacetyl cellulose-based film is laminated on a polarizer with an aqueous adhesive made of a polyvinyl alcohol-based aqueous solution. As a polarizer, a polarizer having a structure in which a polyvinyl alcohol-based molecular chain is aligned in a predetermined direction and includes an iodine compound or a dichroic polarizer is used. Or the polarizer which has a polyene structure which has a polyvinylene structure by the dehydration reaction of a polyvinyl alcohol film is used.
요오드계 화합물 또는 이색성 편광물질을 포함하는 편광자는 편광자가 박막일 경우 편광 성능은 높지만 내구성이 낮다는 문제점이 있다. 폴리엔형 편광자는 박막의 경우에도 내구성은 우수하다. 그러나, 폴리엔 편광자의 제조 과정은 폴리비닐알콜계 필름을 염산에서 침지하고 팽윤시키는 과정을 포함한다. 이러한 산 처리 공정은 폴리엔화를 위해 기본적으로 포함되어야 하는 것으로 생산 공정이 복잡해지고 편광자 제조 비용이 상승한다는 문제점이 있다.A polarizer including an iodine compound or a dichroic polarizing material has a problem in that polarization performance is high but durability is low when the polarizer is a thin film. Polyene type polarizer is excellent also in the case of a thin film. However, the manufacturing process of a polyene polarizer includes the process of immersing and swelling a polyvinyl alcohol-type film in hydrochloric acid. Such acid treatment process is basically to be included for polyenization, there is a problem that the production process is complicated and the polarizer manufacturing cost increases.
본 발명의 목적은 폴리비닐알콜계 필름의 산 처리 공정이 필요없게 하는 폴리엔 편광자를 포함하는 편광판의 제조방법을 제공하는 것이다.It is an object of the present invention to provide a method for producing a polarizing plate including a polyene polarizer which eliminates the need for an acid treatment step of a polyvinyl alcohol-based film.
본 발명의 다른 목적은 박막 형태로서 편광 성능을 가지며 내구성이 좋은 폴리엔 편광자를 포함하는 편광판의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing a polarizing plate including a polyene polarizer having a polarizing performance and excellent durability as a thin film form.
본 발명의 또 다른 목적은 상기 제조방법으로 제조된 편광판 및 이를 포함하는 광학표시장치를 제공하는 것이다.Still another object of the present invention is to provide a polarizing plate manufactured by the manufacturing method and an optical display device including the same.
본 발명의 일 관점인 편광판의 제조 방법은 유기산을 포함하는 폴리비닐알콜계 필름을 제조하고, 상기 폴리비닐알콜계 필름을 탈수 및 건식 연신하여 폴리엔 편광자를 제조하는 단계를 포함할 수 있다.According to an aspect of the present invention, a method of manufacturing a polarizing plate may include preparing a polyvinyl alcohol-based film including an organic acid, and dehydrating and dry stretching the polyvinyl alcohol-based film to prepare a polyene polarizer.
본 발명의 다른 관점인 편광판은 상기 제조 방법으로 제조될 수 있다.The polarizing plate which is another aspect of this invention can be manufactured by the said manufacturing method.
본 발명의 또 다른 관점인 광학표시장치는 상기 편광판을 포함할 수 있다.In another aspect of the present invention, an optical display device may include the polarizing plate.
본 발명은 폴리비닐알콜계 필름의 산 처리 공정이 필요없게 하는 폴리엔 편광자를 포함하는 편광판의 제조방법을 제공하였다. 또한, 본 발명은 박막 형태로 편광 성능을 갖는 폴리엔 편광자를 포함하는 편광판의 제조방법을 제공하였다.The present invention provides a method for producing a polarizing plate including a polyene polarizer which eliminates the need for an acid treatment step of a polyvinyl alcohol-based film. In addition, the present invention provides a method of manufacturing a polarizing plate comprising a polyene polarizer having a polarizing performance in the form of a thin film.
도 1은 본 발명 일 실시예의 편광판의 단면도이다.1 is a cross-sectional view of a polarizing plate of an embodiment of the present invention.
도 2는 본 발명 일 실시예의 광학표시장치의 단면도이다.2 is a cross-sectional view of an optical display device according to an exemplary embodiment of the present invention.
첨부한 도면을 참고하여 실시예에 의해 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 동일 또는 유사한 구성 요소에 대해서는 동일한 도면 부호를 붙였다. 본 명세서에서, '상부'와 '하부'는 도면을 기준으로 정의한 것으로, 보는 시각에 따라 '상부'가 하부'로, '하부'가 '상부'로 변경될 수 있다.DETAILED DESCRIPTION Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification. In the present specification, 'upper' and 'lower' are defined based on the drawings, and according to the viewing time, 'upper' may be changed to 'lower' and 'lower' may be changed to 'upper'.
본 발명 일 실시예에 따른 편광판의 제조방법은 유기산을 포함하는 폴리비닐알콜계 필름을 제조하고, 유기산을 포함하는 폴리비닐알콜계 필름을 탈수 및 건식 연신하여 폴리엔 편광자를 제조하는 단계를 포함할 수 있다.The method of manufacturing a polarizing plate according to an embodiment of the present invention may include preparing a polyvinyl alcohol-based film including an organic acid and dehydrating and dry stretching the polyvinyl alcohol-based film including an organic acid to prepare a polyene polarizer. Can be.
(1) 유기산을 포함하는 폴리비닐알콜계 필름 제조(1) Preparation of polyvinyl alcohol-based film containing organic acid
유기산은 폴리비닐알콜계 필름에 포함되어 폴리비닐알콜의 폴리엔화를 위한 탈수 반응에서 탈수 촉진제로 사용할 수 있다. 즉, 폴리비닐알콜계 필름이 유기산을 이미 포함하고 있으므로 폴리엔 편광자 제조 과정 중 폴리비닐알콜계 필름을 추가적으로 산 처리하는 공정이 필요하지 않는다. 또한, 유기산은 휘발성이 낮아 소량의 유기산으로도 폴리엔화를 충분히 달성할 수 있어 추후 편광자에서 산 제거를 할 필요가 없고 산이 있더라도 쉽게 제거될 수 있다.The organic acid may be included in the polyvinyl alcohol-based film and used as a dehydration accelerator in the dehydration reaction for polyenylation of polyvinyl alcohol. That is, since the polyvinyl alcohol-based film already contains an organic acid, a process of additionally acid-processing the polyvinyl alcohol-based film during the polyene polarizer manufacturing process is not required. In addition, the organic acid is low in volatility, so that even with a small amount of organic acid, polyenylation can be sufficiently achieved, so that it is not necessary to remove the acid later in the polarizer and can be easily removed even if there is an acid.
일반적으로, 폴리비닐알콜을 탈수 반응시켜 폴리엔화하기 위한 탈수 촉진제로서 산 촉매를 사용할 수 있다. 염산은 휘발성으로 인해 필름 내에서 산 농도가 불안정하여 온도와 습도 제어가 필요하다는 문제점이 있고, 폴리비닐알콜계 필름을 박막으로 제조하여야 할 때 일반 오븐에서는 폴리비닐알콜계 필름의 폴리엔화가 어렵다는 문제점이 있다. 또한, 황산은 최종 제조된 편광자의 투과율이 저하될 수 있고 산 제거가 어려워 편광판의 내열 신뢰성이 저하될 수 있다. 또한, 인산은 폴리비닐알콜을 폴리엔화하기 위해 폴리비닐알콜계 수지 100중량부에 대해 20중량부 이상이 필요하며 폴리엔화 후에 산 제거가 어렵다는 문제점이 있다.In general, an acid catalyst may be used as a dehydration accelerator for dehydration of polyvinyl alcohol to polyenize. Hydrochloric acid has a problem that temperature and humidity control is necessary because of the instability of acid concentration in the film due to volatility, and when polyvinyl alcohol-based film has to be manufactured in a thin film, it is difficult to polyenize polyvinyl alcohol-based film in a general oven. There is this. In addition, sulfuric acid may lower the transmittance of the final polarizer produced and difficult to remove acid may lower the heat resistance reliability of the polarizing plate. In addition, phosphoric acid requires 20 parts by weight or more based on 100 parts by weight of polyvinyl alcohol-based resin in order to polyenize the polyvinyl alcohol, and there is a problem in that acid removal is difficult after polyenylation.
반면에, 본 발명의 일 실시예에 따른 제조 방법은 산 촉매로서 유기산을 사용하였다. 유기산은 휘발성이 낮아 탈수 반응시 폴리비닐알콜계 필름 중 산 농도가 일정하게 유지되도록 할 수 있고, 폴리비닐알콜 수지와의 조합도 가능하며, 폴리엔화 후에 산 제거가 용이하다는 장점이 있다. 구체예에서, 유기산은 폴리비닐알콜계 필름 중 약 5중량% 이하, 구체적으로 약 0.5 내지 5중량%, 더 구체적으로 약 4 내지 4.9중량%로 포함될 수 있다. 상기 범위에서, 폴리비닐알콜의 폴리엔화가 충분히 되도록 할 수 있고 최종 제조된 편광자에서 쉽게 제거될 수 있어 편광자에 산이 남는 것을 막을 수 있다.On the other hand, the production method according to an embodiment of the present invention used an organic acid as an acid catalyst. The organic acid has a low volatility, so that the acid concentration in the polyvinyl alcohol-based film can be kept constant during the dehydration reaction, can be combined with a polyvinyl alcohol resin, and the acid can be easily removed after polyenylation. In embodiments, the organic acid may be included in about 5% by weight or less, specifically about 0.5 to 5% by weight, more specifically about 4 to 4.9% by weight of the polyvinyl alcohol-based film. In the above range, the polyvinyl alcohol of the polyvinyl alcohol can be sufficient and can be easily removed from the final polarizer to prevent the acid left in the polarizer.
유기산은 방향족 탄화수소의 술폰산을 포함할 수 있다. 방향족 탄화수소의 술폰산은 휘발성이 낮아 탈수 반응시 산 농도가 일정하게 유지될 수 있고, 폴리비닐알콜 수지와의 조합도 가능하며, 폴리엔화 후에 산 제거가 용이하다는 효과가 있을 수 있다. 구체적으로, 유기산은 탄소수 6 내지 20의 방향족 탄화수소 술폰산으로서, 톨루엔 술폰산, 예를 들면 파라 톨루엔 술폰산 또는 이를 포함하는 혼합물을 사용할 수 있다.The organic acid may comprise sulfonic acids of aromatic hydrocarbons. The sulfonic acid of the aromatic hydrocarbon has low volatility, so that the acid concentration may be maintained constant during the dehydration reaction, may be combined with a polyvinyl alcohol resin, and the acid may be easily removed after polyenylation. Specifically, the organic acid may be an aromatic hydrocarbon sulfonic acid having 6 to 20 carbon atoms, toluene sulfonic acid, for example, para toluene sulfonic acid or a mixture containing the same.
유기산을 포함하는 폴리비닐알콜계 필름은 폴리비닐알콜계 수지와 유기산을 포함하는 폴리비닐알콜계 수지 용액을 사용하여 제조될 수 있다. 폴리비닐알콜계 수지의 중합도는 약 2000 이상, 구체적으로 약 2600 내지 4000이 될 수 있다. 상기 범위에서, 필름의 습식 연신에도 필름이 파단되는 문제점이 없을 수 있다. 폴리비닐알콜계 수지의 검화도는 약 99mol% 이상, 구체적으로 약 99 내지 99.9mol%가 될 수 있다. 상기 범위에서, 내구성이 우수하고 고연신이 가능한 효과가 있을 수 있다. 유기산은 폴리비닐알콜계 수지 100중량부에 대해 약 5중량부 이하, 구체적으로 약 0.5 내지 5중량부, 더 구체적으로 약 4 내지 5중량부로 포함될 수 있다. 상기 범위에서, 폴리비닐알콜의 폴리엔화가 충분히 되도록 할 수 있고 쉽게 제거될 수 있어 편광자에 산이 남는 것을 막을 수 있다.The polyvinyl alcohol-based film including an organic acid may be prepared using a polyvinyl alcohol-based resin solution and a polyvinyl alcohol-based resin solution containing an organic acid. The degree of polymerization of the polyvinyl alcohol-based resin may be about 2000 or more, specifically about 2600 to 4000. In the above range, there may be no problem that the film breaks even in the wet stretching of the film. The saponification degree of the polyvinyl alcohol-based resin may be about 99 mol% or more, specifically about 99 to 99.9 mol%. In the above range, there may be an effect capable of excellent durability and high stretching. The organic acid may be included in about 5 parts by weight or less, specifically about 0.5 to 5 parts by weight, and more specifically about 4 to 5 parts by weight, based on 100 parts by weight of the polyvinyl alcohol-based resin. Within this range, the polyenylated polyvinyl alcohol can be made sufficiently and can be easily removed to prevent the acid from remaining in the polarizer.
폴리비닐알콜계 수지 용액은 폴리비닐알콜계 수지, 유기산 이외에 통상의 용매를 더 포함할 수 있다. 예를 들면, 물, 유기 용매 등을 포함할 수 있다. 유기산을 포함하는 폴리비닐알콜계 필름은 폴리비닐알콜계 수지 용액을 사용하여 통상의 필름 제조 공정으로 제조될 수 있다. 구체적으로, 폴리비닐알콜계 수지 용액을 기재에 코팅하여 기재 일체형으로 제조될 수 있다. 폴리비닐알콜계 필름을 기재 일체형으로 제조함으로써 박형의 폴리비닐알콜계 필름을 제조할 수 있고 추후 연신시 필름이 파단되는 것을 막을 수 있고, 박형의 폴리비닐알콜계 필름 또는 폴리엔 편광자를 제조하게 할 수 있다. 상기 "기재 일체형"은 유리산을 포함하는 폴리비닐알콜계 필름이 기재 필름의 일면 또는 양면에 적층된 상태를 의미할 수 있다. 기재 필름은 폴리프로필렌계 등을 포함하는 폴리올레핀계, 폴리에틸렌테레프탈레이트 또는 폴리에틸렌나프탈레이트 등을 폴리에스테르계 트리아세틸셀룰로오스(TAC) 등을 포함하는 셀룰로오스계, 아크릴계, 고리형 폴리올레핀(COP)계, 폴리카보네이트계, 폴리에테르술폰계, 폴리술폰계, 폴리아미드계, 폴리이미드계, 폴리아릴레이트계, 폴리비닐알코올계, 폴리염화비닐계, 폴리염화비닐리덴계 등이 될 수 있지만, 이에 제한되지 않고, 기재필름의 두께는 약 5 내지 500㎛가 될 수 있고, 기재필름은 습식 연신 후 제거될 수도 있지만, 습식 연신 후 기재필름을 제거하지 않고 기재필름과 폴리엔 편광자의 적층체가 편광판이 될 수도 있다. 기재 일체형의 적층체는 두께가 약 5 내지 500㎛, 구체적으로 약 5 내지 100㎛가 될 수 있다. 상기 범위에서, 연신시 파단을 막을 수 있고 박형의 편광자를 제조할 수 있다.The polyvinyl alcohol resin solution may further include a conventional solvent in addition to the polyvinyl alcohol resin and the organic acid. For example, it may include water, an organic solvent, and the like. Polyvinyl alcohol-based film containing an organic acid can be produced by a conventional film production process using a polyvinyl alcohol-based resin solution. Specifically, the polyvinyl alcohol-based resin solution may be coated on a substrate to prepare the substrate as an integrated body. By manufacturing a polyvinyl alcohol-based film as a substrate, a thin polyvinyl alcohol-based film can be produced, and the film can be prevented from breaking during subsequent stretching, and a thin polyvinyl alcohol-based film or a polyene polarizer can be produced. Can be. The "substrate integrated type" may mean a state in which a polyvinyl alcohol-based film including a free acid is laminated on one or both surfaces of the base film. The base film is a polyolefin-based, polyethylene-terephthalate or polyethylenenaphthalate, including polypropylene-based, cellulose-based, acrylic-based, cyclic polyolefin-based (COP) -based, polycarbonate-containing triacetylcellulose (TAC), etc. The polyether sulfone series, polysulfone series, polyamide series, polyimide series, polyarylate series, polyvinyl alcohol series, polyvinyl chloride series, polyvinylidene chloride series, and the like, but are not limited thereto. The thickness of the film may be about 5 to 500 μm, and the base film may be removed after wet stretching, but a laminate of the base film and the polyene polarizer may be a polarizing plate without removing the base film after wet stretching. The laminate of the substrate integrated may have a thickness of about 5 to 500 μm, specifically about 5 to 100 μm. Within this range, it is possible to prevent the break during stretching and to produce a thin polarizer.
유기산을 포함하는 폴리비닐알콜계 필름의 두께는 약 5㎛ 내지 100㎛, 구체적으로 약 5㎛ 내지 30㎛가 될 수 있다. 상기 범위에서, 편광판 용도로 사용될 수 있고 연신시 파단을 막을 수 있고 박형의 편광자를 제조할 수 있다.The polyvinyl alcohol-based film including the organic acid may have a thickness of about 5 μm to 100 μm, specifically about 5 μm to 30 μm. In the above range, it can be used for the polarizing plate application, it is possible to prevent the break during stretching and to produce a thin polarizer.
(2)폴리엔 편광자의 제조(2) Production of polyene polarizer
폴리엔 편광자는 유기산을 포함하는 폴리비닐알콜계 필름을 탈수 및 건식(dry) 연신시켜 제조될 수 있다. 탈수는 폴리비닐알콜을 탈수 촉매인 유기산 존재 하에 폴리엔화하는 단계를 포함할 수 있다.The polyene polarizer may be prepared by dehydrating and dry stretching a polyvinyl alcohol-based film including an organic acid. Dehydration may comprise polyenylating polyvinyl alcohol in the presence of an organic acid that is a dehydration catalyst.
탈수와 건식 연신은 동시에 수행될 수 있다. 즉, 유기산을 포함하는 폴리비닐알콜계 필름을 건식 연신하는 중에 탈수 처리할 수 있다. 이를 통해 탈수 에 의한 폴리엔화 효과와 함께 연신 효과를 동시에 얻을 수 있다.Dehydration and dry stretching can be performed simultaneously. That is, dehydration process can be carried out while dry-stretching the polyvinyl alcohol-type film containing an organic acid. Through this, it is possible to obtain a stretching effect together with the polyenization effect by dehydration.
구체예에서, 탈수와 건식 연신은 유기산을 포함하는 폴리비닐알콜계 필름을 약 100℃ 이상, 구체적으로 약 100 내지 160℃에서 처리하는 단계를 포함할 수 있다. 상기 범위에서, 충분한 탈수 효과를 얻을 수 있다.In embodiments, dehydration and dry stretching may comprise treating a polyvinyl alcohol-based film comprising an organic acid at about 100 ° C. or greater, specifically about 100 to 160 ° C. Within this range, sufficient dehydration effect can be obtained.
구체예에서, 탈수와 건식 연신은 유기산을 포함하는 폴리비닐알콜계 필름을 약 1 내지 10분 동안 처리하는 단계를 포함할 수 있다. 상기 범위에서, 충분한 탈수 효과를 얻을 수 있다.In embodiments, dehydration and dry stretching may comprise treating the polyvinyl alcohol-based film comprising organic acid for about 1 to 10 minutes. Within this range, sufficient dehydration effect can be obtained.
구체예에서, 건식 연신은 폴리비닐알콜계 필름을 연신비 약 2 내지 6배로 연신하는 단계를 포함할 수 있다. 상기 범위에서, 폴리비닐알콜계 수지의 배향성을 향상시키는 효과가 있을 수 있다.In an embodiment, dry stretching can include stretching the polyvinyl alcohol-based film at a draw ratio of about 2 to 6 times. In the above range, there may be an effect of improving the orientation of the polyvinyl alcohol-based resin.
본 발명의 일 실시예에 따른 편광판 제조 방법은 건식 연신 단계 이후에, 건식 연신된 폴리비닐알콜계 필름을 습식(wet) 연신 처리하는 단계를 더 포함할 수 있다. 습식 연신은 폴리엔의 이중 결합을 고정시키고 가교 효과를 제공할 수 있다.The method of manufacturing a polarizing plate according to an embodiment of the present invention may further include performing a wet stretching process of the dry stretched polyvinyl alcohol-based film after the dry stretching step. Wet stretching can fix the double bonds of the polyene and provide a crosslinking effect.
습식 연신은 붕산 수용액에서 수행될 수 있다. 구체예에서, 붕산 수용액은 붕산 약 1 내지 10중량%의 수용액이 될 수 있다. 상기 범위에서, 폴리엔의 이중 결합 고정화 효과가 좋을 수 있다.Wet stretching can be performed in an aqueous boric acid solution. In an embodiment, the aqueous boric acid solution can be an aqueous solution of about 1 to 10 weight percent boric acid. In the above range, the double bond immobilization effect of the polyene may be good.
습식 연신에서 연신비는 건식 연신을 거친 폴리비닐알콜계 필름에 대해 약 1배 이상, 구체적으로 약 1 내지 1.5배가 될 수 있다. 상기 범위에서, 폴리비닐알콜계필름의 연신 효과가 있을 수 있다. 건식 연신과 상기 습식 연신에 의한 전체 연신비는 최초 폴리비닐알콜계 필름에 대해 약 6 내지 8배가 될 수 있다. 상기 범위에서, 박형 고기능 편광막의 광학 특성에 효과가 있을 수 있다.In wet stretching, the stretching ratio may be about 1 times or more, specifically about 1 to 1.5 times, based on the polyvinyl alcohol-based film subjected to dry stretching. In the above range, there may be a stretching effect of the polyvinyl alcohol-based film. The total draw ratio by dry stretching and wet drawing can be about 6 to 8 times that of the original polyvinyl alcohol-based film. In the above range, there may be an effect on the optical properties of the thin high performance polarizing film.
습식 연신은 약 60℃ 이상, 구체적으로 약 60 내지 85℃에서 처리하는 단계를 포함할 수 있다. 상기 범위에서, 연신 효과와 함께 이중결합의 고정화 효과를 얻을 수 있다.Wet stretching may include treating at about 60 ° C. or higher, specifically about 60 to 85 ° C. Within this range, the immobilization effect of the double bond can be obtained together with the stretching effect.
본 발명의 일 실시예에 따른 편광판 제조 방법은 폴리엔 편광자에서 유기산을 제거하는 단계를 더 포함할 수 있다. 유기산이 편광자에 남을 경우 고온에서 편광자의 편광 성능을 변화시킬 수 있기 때문이다. 구체예에서, 폴리엔 편광자를 물, 약알칼리수 용액, 식염수 등의 무기물 수용액에 침지하는 단계를 포함할 수 있다. Polarizing plate manufacturing method according to an embodiment of the present invention may further comprise the step of removing the organic acid from the polyene polarizer. This is because when the organic acid remains in the polarizer, the polarization performance of the polarizer can be changed at high temperature. In an embodiment, the method may include immersing the polyene polarizer in an aqueous inorganic solution such as water, a weak alkaline water solution, and saline solution.
본 발명의 일 실시예에 따른 편광판 제조 방법은 폴리엔 편광자를 건조시키는 단계를 더 포함할 수 있다. 구체예에서, 폴리엔 편광자를 약 80℃ 이상, 구체적으로 80 내지 120℃에서 약 1 내지 10분 동안 처리하는 단계를 포함할 수 있다.The polarizing plate manufacturing method according to an embodiment of the present invention may further include the step of drying the polyene polarizer. In embodiments, the method may comprise treating the polyene polarizer at about 80 ° C. or higher, specifically 80 to 120 ° C. for about 1 to 10 minutes.
본 발명의 일 실시예에 따른 편광판 제조 방법은 폴리비닐알콜계 필름을 요오드 또는 이색성 색소로 염색하는 단계를 포함하지 않을 수 있다. 요오드 또는 이색성 색소를 포함하지 않더라도 상기 편광자는 편광 성능을 가질 수 있다.Polarizing plate manufacturing method according to an embodiment of the present invention may not include the step of dyeing the polyvinyl alcohol-based film with iodine or dichroic dye. The polarizer may have polarization performance even if it does not contain iodine or dichroic dye.
본 발명의 일 실시예에 따른 편광판 제조 방법은 습식 연신된 기재 필름과 폴리엔 편광자의 적층체로부터 기재필름을 제거하는 단계를 더 포함할 수 있다. 기재필름 제거는 기재 필름의 반대편에 이형필름을 접착한 후 기재 필름과 이형필름을 모두 제거하는 방법 등으로 수행될 수 있다.The polarizing plate manufacturing method according to an embodiment of the present invention may further include removing the base film from the laminate of the wet stretched base film and the polyene polarizer. The base film may be removed by attaching a release film to the opposite side of the base film and then removing both the base film and the release film.
또한, 최종 연신된 기재 필름과 폴리엔 편광자의 적층체로부터 기재필름을 제거하지 않고, 기재필름과 폴리엔 편광자의 일체형을 편광판으로도 사용할 수 있 다.In addition, the integrated film of the base film and the polyene polarizer can be used as a polarizing plate without removing the base film from the laminate of the finally stretched base film and the polyene polarizer.
폴리엔 편광자의 두께는 약 5㎛ 이하, 구체적으로 약 1 내지 5㎛가 될 수 있다. 상기 범위에서, 편광판 용도로 사용할 수 있고, 박형 효과를 얻을 수 있다. 일반적으로 폴리엔 편광자는 두께가 얇아질수록 편광도가 감소하지만, 본 발명의 폴리엔 편광자는 박형의 두께에도 고편광도를 유지할 수 있다.The thickness of the polyene polarizer may be about 5 μm or less, specifically about 1 to 5 μm. In the above range, the polarizing plate can be used, and a thin effect can be obtained. In general, as the thickness of the polyene polarizer decreases, the degree of polarization decreases, but the polyene polarizer of the present invention can maintain high polarization degree even with a thin thickness.
폴리엔 편광자 중 요오드 또는 이색성 색소의 함량은 약 0.3중량%이하, 구체적으로 약 0 내지 0.3중량%가 될 수 있다. 본 발명의 폴리엔 편광자는 이색성 색소를 포함하지 않더라도 충분히 편광 효과를 구현할 수 있다. 폴리엔 편광자 중 요오드 또는 이색성 색소의 함량이 0.3중량%를 초과할 경우 편광판의 투과도가 저하될 수 있다. 폴리엔 편광자 중 유기산의 함량은 약 0.001중량% 이하, 구체적으로 약 0 내지 0.001중량%가 될 수 있다. 상기 범위에서, 폴리엔 편광자의 편광 성능을 저하시키지 않을 수 있다.The content of iodine or dichroic pigment in the polyene polarizer may be about 0.3% by weight or less, specifically about 0 to 0.3% by weight. The polyene polarizer of this invention can fully implement a polarizing effect, even if it does not contain a dichroic dye. If the content of iodine or dichroic dye in the polyene polarizer exceeds 0.3% by weight, the transmittance of the polarizing plate may be reduced. The content of the organic acid in the polyene polarizer may be about 0.001 wt% or less, specifically about 0 to 0.001 wt%. In the above range, it may not lower the polarization performance of the polyene polarizer.
본 발명의 일 실시예에 따른 편광판 제조 방법은 폴리엔 편광자의 적어도 일면에 광학필름을 적층하는 단계를 더 포함할 수 있다. 광학필름은 보호필름, 또는 위상차필름 중 하나 이상을 포함할 수 있다.Polarizing plate manufacturing method according to an embodiment of the present invention may further comprise the step of laminating an optical film on at least one surface of the polyene polarizer. The optical film may include one or more of a protective film or a retardation film.
구체예에서, 광학필름은 트리아세틸셀룰로오스(TAC) 등을 포함하는 셀룰로오스계, 폴리에틸렌테레프탈레이트(PET) 등을 포함하는 폴리에스테르계, 아크릴계, 고리형 폴리올레핀(COP)계, 폴리카보네이트계, 폴리에테르술폰계, 폴리술폰계, 폴리아미드계, 폴리이미드계, 폴리올레핀계, 폴리아릴레이트계, 폴리비닐알코올계, 폴리염화비닐계, 폴리염화비닐리덴계 중 하나 이상의 재질로 된 필름일 수 있다. 광학필름의 두께는 약 20 내지 100㎛가 될 수 있다. 상기 범위에서, 편광판 용도로 사용할 수 있다.In an embodiment, the optical film is a cellulose-based, tritere-based cellulose (TAC) or the like, polyester-based, such as polyethylene terephthalate (PET), acrylic, cyclic polyolefin (COP) -based, polycarbonate-based, polyether The film may be made of at least one of sulfone, polysulfone, polyamide, polyimide, polyolefin, polyarylate, polyvinyl alcohol, polyvinyl chloride, and polyvinylidene chloride. The thickness of the optical film may be about 20 to 100㎛. In the said range, it can use for a polarizing plate use.
광학필름은 통상의 방법으로 폴리엔 편광자에 적층될 수 있다. 구체예에서, 광학필름은 편광판용 접착제, 예를 들면 폴리비닐알콜계 수계 접착제, 감압형 접착제로 적층될 수 있다. 상기 접착층의 두께는 약 80 내지 200nm가 될 수 있다.The optical film may be laminated on the polyene polarizer by conventional methods. In an embodiment, the optical film may be laminated with a polarizing plate adhesive, for example, a polyvinyl alcohol-based water-based adhesive or a pressure-sensitive adhesive. The adhesive layer may have a thickness of about 80 to 200 nm.
본 발명의 다른 관점인 편광판은 폴리엔 편광자; 및 상기 편광자의 일면 또는 양면에 형성된 광학필름 또는 기재 필름을 포함할 수 있다. 광학필름은 통상의 보호필름, 또는 위상차필름 중 하나 이상을 포함할 수 있고, 기재 필름은 폴리엔 편광자 제조시 사용되었던 기재 필름이다.Another polarizing plate of the present invention is a polyene polarizer; And it may include an optical film or a base film formed on one side or both sides of the polarizer. The optical film may include one or more of a conventional protective film or a retardation film, and the base film is a base film that has been used in manufacturing a polyene polarizer.
도 1은 본 발명 일 실시예의 편광판의 단면도이다. 도 1에 의하면, 편광판(100)은 폴리엔 편광자(10); 폴리엔 편광자(10)의 상부면에 형성된 제1광학필름(20); 및 폴리엔 편광자(10)의 하부면에 형성된 제2광학필름(30)을 포함할 수 있다.1 is a cross-sectional view of a polarizing plate of an embodiment of the present invention. Referring to FIG. 1, the polarizing plate 100 includes a polyene polarizer 10; A first optical film 20 formed on an upper surface of the polyene polarizer 10; And a second optical film 30 formed on the lower surface of the polyene polarizer 10.
편광판은 하기 식 1로 표시되는 편광도(PE) 변화율이 약 3% 미만, 구체적으로 약 0.1 내지 2.9%가 될 수 있다:The polarizing plate may have a change in polarization degree (PE) represented by Equation 1 below about 3%, specifically about 0.1 to 2.9%:
<식 1><Equation 1>
편광도 변화율(%) = │B-A│/A x 100% Change in polarization degree = │B-A│ / A x 100
(상기에서, A는 편광판의 초기 편광도이고,(In the above, A is the initial degree of polarization of the polarizing plate,
B는 상기 편광판을 80℃ 및 90% 상대습도 조건에서 500시간 동안 방치한 후 편광판의 편광도이다).B is the polarization degree of the polarizing plate after leaving the polarizing plate for 500 hours at 80 ℃ and 90% relative humidity conditions).
상기 범위에서, 편광판의 내구성과 신뢰성이 좋을 수 있다. 편광도 변화율에 있어서, 편광도는 편광자에 의해서만 좌우되고, 보호필름에 의해서는 거의 영향을 받지 않는다.In the above range, durability and reliability of the polarizing plate may be good. In the rate of change of polarization degree, the degree of polarization depends only on the polarizer and is hardly affected by the protective film.
편광판은 투과율이 약 42.5% 이상, 구체적으로 약 43 내지 45%가 될 수 있다. 상기 범위에서, 고투과율로 광학표시장치에 사용할 수 있다. 투과율은 파장 380nm 내지 780nm에서 측정된 값일 수 있지만, 이에 제한되지 않는다.The polarizing plate may have a transmittance of about 42.5% or more, specifically about 43 to 45%. Within this range, it is possible to use the optical display device with high transmittance. The transmittance may be a value measured at a wavelength of 380 nm to 780 nm, but is not limited thereto.
기재 필름은 상술한 바와 같이 폴리엔 편광자 제조시 사용된 것으로서, 폴리프로필렌계 등을 포함하는 폴리올레핀계, 폴리에틸렌테레프탈레이트 또는 폴리에틸렌나프탈레이트 등을 폴리에스테르계 트리아세틸셀룰로오스(TAC) 등을 포함하는 셀룰로오스계, 아크릴계, 고리형 폴리올레핀(COP)계, 폴리카보네이트계, 폴리에테르술폰계, 폴리술폰계, 폴리아미드계, 폴리이미드계, 폴리아릴레이트계, 폴리비닐알코올계, 폴리염화비닐계, 폴리염화비닐리덴계 등이 될 수 있다. 기재필름의 두께는 폴리엔 편광자 제조시 연신에 의해 제어될 수 있는데, 두께는 약 20 내지 200㎛가 될 수 있다. 상기 범위에서, 편광판 용도로 사용할 수 있다. As described above, the base film is used in the production of a polyene polarizer, and a polyolefin-based, polyethylene terephthalate or polyethylenenaphthalate, including polypropylene-based, and the like, and a cellulose-based triacetyl cellulose (TAC). , Acrylic, cyclic polyolefin (COP), polycarbonate, polyether sulfone, polysulfone, polyamide, polyimide, polyarylate, polyvinyl alcohol, polyvinyl chloride, polyvinyl chloride It may be a den system or the like. The thickness of the base film may be controlled by stretching during the production of the polyene polarizer, the thickness may be about 20 to 200㎛. In the said range, it can use for a polarizing plate use.
본 발명의 또 다른 관점인 광학표시장치는 상기 편광판을 포함할 수 있다. 광학표시장치는 유기발광다이오드(OLED) 디스플레이 장치를 포함할 수 있지만, 이에 제한되지 않는다. 도 2는 본 발명 일 실시예의 광학표시장치의 단면도이다. 도 2를 참조하면, 광학표시장치는 OLED 패널(200); 및 OLED 패널(200)의 상부에 형성된 편광판(110)을 포함할 수 있다.In another aspect of the present invention, an optical display device may include the polarizing plate. The optical display device may include, but is not limited to, an organic light emitting diode (OLED) display device. 2 is a cross-sectional view of an optical display device according to an exemplary embodiment of the present invention. Referring to FIG. 2, an optical display device includes an OLED panel 200; And a polarizer 110 formed on the OLED panel 200.
이하, 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만, 이는 본 발명의 바람직한 예시로 제시된 것이며 어떠한 의미로도 이에 의해 본 발명이 제한되는 것으로 해석될 수는 없다.Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.
실시예 1Example 1
PVA(폴리비닐알코올, 중합도 2600, 검화도 99.9mol%) 수지 100중량부, 유기산(pTSA, p-toluenesulfonic acid) 5중량부를 포함하는 PVA 수지 수용액을 A-PET 기재 필름에 코팅하여 두께 15㎛의 기재 일체형의 유기산 포한 PVA 필름을 제조하였다. 제조한 필름을 열풍 순환식 OVEN 140℃에서 4배 건식 연신했다. 다음에 5wt% 붕산 수용액에 2분간 침지하고 1.5배 습식 연신을 85℃에서 동시에 진행했다. 80℃ OVEN에서 3분 건조시키고, 기재 필름을 제거하여 두께 5㎛(Mitutoyo사 micrometer로 측정) 폴리엔 구조를 가지는 편광자를 제조하였다.An aqueous PVA resin solution containing 100 parts by weight of PVA (polyvinyl alcohol, polymerization degree 2600, saponification degree 99.9 mol%) resin and 5 parts by weight of organic acid (pTSA, p-toluenesulfonic acid) was coated on the A-PET base film to have a thickness of 15 μm. The PVA film containing the organic acid of the substrate integrated type was produced. The produced film was dry-stretched 4 times at hot air circulation type OVEN 140 degreeC. Subsequently, it was immersed in a 5 wt% aqueous solution of boric acid for 2 minutes, and 1.5-fold wet stretching was simultaneously performed at 85 ° C. After drying at 80 ° C. OVEN for 3 minutes, the substrate film was removed to prepare a polarizer having a polyene structure having a thickness of 5 μm (measured by Mitutoyo Micrometer).
실시예 2Example 2
실시예 1에서 중합도 2600 PVA 수지 대신에 중합도 3300 PVA 수지를 사용한 것을 제외하고는 동일한 방법을 사용하여 편광자를 제조하였다.A polarizer was prepared in the same manner as in Example 1, except that polymerization degree 3300 PVA resin was used instead of polymerization degree 2600 PVA resin.
실시예 3Example 3
실시예 1에서 중합도 2600 PVA 수지 대신에 중합도 4000 PVA 수지를 사용한 것을 제외하고는 동일한 방법을 사용하여 편광자를 제조하였다.A polarizer was prepared in the same manner as in Example 1 except that a polymerization degree of 4000 PVA resin was used instead of a polymerization degree of 2600 PVA resin.
비교예 1Comparative Example 1
PVA(중합도 3300, 검화도 99.9mol%) 수지 100중량부를 포함하는 PVA 수지 수용액을 A-PET 필름에 코팅하여 두께 15㎛의 기재 일체형의 PVA 필름을 제조하였다. 제조한 필름을 염산 수용액에 2분간 침지하여 산 처리하고 4배 건식 연신하며 2분 동안 탈수했다. 5wt% 붕산 수용액에 2분 침지와 1.5배 습식 연신을 85℃에서 동시에 진행했다. 80℃ OVEN에서 3분 건조하는 것에 의해 두께 5㎛ 폴리엔 구조를 가지는 편광자를 제조하였다.A PVA resin aqueous solution containing 100 parts by weight of a PVA (polymerization degree 3300, saponification degree 99.9 mol%) resin was coated on an A-PET film to prepare a PVA film having a substrate integral type having a thickness of 15 μm. The film thus prepared was immersed in an aqueous hydrochloric acid solution for 2 minutes, acid treated, 4 times dry stretched, and dehydrated for 2 minutes. 2 minutes immersion and 1.5 times wet drawing were performed simultaneously at 85 degreeC in 5 wt% boric-acid aqueous solution. The polarizer which has a thickness of 5 micrometers polyene structure was produced by drying for 3 minutes at 80 degreeC OVEN.
비교예 2Comparative Example 2
PVA(중합도 3300, 검화도 99.9mol%) 수지 100중량부를 포함하는 PVA 수지 수용액을 A-PET 필름에 코팅하여 두께 15㎛의 기재 일체형의 PVA 필름을 제조하였다. 제조한 필름을 요오드계 화합물에 염착하여 전체 6배로 연신하고 70℃ OVEN에서 3분 건조하는 것에 의해 두께 5㎛ 폴리엔 구조를 가지는 편광자를 얻었다.A PVA resin aqueous solution containing 100 parts by weight of a PVA (polymerization degree 3300, saponification degree 99.9 mol%) resin was coated on an A-PET film to prepare a PVA film having a substrate integral type having a thickness of 15 μm. The polarizer which has a 5-micrometer-thick polyene structure was obtained by dyeing the produced film to the iodine type compound, extending | stretching 6 times in total, and drying for 3 minutes at 70 degreeC OVEN.
실시예와 비교예에서 제조한 편광자의 양면에 보호필름인 트리아세틸셀룰로오스 필름(Konica社 40tac)을 붙여 편광판을 제조하였다. 제조한 편광판에 대해 하기 물성을 평가하였다.A triacetyl cellulose film (Konica Co., Ltd. 40tac), which is a protective film, was attached to both surfaces of the polarizers prepared in Examples and Comparative Examples to prepare a polarizing plate. The following physical properties were evaluated about the manufactured polarizing plate.
(1)투과율(%)과 편광도(%): 편광판에 대해 V-7100(JASCO사, 일본)을 사용하여 측정하였다.(1) Transmittance (%) and polarization degree (%): It measured using V-7100 (JASCO Corporation, Japan) about a polarizing plate.
(2)신뢰성: V-7100(JASCO사, 일본)을 사용하여 편광도를 측정하였다. 편광판의 초기 편광도(A)을 측정하였다. 상기 편광판을 80℃, 90% 상대습도(RH) 조건에서 500시간 동안 방치한 후 편광판에 대해 편광도(B)을 측정하였다. 신뢰성은 편광도 변화율 │B-A│/A x 100으로 평가하였다. 편광도 변화율이 3% 미만인 경우 ○로 평가하고, 편광도 변화율이 3% 이상인 경우 ×로 평가하였다.(2) Reliability: The polarization degree was measured using V-7100 (JASCO, Japan). The initial polarization degree A of the polarizing plate was measured. After the polarizing plate was allowed to stand at 80 ° C. and 90% relative humidity (RH) for 500 hours, the polarization degree (B) was measured for the polarizing plate. Reliability was evaluated by the rate of change of polarization degree | B-A | / A x 100. When the degree of polarization change was less than 3%, the evaluation was evaluated as ○, and when the degree of polarization change was 3% or more, it was evaluated as x.
표 1
실시예 1 실시예 2 실시예 3 비교예 1 비교예2
편광자 두께(㎛) 5 5 5 5 5
투과율(%) 44.8 44.9 44.2 44.8 45.3
편광도(%) 98.9 98.9 98.6 98.8 98.8
신뢰성(80℃, 90% RH, 500시간) (편광도 변화율) ○ ○ ○ ○ ×
0.3% 0.3% 0.2% 0.3% 3.5%
Table 1
Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2
Polarizer thickness (μm) 5 5 5 5 5
Transmittance (%) 44.8 44.9 44.2 44.8 45.3
% Polarization 98.9 98.9 98.6 98.8 98.8
Reliability (80 ° C, 90% RH, 500 hours) (polarization rate change rate) ○ ○ ○ ○ ×
0.3% 0.3% 0.2% 0.3% 3.5%
상기 표 1에서 나타난 바와 같이, 본 발명의 편광자로 제조된 편광판은 박막 두께의 편광자에도 투과율과 편광도가 좋았으며, 신뢰성이 좋아 내구성이 좋았고, 제조 방법에 있어서도 산 처리 공정을 포함하지 않아 제조 공정이 간단하였다. 반면에, 기존의 염산 산 처리 공정으로 제조된 비교예 1의 편광판은 산 처리 공정이 필요하여 번거롭다는 문제점이 있었다. 또한, 기존의 요오드로 염색된 편광자를 포함하는 비교예 2의 편광판은 신뢰성이 좋지 않아 내구성이 좋지 않았다.As shown in Table 1, the polarizing plate manufactured with the polarizer of the present invention had a good transmittance and polarization degree even with a thin film thickness polarizer, good reliability and good durability, and does not include an acid treatment step in the manufacturing method, so that the manufacturing process is It was simple. On the other hand, the polarizing plate of Comparative Example 1 prepared by the conventional hydrochloric acid treatment process has a problem that the acid treatment process is required and cumbersome. In addition, the polarizing plate of Comparative Example 2 including a polarizer dyed with conventional iodine was not good reliability and poor durability.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (18)

  1. 유기산을 포함하는 폴리비닐알콜계 필름을 제조하고,To prepare a polyvinyl alcohol film containing an organic acid,
    상기 유기산을 포함하는 폴리비닐알콜계 필름을 탈수 및 건식 연신하여 폴리엔 편광자를 제조하는 단계를 포함하는, 편광판의 제조 방법.Dehydrating and dry stretching the polyvinyl alcohol-based film comprising the organic acid to produce a polyene polarizer, a manufacturing method of a polarizing plate.
  2. 제1항에 있어서, 상기 탈수와 상기 건식 연신은 동시에 수행되는, 편광판의 제조 방법.The method of claim 1, wherein the dehydration and the dry stretching are performed simultaneously.
  3. 제1항에 있어서, 상기 건식 연신하는 단계 이후에 상기 필름을 습식 연신하는 단계를 더 포함하는, 편광판의 제조 방법.The method of claim 1, further comprising wet stretching the film after the dry stretching step.
  4. 제1항에 있어서, 상기 유기산은 상기 폴리비닐알콜계 필름 중 약 5중량% 이하로 포함되는, 편광판의 제조 방법.The method of claim 1, wherein the organic acid is included in about 5% by weight or less of the polyvinyl alcohol-based film.
  5. 제1항에 있어서, 상기 유기산은 탄소수 6 내지 20의 방향족 탄화수소의 술폰산을 포함하는, 편광판의 제조 방법.The manufacturing method of the polarizing plate of Claim 1 in which the said organic acid contains the sulfonic acid of C6-C20 aromatic hydrocarbon.
  6. 제1항에 있어서, 상기 폴리비닐알콜계 필름은 상기 유기산과 폴리비닐알콜계 수지를 포함하는 용액을 기재 필름에 코팅하여 기재 일체형의 필름으로 제조되는, 편광판의 제조 방법.The method according to claim 1, wherein the polyvinyl alcohol-based film is made of a substrate-integrated film by coating a solution containing the organic acid and polyvinyl alcohol-based resin on a base film.
  7. 제6항에 있어서, 상기 유기산은 상기 폴리비닐알콜계 수지 100중량부에 대해 약 0.5 내지 5중량부로 포함되는, 편광판의 제조 방법.The method of claim 6, wherein the organic acid is included in about 0.5 to 5 parts by weight based on 100 parts by weight of the polyvinyl alcohol-based resin.
  8. 제6항에 있어서, 상기 폴리비닐알콜계 수지의 중합도는 약 2600 내지 4000인, 편광판의 제조 방법.The method of claim 6, wherein the polyvinyl alcohol-based resin has a degree of polymerization of about 2600 to 4,000.
  9. 제1항에 있어서, 상기 탈수는 상기 폴리비닐알콜계 필름을 약 100 내지 160℃에서 약 1 내지 10분 동안 처리하는 단계를 포함하는, 편광판의 제조 방법.The method of claim 1, wherein the dehydration comprises treating the polyvinyl alcohol-based film at about 100 to 160 ° C. for about 1 to 10 minutes.
  10. 제1항에 있어서, 상기 건식 연신은 상기 폴리비닐알콜계 필름을 약 2 내지 6배의 연신비로 연신하는 단계를 포함하는, 편광판의 제조 방법.The method of claim 1, wherein the dry stretching comprises stretching the polyvinyl alcohol-based film at a draw ratio of about 2 to 6 times.
  11. 제3항에 있어서, 상기 습식 연신은 상기 건식 연신을 거친 상기 폴리비닐알콜계 필름에 대해 연신비 약 1 내지 1.5배로 붕산 약 1 내지 10중량%의 붕산 수용액에서 연신하는 단계를 포함하는, 편광판의 제조방법.The method of claim 3, wherein the wet stretching comprises stretching in an aqueous boric acid solution of about 1 to 10% by weight of boric acid at a draw ratio of about 1 to 1.5 times the polyvinyl alcohol-based film subjected to the dry stretching. Way.
  12. 제1항에 있어서, 상기 폴리엔 편광자의 두께는 약 5㎛ 이하인, 편광판의 제조 방법.The method of claim 1, wherein the polyene polarizer has a thickness of about 5 μm or less.
  13. 제1항에 있어서, 상기 폴리엔 편광자 중 요오드 또는 이색성 색소의 함량은 약 0.3중량% 이하인, 편광판의 제조 방법.The method of claim 1, wherein the content of iodine or dichroic pigment in the polyene polarizer is about 0.3 wt% or less.
  14. 제1항에 있어서, 상기 폴리엔 편광자의 적어도 일면에 광학필름을 적층하는 단계를 더 포함하는, 편광판의 제조방법.The method of claim 1, further comprising laminating an optical film on at least one surface of the polyene polarizer.
  15. 제14항에 있어서, 상기 광학필름은 보호필름, 위상차필름 중 하나 이상을 포함하는, 편광판의 제조방법.The method of claim 14, wherein the optical film comprises at least one of a protective film and a retardation film.
  16. 제1항 내지 제15항 중 어느 한 항의 제조방법으로 제조된 편광판.The polarizing plate manufactured by the manufacturing method of any one of Claims 1-15.
  17. 제16항에 있어서, 상기 편광판은 하기 식 1로 표시되는 편광도 변화율이 약 3% 미만인 편광판:The polarizing plate of claim 16, wherein the polarizing plate has a change in polarization degree of less than about 3% represented by the following Equation 1.
    <식 1><Equation 1>
    편광도 변화율(%) = │B-A│/A x 100% Change in polarization degree = │B-A│ / A x 100
    (상기에서, A는 편광판의 초기 편광도이고, (In the above, A is the initial degree of polarization of the polarizing plate,
    B는 상기 편광판을 80℃, 90% 상대습도 조건에서 500시간 동안 방치한 후 편광판의 편광도이다).B is the polarization degree of a polarizing plate after leaving the said polarizing plate for 500 hours at 80 degreeC and 90% relative humidity conditions.
  18. 제16항의 편광판을 포함하는 광학표시장치.An optical display device comprising the polarizing plate of claim 16.
PCT/KR2013/006818 2012-12-24 2013-07-30 Method for manufacturing polarizing plate, polarizing plate manufactured by same, and optical display device including same WO2014104519A1 (en)

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