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WO2025048449A1 - Plaque de polarisation et appareil d'affichage optique - Google Patents

Plaque de polarisation et appareil d'affichage optique Download PDF

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Publication number
WO2025048449A1
WO2025048449A1 PCT/KR2024/012762 KR2024012762W WO2025048449A1 WO 2025048449 A1 WO2025048449 A1 WO 2025048449A1 KR 2024012762 W KR2024012762 W KR 2024012762W WO 2025048449 A1 WO2025048449 A1 WO 2025048449A1
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WIPO (PCT)
Prior art keywords
polarizer
polarizing plate
polyvinyl alcohol
zinc
boron
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/KR2024/012762
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English (en)
Korean (ko)
Inventor
김나영
김민정
황선오
박은수
윤여일
김윤정
신광호
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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Publication date
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Publication of WO2025048449A1 publication Critical patent/WO2025048449A1/fr
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0818—Alkali metal
    • C08K2003/0825—Potassium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc

Definitions

  • the present invention relates to a polarizing plate and an optical display device including the same.
  • Polarizing plates are commonly used in light-emitting displays or liquid crystal displays.
  • Polarizing plates essentially include polarizers, which provide polarizing functions.
  • the polarizing function can be implemented by dichroic materials including iodine-based or dichroic dyes.
  • the polarizing plate should have an appropriate range of color values.
  • the appropriate range of color values can provide excellent screen quality without affecting the screen quality when the polarizing plate is applied to an optical display device.
  • the polarizing plate is generally required to have high reliability after being left at high temperature for a long period of time.
  • the polarizing plate needs to have a low change in color value after being left at high temperature for a long period of time.
  • a polarizing plate with a high change in color value after being left at high temperature for a long period of time can affect the color of the screen in the optical display device, which can adversely affect the reliability of the optical display device.
  • the background technology of the present invention is disclosed in Korean Patent Publication No. 2020-0115071, etc.
  • the purpose is to provide a polarizing plate that provides excellent screen quality when applied to an optical display device.
  • the purpose is to provide a polarizing plate having excellent reliability at high temperatures, with a significantly low change in color value after long-term exposure to high temperatures.
  • a polarizing plate is provided.
  • a polarizing plate has a polarizer, and the polarizer is composed of a polyvinyl alcohol-based film containing a dichroic material.
  • the polarizer contains 1.5 to 5.0 wt% of boron, 0.3 to 1.0 wt% of potassium, 0.1 to 1.0 wt% of zinc, and 0.0001 to 0.1 wt% of nitrogen.
  • the ratio of the boron content to the nitrogen content in the polarizer may be 2000 or more.
  • the ratio of the nitrogen content to the potassium content in the polarizer may be 200 or more.
  • the ratio of the nitrogen content to the zinc content in the polarizer may be 300 or more.
  • the weight ratio of boron to the total sum of potassium and zinc in the polarizer may be 2 or more.
  • the total amount of zinc, boron and potassium in the polarizer may be 95 wt% or more of the total amount of metals and metalloids in the polarizer.
  • the polyvinyl alcohol-based film may include a polyvinyl alcohol resin having a polymerization degree of 3000 to 5000, or a derivative resin of the polyvinyl alcohol.
  • a protective layer may be further laminated on at least one surface of the polarizer.
  • an optical display device is provided.
  • the optical display device includes the above polarizing plate.
  • a polarizing plate providing excellent screen quality when applied to an optical display device is provided.
  • Figure 1 is a cross-sectional view of a polarizing plate of one embodiment.
  • Figure 2 shows the results of the appearance evaluation after leaving the sample at 105°C for 48 hours in Example 1
  • Figure 3 shows the results of the appearance evaluation after leaving the sample at 105°C for 250 hours in Example 1.
  • Figure 4 shows the results of the appearance evaluation after leaving the sample at 105°C for 48 hours in Example 2
  • Figure 5 shows the results of the appearance evaluation after leaving the sample at 105°C for 250 hours in Example 2.
  • Figure 6 shows the results of the appearance evaluation after leaving Comparative Example 1 at 105°C for 48 hours
  • Figure 7 shows the results of the appearance evaluation after leaving Comparative Example 1 at 105°C for 250 hours.
  • Figure 8 shows the results of the appearance evaluation of Comparative Example 2 after being left at 105°C for 48 hours
  • Figure 9 shows the results of the appearance evaluation of Comparative Example 2 after being left at 105°C for 250 hours.
  • X to Y means X or more and Y or less (X ⁇ and ⁇ Y).
  • (meth)acrylic means acrylic and/or methacrylic.
  • zinc, potassium and boron among polarizers can be measured by the following methods.
  • ⁇ E1 [( ⁇ L) 2 + ( ⁇ a*) 2 + ( ⁇ b*) 2 ] 1/2
  • ⁇ b* is (b*) 2 - (b*) 1 ,
  • L 1 is the L of the initial polarizing plate
  • L 2 is the L of the initial polarizing plate after leaving it at 105°C for 250 hours.
  • (a*) 1 is the a* of the initial polarizing plate
  • (a*) 2 is the a* of the initial polarizing plate after leaving it at 105°C for 250 hours
  • (b*) 1 is the b* of the initial polarizing plate
  • (b*) 2 is the b* of the initial polarizing plate after leaving it at 105°C for 250 hours.
  • ⁇ E2 [( ⁇ L) 2 + ( ⁇ a*) 2 + ( ⁇ b*) 2 ] 1/2
  • ⁇ a* is (a*) 2 - (a*) 1
  • ⁇ b* is (b*) 2 - (b*) 1 ,
  • L 1 is the L of the initial polarizing plate
  • L 2 is the L of the initial polarizing plate after leaving it at 105°C for 48 hours.
  • (a*) 1 is the a* of the initial polarizing plate
  • (a*) 2 is the a* of the initial polarizing plate after leaving it at 105°C for 48 hours
  • (b*) 1 is the b* of the initial polarizing plate
  • (b*) 2 is the b* of the initial polarizing plate after leaving it at 105°C for 48 hours.
  • the ‘initial polarizing plate’ refers to the polarizing plate before being left at 105°C for 250 hours and before being left at 105°C for 48 hours.
  • 'L', 'a*', and 'b*' refer to color values according to the CIE 1976 standard, and can be measured with a colorimeter (e.g., Konica Minolta, CM-3700A), but are not limited thereto.
  • a colorimeter e.g., Konica Minolta, CM-3700A
  • the “polarization degree (PE)” of the polarizing plate is a value measured at a wavelength of 380 to 780 nm.
  • the “group transmittance (Ts)” of the polarizing plate may be the average value of the total optical transmittance measured at a wavelength of 380 to 780 nm.
  • the “orthogonal transmittance (Tc)” of the polarizing plate may be an average value of the orthogonal transmittance measured at a wavelength of 380 to 780 nm.
  • a polarizing plate providing excellent screen quality when applied to an optical display device. Specifically, the polarizing plate provides excellent screen quality by having an appropriate range of color values.
  • the polarizing plate can have a color value as value of -2.0 to 0, for example, -2.0, -1.9, -1.8, -1.7, -1.6, -1.5, -1.4, -1.3, -1.2, -1.1, -1.0, -0.9, -0.8, -0.7, -0.6, -0.5, -0.4, -0.3, -0.2, -0.1, or 0, for example, -1.5 to 0, and a color value bs value of 1.0 to 4.0, for example, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1.
  • a polarizing plate having excellent reliability at high temperatures since the amount of change in color value is remarkably low after long-term storage at high temperatures.
  • the polarizing plate has a polarizer including zinc, boron, and potassium in the content ranges described below, so that the amount of change in color value is remarkably low after long-term storage at high temperatures, thus remarkably improving reliability at high temperatures.
  • the polarizing plate has a polarizer
  • the polarizer is composed of a polyvinyl alcohol-based film containing a dichroic material
  • the polarizer contains 1.5 to 5.0 wt% of boron, 0.3 to 1.0 wt% of potassium, 0.1 to 1.0 wt% of zinc, and 0.0001 to 0.1 wt% of nitrogen.
  • the above polarizing plate may have a group transmittance of 40% or more, for example, 40 to 45%. In the above range, when the polarizing plate is applied to an optical display device, excellent screen quality can be provided.
  • the polarizing plate may have an orthogonal transmittance of 0.001% or less, for example, 0.0001, 0.0002, 0.0003, 0.0004, 0.0005, 0.0006, 0.0007, 0.0008, 0.0009, or 0.001%, for example, 0.0001 to 0.001%. In the above range, when the polarizing plate is applied to an optical display device, excellent screen quality can be provided.
  • the above polarizer is a linear light absorption polarizer that can provide a polarization function by transmitting only light in one direction among the incident light and absorbing light in a direction perpendicular to the one direction.
  • the above polarizer is a polyvinyl alcohol (PVA) film polarizer.
  • the polyvinyl alcohol film may include at least one of a polyvinyl alcohol resin and a polyvinyl alcohol derivative resin.
  • the derivative of the polyvinyl alcohol may contain a hydrophilic functional group and a hydrophobic functional group.
  • the hydrophobic functional group is additionally present in addition to a hydroxyl group (OH group), which is a hydrophilic functional group present in the polyvinyl alcohol.
  • the hydrophobic functional group may be present in at least one of the main chain and the side chain of the polyvinyl alcohol derivative resin.
  • the "main chain” refers to a portion forming the main skeleton of the polyvinyl alcohol derivative, and the "side chain” refers to a skeleton connected to the main chain.
  • the hydrophobic functional group may be present in the main chain of the polyvinyl alcohol derivative.
  • a polyvinyl alcohol derivative having a hydrophilic functional group and a hydrophobic functional group introduced therein can be produced by polymerizing one or more vinyl ester monomers such as vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, and isopropenyl acetate, and a monomer providing a hydrophobic functional group.
  • the vinyl ester monomer may include vinyl acetate.
  • the monomer providing the hydrophobic functional group may include a monomer providing a hydrocarbon repeating unit including ethylene, propylene, and the like.
  • the above polyvinyl alcohol resin and the polyvinyl alcohol derivative resin may each have a polymerization degree of 3000 to 5000, for example, 3000 to 4000.
  • the polarizer containing the above-described zinc, boron, potassium, and nitrogen may be easily manufactured.
  • the 'polymerization degree' may be an average polymerization degree measured according to the JIS K6726-1994 standard.
  • the polarizer may include a cross-linked structure by a boron compound such as boric acid.
  • a boron compound such as boric acid.
  • the polymerization degree of the polarizer may be substantially the same as the polymerization degree of the polyvinyl alcohol resin or the derivative resin of polyvinyl alcohol.
  • the polyvinyl alcohol resin and the polyvinyl alcohol derivative resin may each have a saponification degree of 98 mol% or more, for example, 98 to 100 mol%. In the above range, polyvinyl alcohol is not eluted during the manufacturing process of the polarizer, there is no deterioration in polarization performance, and the manufacturing of the polarizer containing zinc, boron, potassium, and nitrogen of the above-described polarizer can be facilitated.
  • the degree of saponification of each of a polyvinyl alcohol resin and a polyvinyl alcohol derivative resin refers to the ratio (mol%) of the number of moles of the vinyl alcohol unit to the total number of moles of the vinyl alcohol unit and the structural unit (typically a vinyl ester unit) that can be converted into a vinyl alcohol unit by saponification of the polyvinyl alcohol resin or the polyvinyl alcohol derivative resin.
  • the above saponification degree can be measured according to the description of JIS K6726-1994.
  • the polyvinyl alcohol resin or polyvinyl alcohol derivative resin film, which is the raw film of the polarizer, and the polyvinyl alcohol resin or polyvinyl alcohol derivative resin film in the obtained polarizer can have substantially the same saponification degree.
  • the above polyvinyl alcohol-based film may have a thickness of 50 ⁇ m or less, for example, 10 ⁇ m to 50 ⁇ m. In the above range, there may be no melting or breakage of the film when the film is stretched.
  • the above polyvinyl alcohol-based film may use M4516 (above, Mitsubishi, Japan) polyvinyl alcohol-based film, but is not limited thereto.
  • the polarizer contains a dichroic material.
  • the dichroic material can be dyed onto the polarizer.
  • the dichroic material may be an iodine-based material, or may include a dichroic dye such as an azo dye as a non-iodine-based material.
  • polarizers can be classified into a polarizer containing an iodine-based material as an iodine-based polarizer, and a polarizer containing a dichroic dye as a dye-based polarizer.
  • an iodine-based polarizer easily generates an I 2 substance due to decomposition of the iodine-based material at high temperature and/or high temperature and high humidity, compared to a dye-based polarizer, which can cause a color change through improper absorption in the visible light region.
  • the nitrogen content in the polyvinyl alcohol-based film may be 0 wt%.
  • nitrogen is contained in an amount of 0.0001 to 0.1 wt%.
  • the nitrogen content among the polarizers was considered to significantly reduce the color value change amount, i.e., the above-described ⁇ E1, after long-term storage at high temperatures in a polarizing plate having a polarizer containing boron, potassium, and zinc among the polarizers described below.
  • the nitrogen content among the polarizers was considered to significantly reduce the amount of color value change in both the cases where the polarizing plate was left at 105°C for 48 hours and the cases where it was left at 105°C for 250 hours, when comparing the cases where the polarizing plate was left at 105°C for 48 hours and the cases where it was left at 105°C for 250 hours. Even if the amount of color value change in a polarizing plate is low when left at 105°C for 48 hours, the amount of color value change may be high when left at 105°C for 250 hours. On the other hand, the polarizing plate according to one embodiment had a significantly low amount of color value change in both the cases where it was left at 105°C for 48 hours and the cases where it was left at 105°C for 250 hours.
  • the polarizing plate may have a color value change amount ⁇ E1 of the above formula 1 of 7.0 or less, for example, 0 to 7.0, 0.1 to 7.0. In the above range, the reliability of the polarizing plate and the optical display device at high temperatures may be excellent.
  • the polarizing plate may have a color value change amount ⁇ E2 of the above formula 2 of 5.0 or less, for example, 0 to 5.0, or 0.1 to 5.0.
  • the nitrogen content in the polarizer is less than 0.0001 wt%, the effect of reducing the color value change may be insignificant even after the polarizer is left at high temperature for a long period of time. If the nitrogen content in the polarizer is more than 0.1 wt%, the effect of reducing the color value change may be insignificant even after the polarizer is left at high temperature for a long period of time, or it may be difficult to control the zinc content in the polarizer, making it difficult to manufacture a polarizer that satisfies the zinc content range in the polarizer of the present invention, or there may be a problem in that the appearance and optical properties (e.g., polarization degree and/or light transmittance) of the polarizer deteriorate.
  • the appearance and optical properties e.g., polarization degree and/or light transmittance
  • the nitrogen content in the polarizer is, for example, 0.0001, 0.0002, 0.0003, 0.0004, 0.0005, 0.0006, 0.0007, 0.0008, 0.0009, 0.001, 0.0011, 0.0012, 0.0013, 0.0014, 0.0015, 0.0016, 0.0017, 0.0018, 0.0019, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1%, for example, 0.0005 to 0.01 wt%, 0.0005 to 0.005 wt%, 0.0005 to 0.002 wt%.
  • the nitrogen content in the above polarizer can be measured by combustion-ion chromatography, which is a method of burning the polarizer and then performing ion chromatography treatment.
  • combustion-ion chromatography is a method of burning the polarizer and then performing ion chromatography treatment.
  • the nitrogen content of the above polarizer can be implemented by controlling the polymerization degree of the polyvinyl alcohol resin or polyvinyl alcohol derivative resin in the polyvinyl alcohol film during the polarizer manufacturing process and the content of the nitrogen-containing source in the complementary color solution. This will be described in detail in the polarizer manufacturing process below.
  • boron is contained in an amount of 1.5 to 5.0 wt%. In the above range, the color values a* and b* of the polarizing plate can be easily achieved.
  • the boron in the polarizer may be present in an amount of 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0%, for example, 1.5 to 4.0 wt%, 2.0 to 4.0 wt%, or 2.5 to 4.0 wt%.
  • the boron content of the above polarizer can be implemented by using a boron-containing source during the manufacture of the polarizer and controlling the amount of the boron-containing source used. This will be described in detail in the manufacturing process of the polarizer below.
  • the potassium in the polarizer is contained in an amount of 0.3 to 1.0 wt%. In the above range, the color values a* and b* of the polarizing plate can be easily reached.
  • the potassium in the polarizer can be, for example, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0 wt%, for example, 0.3 to 0.8 wt%, 0.3 to 0.6 wt%, or 0.3 to 0.5 wt%.
  • the content of potassium in the above polarizer can be implemented by using a potassium-containing source when manufacturing the polarizer and controlling the amount of the potassium-containing source used. This is described in detail in the manufacturing process of the polarizer below.
  • the above polarizer contains zinc in an amount of 0.1 to 1.0 wt%.
  • the color values a* and b* of the polarizing plate can be easily achieved, and the appearance of the polarizer can be excellent.
  • the amount of zinc in the polarizer can be 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0%, for example, 0.1 to 0.8 wt%, or 0.3 to 0.8 wt%.
  • the content of zinc in the above polarizer can be implemented by using a zinc-containing source during the manufacture of the polarizer and controlling the amount of the zinc-containing source used. This will be described in detail in the manufacturing process of the polarizer below.
  • the contents of boron, zinc and potassium in the polarizer can be measured by ICP-OES (inductively coupled plasma optical emission spectrometry) without burning the polarizer.
  • ICP-OES inductively coupled plasma optical emission spectrometry
  • the ICP-OES is a method for measuring boron, zinc and potassium themselves or their cations.
  • the weight ratio of boron to the total sum of potassium and zinc in the polarizer may be 2 or more, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, for example, 2 to 10, for example, 2 to 8, 2 to 5. In this range, the present effect may be easily implemented.
  • the ratio of the boron content to the nitrogen content in the polarizer may be 2000 or more, for example, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, for example, 2000 to 6000. In this range, the present effect may be easily implemented.
  • the ratio of the potassium content to the nitrogen content in the polarizer may be 200 or more, for example, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, for example, 200 to 800. In this range, the present effect may be easily implemented.
  • the ratio of the zinc content to the nitrogen content in the polarizer may be 300 or more, for example, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, for example, 300 to 800. In this range, the present effect may be easily implemented.
  • the total amount of zinc, boron, and potassium in the polarizer may be 95 wt% or more, for example, 95 to 100 wt%, of the total amount of metals and metalloids in the polarizer. In this range, the present invention can be easily implemented.
  • the polarizer may have a thickness of 30 ⁇ m or less, for example, more than 0 ⁇ m and less than or equal to 30 ⁇ m, for example, from 10 ⁇ m to 25 ⁇ m. In the above range, it may be used in a polarizing plate.
  • the polarizer can be manufactured by a manufacturing method including a dyeing process, a stretching process, and a complementary color process.
  • the polarizer can be manufactured in the order of the dyeing process, the stretching process, and the complementary color process. In this case, the order of the dyeing process and the stretching process may be changed.
  • the content of boron, potassium, and zinc in the polarizer may be derived from a material used in a dyeing process, a stretching process, or a complementary color process during the polarizer manufacturing process.
  • the content of nitrogen in the polarizer may be derived from a material used in a complementary color process during the polarizer manufacturing process.
  • the polyvinyl alcohol-based film may additionally include at least one of a first washing process and a swelling process.
  • the first washing process is to wash the polyvinyl alcohol film with water to remove foreign substances on the polyvinyl alcohol film.
  • the swelling process can facilitate the dyeing and stretching of a dichroic material by immersing a polyvinyl alcohol-based film in a swelling bath at a predetermined temperature range.
  • the swelling process can include processing at 15° C. to 35° C., preferably 20° C. to 30° C., for 30 to 50 seconds.
  • the dyeing process includes treating a polyvinyl alcohol-based film in a dyeing tank with a dyeing solution containing a dichroic substance.
  • the dyeing process may be immersing the polyvinyl alcohol-based film in the dyeing solution containing the dichroic substance.
  • the dyeing solution containing the above-mentioned dichroic substance may include an aqueous solution containing the dichroic substance.
  • the above-mentioned dichroic substance is a substance containing iodine, and may include, for example, at least one of iodine (I 2 ), potassium iodide, hydrogen iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, and copper iodide.
  • iodine in the dyeing solution is included in a small amount relative to potassium iodide, and iodine may be included in an amount of 0.05 to 0.5 wt%, for example, 0.05 to 0.3 wt%, and potassium iodide may be included in an amount of 0.1 to 5 wt%, for example, 0.1 to 1 wt%.
  • the polarizer having the content of the above-described polarizer may be easily manufactured.
  • the above-mentioned dichroic material may be included in the dyeing solution at 0.1 to 10 wt%, for example, 0.5 to 5 wt%. In the above range, the effect of enabling uniform dyeing may be achieved.
  • the above dyeing solution may further include a boron compound.
  • the boron compound may help to prevent melting and fracture of the polyvinyl alcohol-based film during stretching of the polyvinyl alcohol-based film.
  • the boron compound may help to prevent melting and fracture of the film even when the polyvinyl alcohol-based film is stretched at a high temperature and a high stretching ratio in a stretching process performed after the dyeing process.
  • the above boron compound may include at least one of boric acid and borax.
  • the boron compound may be included in the dyeing solution at 0.1 to 5 wt%, preferably 0.3 to 3 wt%. In the above range, there may be an effect of achieving high reliability without melting and fracture in the stretching process.
  • the temperature of the dyeing solution may preferably be 20° C. to 50° C., specifically 25° C. to 40° C.
  • the dyeing process may be performed by immersing the polyvinyl alcohol-based film in the dyeing solution for 100 to 180 seconds, specifically 120 to 150 seconds. In the above range, the polarizer of one embodiment may be easily manufactured.
  • a polyvinyl alcohol-based film that has undergone a dyeing process may be additionally subjected to a cleaning process before being subjected to the following stretching process.
  • the above cleaning process is to clean a polyvinyl alcohol-based film that has undergone a dyeing process with a cleaning solution.
  • the above cleaning solution may contain at least one of the boron compounds, preferably boric acid and borax.
  • the boron compound may be contained in the cleaning solution in an amount of 0.1 to 5 wt%, preferably 0.3 to 3 wt%.
  • the stretching process includes stretching the dyed polyvinyl alcohol-based film at a stretching ratio of 5 times or more, for example, 6 to 7 times, at a stretching temperature of 55°C or more, for example, 55 to 65°C.
  • stretching a conventional polyvinyl alcohol-based film at the stretching ratio and stretching temperature described above melting and/or fracture of the polyvinyl alcohol-based film occurs, making it impossible to manufacture a polarizer.
  • the stretching process is carried out either wet stretching or dry stretching.
  • the stretching process comprises wet stretching in order to apply the boron compound in the stretching process.
  • the wet stretching may comprise uniaxial stretching of the polyvinyl alcohol-based film in the mechanical direction in a stretching solution comprising the boron compound.
  • the boron compound may include at least one of boric acid and borax, preferably boric acid.
  • the boron compound may be included in the stretching solution, preferably the stretching aqueous solution, in an amount of 0.5 wt% to 10 wt%, preferably 1 wt% to 5 wt%. In the above range, there may be an effect of achieving high reliability without melting and fracture during the stretching process.
  • the above stretching solution may further contain the above dichroic material.
  • the above stretching solution may further contain one or more of potassium iodide, hydrogen iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, and copper iodide, preferably potassium iodide.
  • a polyvinyl alcohol-based film that has undergone a stretching process may be additionally treated with a second washing process before being treated with the following complementary color process.
  • the above second washing process is to wash the polyvinyl alcohol-based film that has undergone the stretching process with a second washing solution.
  • the second washing solution may be water.
  • the second washing solution may preferably be at a temperature of 10° C. to 50° C., specifically 15° C. to 25° C.
  • the second washing process may be performed by immersing the polyvinyl alcohol-based film in the second washing solution for 1 second to 20 seconds, specifically 5 seconds to 10 seconds.
  • the complementary color process includes treating the polyvinyl alcohol-based film that has undergone the stretching process in a complementary color solution.
  • the complementary color process can enable the production of a polarizer having the nitrogen content described above.
  • the complementary color process can facilitate the adjustment of the color value of the polarizer.
  • the above complementary color process can be performed by placing a polyvinyl alcohol-based film in a complementary color bath containing a complementary color solution and leaving it there. It may be preferable that the complementary color solution be at a temperature of 10°C to 50°C, specifically, 15°C to 25°C.
  • the above complementary solution may include a nitrogen-containing source.
  • the nitrogen-containing source may be a nitrogen-containing salt, for example, at least one of zinc nitrate (Zn(NO 3 ) 2 ) and sodium nitrate (NaNO 3 ).
  • the nitrogen-containing source may be included in the complementary solution in an amount of 0.1 to 10 wt %, for example, 0.1 to 5 wt %. In this range, the nitrogen concentration in the polarizer of the present invention can be easily reached.
  • the polarizer can be manufactured by applying the nitrogen-containing source in a complementary process.
  • the nitrogen-containing source is applied to a process other than a dyeing process, a stretching process, or a complementary process, it may be difficult for boron, zinc, and potassium from the boron source, the zinc source, and the potassium source to penetrate into the polarizer, and thus it may be difficult to reach a nitrogen concentration in the polarizer.
  • the above complementary solution may further include at least one of a boron source, a zinc source, and a potassium source.
  • the boron source may include at least one of boric acid and borax, preferably boric acid.
  • the boron compound may be included in the complementary solution in an amount of 0.5 wt% to 10 wt%, preferably 1 wt% to 5 wt%. In the above range, the boron compound can be easily reached by the polarizer of the present invention.
  • the zinc source can be one or more of zinc sulfate, zinc chloride, zinc iodide, zinc nitrate, and zinc acetate.
  • the zinc is derived from zinc nitrate, so that the concentration of nitrogen and zinc in the polarizer can be easily adjusted by using one compound.
  • the zinc source may be contained in the complementary solution at 0.01 to 5 wt%, for example, 0.02 to 3 wt%. In this range, it can be easily reached by the polarizer of the present invention.
  • the potassium source may be potassium iodide.
  • Potassium iodide in the complementary solution may be contained in an amount of more than 0 wt% and less than or equal to 10 wt%, preferably from 1 wt% to 5 wt%. In the above range, the polarizer of the present invention can be easily reached.
  • the polarizing plate may further include one or more protective layers on at least one surface of the polarizer.
  • the protective layers may be a first protective layer or a second protective layer.
  • the first protective layer is laminated on the upper surface of the polarizer to protect the polarizer and increase the mechanical strength of the polarizing plate.
  • the first protective layer may include an optically transparent protective film.
  • the above protective film can be formed by melting and extruding a composition for a protective film containing at least one organic component among optically transparent resins, oligomers, and monomers. If necessary, a stretching process can be further added.
  • the organic component can include at least one of a cellulose ester type including triacetyl cellulose and the like, a cyclic polyolefin type including an amorphous cyclic polyolefin (cyclic olefin polymer, COP) and the like, a polycarbonate type, a polyester type including polyethylene terephthalate (PET) and the like, a polyethersulfone type, a polysulfone type, a polyamide type, a polyimide type, an acyclic-polyolefin type, a polyacrylate type including polymethyl methacrylate and the like, a polyvinyl alcohol type, a polyvinyl chloride type, and a polyvinylidene chloride type resin.
  • the first protective layer may be a single-layer or multi-layer film laminate.
  • the first protective layer can be formed of a composition comprising greater than 95 wt% of the organic component.
  • the thickness of the first protective layer may be 5 ⁇ m to 200 ⁇ m, specifically 10 ⁇ m to 100 ⁇ m, and more specifically 60 ⁇ m to 100 ⁇ m. In the above range, it can be used in a polarizing plate.
  • a functional coating layer such as a hard coating layer, an anti-fingerprint layer, an anti-reflection layer, etc., may be further formed on the upper surface of the first protective layer.
  • the second protective layer is laminated on the lower surface of the polarizer to protect the polarizer and increase the mechanical strength of the polarizing plate.
  • the second protective layer may include a film formed of the same or different resin as the first protective layer.
  • the second protective layer may be a cyclic polyolefin resin including amorphous cyclic polyolefin (COP) or a cellulose ester resin film including triacetyl cellulose or the like.
  • COP amorphous cyclic polyolefin
  • cellulose ester resin film including triacetyl cellulose or the like.
  • the second protective layer may be a cellulose ester-based resin film including triacetyl cellulose or the like.
  • the second protective layer may have the same or different thickness compared to the first protective layer.
  • Figure 1 is a cross-sectional view of a polarizing plate according to one embodiment.
  • the polarizing plate may include a polarizer (10), a first protective layer (20) laminated on one side of the polarizer (10), and a second protective layer (30) laminated on the other side of the polarizer (10).
  • the first protective layer and the second protective layer may be laminated to the polarizer by an adhesive layer.
  • the adhesive layer can be formed by a conventional polarizing plate adhesive known to those skilled in the art.
  • the adhesive layer can be formed by a water-based adhesive or a photocurable adhesive.
  • the water-based adhesive may include a polyvinyl alcohol-based adhesive resin, a crosslinking agent, etc.
  • the photocurable adhesive may include at least one of an epoxy compound, a (meth)acrylic compound, and an initiator.
  • the initiator may include at least one of a photoradical initiator and a photocationic initiator, preferably a mixture of a photoradical initiator and a photocationic initiator.
  • the photocurable adhesive may further include conventional additives such as an antioxidant and a pigment.
  • the adhesive layer may have a thickness of 0.05 ⁇ m to 10 ⁇ m. It can be used in an optical display device within the above range.
  • the optical display device includes the polarizing plate.
  • the optical display device may include one or more of a liquid crystal display device and a light-emitting display device.
  • a light-emitting display device is a light-emitting element, and may refer to an element including an organic or organic-inorganic light-emitting element, and a light-emitting material such as an LED (light emitting diode), an OLED (organic light emitting diode), a QLED (quantum dot light emitting diode), or a fluorescent substance.
  • the light-emitting display device may include a light-emitting element and a polarizing plate of the present invention laminated on a light-emitting surface emitted from the light-emitting element.
  • a liquid crystal display device includes a backlight unit, a liquid crystal panel, a light source-side polarizing plate arranged between the backlight unit and one side of the liquid crystal panel, and a viewer-side polarizing plate arranged on the other side of the liquid crystal panel, and at least one of the light source-side polarizing plate and the viewer-side polarizing plate may include the polarizing plate of the present invention.
  • a polyvinyl alcohol-based film (M4516, degree of polymerization: 3200, degree of saponification: 98 mol%, Mitsubishi, Japan, containing hydrophobic functional groups in the main chain, thickness: 45 ⁇ m) washed once with water at 25°C was subjected to swelling treatment in a swelling tank with water at 21°C.
  • the film that passed through the swelling tank was treated for 150 seconds in a dyeing tank containing a dyeing solution containing 0.1 wt% of iodine (I 2 ) and 0.2 wt% of potassium iodide (KI) at 30°C.
  • the film that passed through the above dyeing tank was washed by passing it through a washing tank containing a washing solution containing 3 wt% boric acid at 50°C.
  • the film which had passed through the washing tank, was stretched at a stretching ratio of 6 times along the MD axis in a wet stretching tank containing a 60°C stretching solution containing 2.74 wt% of boric acid and 3 wt% of potassium iodide.
  • the film which passed through the above-mentioned stretching tank, was subjected to a second washing treatment by passing it through a second washing tank containing a washing tank containing water at 17°C.
  • the film that passed through the second washing tank was treated for 10 seconds in a complementary bath containing a complementary solution containing 4.5 wt% of potassium iodide, 1 wt% of boric acid, and 2.0 wt% of zinc nitrate at 25°C.
  • the film that passed through the above complementary color filter was washed and dried with hot air to manufacture a polarizer (thickness: 17 ⁇ m).
  • a water-based adhesive (containing polyvinyl alcohol-based adhesive resin) was applied to both surfaces of the polarizer manufactured above, and a triacetyl cellulose film (thickness: 45 ⁇ m, DNP) having a hard coating layer formed on the upper surface of the polarizer was laminated, and a triacetyl cellulose (TAC) film (thickness: 20 ⁇ m, Konica) was laminated on the lower surface of the polarizer to manufacture a polarizing plate.
  • TAC triacetyl cellulose
  • a polarizer and a polarizing plate were manufactured in the same manner as in Example 1, except that the concentrations of each component in the dyeing tank, wet stretching tank, and complementary color tank were changed.
  • Nitrogen content in polarizer (unit: weight %): The polarizers manufactured in the examples and comparative examples were combusted using a combustion device (AQF-2100H, Mitsubishi Chemical Corporation) under the conditions below, and then the nitrogen content was measured using ion chromatography (IC-5000S, DIONEX) under the conditions below.
  • Color value changes of polarizing plates ⁇ E1 and ⁇ E2 The polarizing plates of the examples and comparative examples were cut to the MD x TD (6 cm x 6 cm) of the polarizer, adhered to a glass plate using an acrylic adhesive (SDI), and then the adhesive and the glass plate were covered over the polarizing plate to prepare specimens. The manufactured specimens were left at 105°C for 48 hours and 250 hours, respectively, and then the color values a* and b* were measured using a colorimeter (CM-3700A, Konica Minolta). The color value changes ⁇ E1 and ⁇ E2 were measured, respectively, using the above Equations 1 and 2.
  • the polarizing plate of the present invention satisfies the color value range described above before being left at high temperature. Therefore, it is expected to provide excellent screen quality when applied to an optical display device.
  • the polarizing plate of the present invention showed a remarkably low change in color value after being left at high temperature for a long period of time, so that it had excellent reliability at high temperatures.
  • the change in color value was remarkably low in both cases where it was left at 105°C for 48 hours and 250 hours. This can also be seen in FIGS. 2 to 5. Referring to FIGS. 2 to 5, there was no change in the color value of the polarizing plate in both cases where it was left at 105°C for 48 hours (FIGS. 2 and 4) and where it was left for 250 hours (FIGS. 3 and 5).
  • the polarizing plate of the comparative example could not obtain all the effects of the polarizing plate of the present invention described above.
  • FIGS. 6 to 9 it can be confirmed that the color value of the polarizing plate did not change when left at 105°C for 48 hours (FIGS. 6 and 8), but the color value of the polarizing plate significantly changed when left at 105°C for 250 hours (FIGS. 7 and 9).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention concerne une plaque de polarisation et un appareil d'affichage optique la comprenant, dans laquelle la plaque de polarisation comprend un polariseur, le polariseur est constitué d'un film à base d'alcool polyvinylique contenant un matériau dichroïque, et de 1,5 à 5,0% en poids de bore, de 0,3 à 1,0% en poids de potassium, de 0,1 à 1,0% en poids de zinc, et de 0,0001 à 0,1% en poids d'azote sont contenus dans le polariseur.
PCT/KR2024/012762 2023-08-28 2024-08-27 Plaque de polarisation et appareil d'affichage optique Pending WO2025048449A1 (fr)

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KR10-2023-0113134 2023-08-28
KR1020230113134A KR20250031548A (ko) 2023-08-28 2023-08-28 편광판 및 광학표시장치

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002174726A (ja) * 2000-12-06 2002-06-21 Kuraray Co Ltd 偏光フィルム
KR20100088583A (ko) * 2009-01-30 2010-08-09 주식회사 엘지화학 내구성 및 내열성이 우수한 편광소자, 편광판 및 화상표시장치 및 편광소자 제조방법
CN106483595A (zh) * 2015-08-28 2017-03-08 住华科技股份有限公司 偏光膜的制造方法
KR20180134634A (ko) * 2017-06-09 2018-12-19 주식회사 엘지화학 편광필름 및 이를 포함하는 편광판
KR20220042033A (ko) * 2020-09-25 2022-04-04 삼성에스디아이 주식회사 편광판 이를 포함하는 광학표시장치

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002174726A (ja) * 2000-12-06 2002-06-21 Kuraray Co Ltd 偏光フィルム
KR20100088583A (ko) * 2009-01-30 2010-08-09 주식회사 엘지화학 내구성 및 내열성이 우수한 편광소자, 편광판 및 화상표시장치 및 편광소자 제조방법
CN106483595A (zh) * 2015-08-28 2017-03-08 住华科技股份有限公司 偏光膜的制造方法
KR20180134634A (ko) * 2017-06-09 2018-12-19 주식회사 엘지화학 편광필름 및 이를 포함하는 편광판
KR20220042033A (ko) * 2020-09-25 2022-04-04 삼성에스디아이 주식회사 편광판 이를 포함하는 광학표시장치

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