WO2014204132A1 - Polariseur mince ayant d'excellente propriétés optiques, procédé pour sa fabrication, et plaque de polarisation et dispositif d'affichage comprenant le polariseur mince - Google Patents

Polariseur mince ayant d'excellente propriétés optiques, procédé pour sa fabrication, et plaque de polarisation et dispositif d'affichage comprenant le polariseur mince Download PDF

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Publication number
WO2014204132A1
WO2014204132A1 PCT/KR2014/005184 KR2014005184W WO2014204132A1 WO 2014204132 A1 WO2014204132 A1 WO 2014204132A1 KR 2014005184 W KR2014005184 W KR 2014005184W WO 2014204132 A1 WO2014204132 A1 WO 2014204132A1
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Prior art keywords
film
polyvinyl alcohol
thin polarizer
stretching
polarizer
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PCT/KR2014/005184
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English (en)
Korean (ko)
Inventor
남성현
정종현
나균일
유혜민
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020140067776A external-priority patent/KR20140147009A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US14/386,296 priority Critical patent/US9684104B2/en
Priority to CN201480000908.0A priority patent/CN104395790B/zh
Priority to JP2016518280A priority patent/JP6302053B2/ja
Publication of WO2014204132A1 publication Critical patent/WO2014204132A1/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—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 comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to a thin polarizer, a method for manufacturing the same, a polarizing plate and a display device including the same, more specifically, a thin polarizer having excellent optical properties and having a thickness of 10 ⁇ m or less, a manufacturing method thereof, and a polarizing plate including the same. And a display device.
  • the polarizer used in the polarizing plate is an optical element for making natural light or arbitrary polarization into a polarized light in a specific direction, and is widely used in a display device such as a liquid crystal display device and an organic light emitting device (OLED).
  • a polarizer used in the display device a polyvinyl alcohol polarizing film in which molecular chains containing an iodine compound or a dichroic dye are oriented in a constant direction is generally used.
  • the polyvinyl alcohol polarizing film is prepared by a method of dyeing and crosslinking iodine or dichroic dye on a polyvinyl alcohol-based film, and stretching in a predetermined direction, wherein the stretching process is an aqueous solution of boric acid or an iodine solution. It may be performed by wet stretching performed in solution or dry stretching performed in air.
  • stretching exceeds 60 micrometers.
  • polarizers are also required to have a thinner thickness.
  • a polyvinyl alcohol-based film having a thickness before stretching of more than 60 ⁇ m as in the prior art there is a limit in reducing the thickness of the polarizer. Therefore, studies have been attempted to fabricate thinner polarizers.
  • Korean Unexamined Patent Publication No. 2010-0071998 discloses a method of manufacturing a thin polarizing plate using a laminate prepared by coating a hydrophilic polymer layer on a substrate layer or co-extrusion of a substrate layer forming material and a hydrophilic polymer layer forming material. It is.
  • the separation of the polyvinyl alcohol layer and the base layer is not easy after stretching and a high peel force is required for the separation, the polyvinyl alcohol layer is damaged or deformed during the separation process. Problems tend to occur, and as a result, there is a problem that optical properties such as polarization degree of the polyvinyl alcohol film are inferior.
  • the polyvinyl alcohol resin is manufactured by melting and extruding the polyvinyl alcohol resin or by applying the coating solution after coating and then applying the polyvinyl alcohol according to extrusion conditions, coating conditions or film forming conditions.
  • the physical properties of the film tend to change, and not only the physical properties of the finally produced polyvinyl alcohol are lowered, but also it is difficult to realize uniform physical properties.
  • the present invention is to solve the problems as described above, the polyalcohol-based thin polarizer having a single optical transmittance of 40 ⁇ 45%, a polarization degree of 99.0% or more, excellent in optical properties, and a thickness of 10 ⁇ m or less and its manufacturing method To provide.
  • the present invention comprises the steps of attaching a non-stretched polyvinyl alcohol-based film to the at least one surface of the thermoplastic polyurethane film by using an attractive force or an adhesive to form a film laminate; Stretching the film laminate at a temperature of 45 ° C. to 55 ° C .; And it provides a method for producing a thin polarizer comprising the step of separating the polyurethane film and the polyvinyl alcohol-based film.
  • the unstretched polyvinyl alcohol film is preferably 10 ⁇ m to 60 ⁇ m thickness
  • the stretching step is carried out in boric acid solution of boric acid concentration of 1 to 5%, preferably 1 to 3%. Can be.
  • the separating of the polyurethane film and the polyvinyl alcohol-based film may be performed by applying a peel force of 2N / 2cm or less.
  • the manufacturing method of the thin polarizer of the present invention further comprises the step of dyeing at least one of iodine and dichroic dye on the film laminate before the stretching step, or drying the film laminate after the stretching step It may further comprise a step.
  • the present invention has a polarization degree measured at ten points having a thickness of 10 ⁇ m or less, a single transmittance of 40% to 45%, a degree of polarization of 99.0% or more, and positioned at equal intervals along the width direction of the polarizer.
  • a thin polarizer having a standard deviation of 0.002% or less, a polarizing plate and a display device including the same.
  • the thin polarizer manufactured by the manufacturing method of this invention is not only very thin but 10 micrometers in thickness, and is excellent also in optical properties, such as a single transmittance, polarization degree, and color.
  • 1 is a schematic diagram showing a method for measuring adhesion using a texture analyzer (Texture Analyzer).
  • FIG. 2 is a photograph showing a film laminate in which breakage occurred in the stretching step of Comparative Example 4.
  • the present inventors have conducted a long study to manufacture a polarizer having no optical breakage and excellent in optical properties even though the fracture does not occur in the manufacturing process, and as a result, a weak attraction or adhesive of a polyvinyl alcohol-based film on a polymer film It was found that the above object can be achieved by attaching the same, and stretching the same.
  • Korean Patent Application No. 10-2012-0130576 and Korean Patent Application No. 10-2012-0130577 I've done it.
  • the present inventors conducted further studies in the above-described method for producing a thin polarizer, by using a thermoplastic polyurethane film as a polymer film and performing stretching at a specific temperature, compared to the case of using other types of films It was found out that a thin polarizer having very excellent optical properties could be produced and completed the present invention.
  • a method of manufacturing a thin polarizer includes: attaching an unstretched polyvinyl alcohol-based film to at least one surface of a thermoplastic polyurethane film by using attraction force or an adhesive to form a film laminate; Stretching the film laminate at a temperature of 45 ° C. to 55 ° C .; And separating the polyurethane film and the polyvinyl alcohol-based film.
  • thermoplastic polyurethane film is to prevent the polyvinyl alcohol-based film from breaking, according to the research of the present inventors, when using a polyurethane film as a base film, compared with the case of using a film of a different material Stretching is possible, and since the heat shrinkage property is similar to the polyvinyl alcohol-based film, it can induce smooth width shrinkage without inhibiting the width shrinkage of the stretched polyvinyl alcohol film in the drying process, and thus has excellent optical properties. It has been shown that polarizers can be produced.
  • the polyurethane film usable in the present invention may be a thermoplastic polyurethane film having a maximum draw ratio of 5 times or more, preferably 8 times or more at a temperature of 45 ° C to 55 ° C, and is not particularly limited.
  • the polyurethane film has a thickness of about 20 to 100 ⁇ m, preferably 30 to 80 ⁇ m. This is because if the thickness of the polyurethane film is less than 20 ⁇ m, the breakage probability is high, and if it exceeds 100 ⁇ m, the stretching efficiency after the film laminate is formed may decrease.
  • the polyvinyl alcohol-based film attached to the thermoplastic polyurethane film has a thickness of about 10 ⁇ m to 60 ⁇ m, preferably 10 ⁇ m to 40 ⁇ m.
  • the thickness of the polyvinyl alcohol-based film exceeds 60 ⁇ m, it is difficult to achieve a thickness of less than 10 ⁇ m even when stretched, when the thickness is less than 10 ⁇ m tends to break during stretching.
  • the polyvinyl alcohol-based film is not limited to this, but the degree of polymerization is preferably about 1,000 to 10,000, preferably 1,500 to 5,000. This is because when the degree of polymerization satisfies the above range, the molecular motion is free and can be mixed flexibly with iodine or dichroic dye.
  • polyvinyl alcohol-based film of the present invention a commercially available polyvinyl alcohol-based film may be used.
  • PS30, PE30, PE60 manufactured by Gurere, M2000, M3000 M6000, etc. may be used.
  • thermoplastic polyurethane film and the polyvinyl alcohol-based film is attached by a weak attraction generated on the surface of the thermoplastic polyurethane film and the unstretched polyvinyl alcohol-based film without a separate medium, or mediated adhesive Can be attached.
  • thermoplastic polyurethane film and the polyvinyl alcohol-based film When attaching the thermoplastic polyurethane film and the polyvinyl alcohol-based film by the attraction, it is possible to have a proper adhesion by performing a surface treatment on one or both surfaces of the thermoplastic polyurethane film or polyvinyl alcohol-based film.
  • the surface treatment may be performed through various surface treatment methods well known in the art, for example, corona treatment, plasma treatment, or surface modification treatment using a strong base aqueous solution such as NaOH or KOH.
  • the thickness of the adhesive layer before stretching is about 20 nm to 4000 nm, preferably about 20 nm to 1000 nm, and more preferably 20 nm to 500 nm. May be enough.
  • the thickness of the adhesive layer after the stretching of the film laminate may be about 10nm to 1000nm, preferably 10nm to 500nm, more preferably 10nm to 200nm.
  • the adhesive the material is not particularly limited, various adhesives known in the art can be used without limitation.
  • the adhesive layer may be formed of an aqueous adhesive or an ultraviolet curable adhesive.
  • the adhesive layer may be formed by an aqueous adhesive including at least one selected from the group consisting of polyvinyl alcohol-based resins, acrylic resins, and vinyl acetate-based resins.
  • the adhesive layer may be formed by an aqueous adhesive including a polyvinyl alcohol-based resin having an acrylic group and a hydroxyl group.
  • the polyvinyl alcohol-based resin having an acrylic group and a hydroxyl group may have a degree of polymerization of about 500 to 1800.
  • the adhesive layer may be formed using an aqueous adhesive including an amine-based metal compound crosslinking agent in acetacetyl group-containing polyvinyl alcohol-based resin.
  • the adhesive may be an aqueous solution containing 100 parts by weight of a polyvinyl alcohol-based resin containing an acetacetyl group and 1 to 50 parts by weight of an amine metal compound crosslinking agent.
  • the polymerization degree and saponification degree of the polyvinyl alcohol-based resin are not particularly limited as long as they contain acetacetyl group, but the polymerization degree is 200 to 4,000, and the saponification degree is preferably 70 mol% to 99.9 mol%.
  • the degree of polymerization is 1,500 to 2,500, and the degree of saponification is more preferably 90 mol% to 99.9 mol%.
  • the polyvinyl alcohol-based resin preferably comprises 0.1 to 30 mol% of the acetacetyl group.
  • the reaction with the amine-based metal compound crosslinking agent may be smooth, and may be sufficiently significant for the water resistance of the desired adhesive.
  • the amine-based metal compound crosslinking agent is a water-soluble crosslinking agent having a functional group having reactivity with the polyvinyl alcohol-based resin, preferably in the form of a metal complex containing an amine ligand.
  • Possible metals include zirconium (Zr), titanium (Ti), hafnium (Hf), tungsten (W), iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), osmium (Os), Transition metals such as rhodium (Rh), iridium (Ir), palladium (Pd) and platinum (Pt) are possible, and ligands bound to the central metal are primary amines, secondary amines (diamines), tertiary amines or ammonium hydrides. As long as it contains at least 1 or more amine groups, such as a lockside, it is all possible.
  • the solid content of the polyvinyl alcohol-based resin containing the acetacetyl group is preferably about 1% by weight to about 10% by weight. If the solid content of the polyvinyl alcohol-based resin is less than 1% by weight, the water resistance is not sufficiently secured, so that the effect of lowering the breakage rate in the stretching process is less. If the content is more than 10% by weight, the workability is deteriorated. This is because damage may occur on the alcohol-based film surface.
  • the pH of the adhesive is preferably 4.5 to 9 or so.
  • fills the said numerical range it is because it is more advantageous in storage property and durability in a high humidity environment.
  • the pH of the adhesive can be adjusted by the method of containing an acid in the aqueous solution, wherein the acid used for pH adjustment can be used both strong and weak acid.
  • the acid used for pH adjustment can be used both strong and weak acid.
  • nitric acid, hydrochloric acid, sulfuric acid or acetic acid and the like can be used.
  • the thickness of the adhesive layer formed by the above adhesive is about 80 nm to 200 nm, preferably about 80 nm to 150 nm before stretching the film laminate, and after stretching the film laminate, about 10 nm to 100 nm, preferably 10 nm to It is preferable that it is about 80 nm. This is because when the thickness of the adhesive layer satisfies the above range, the adhesion between the base film and the polyvinyl alcohol-based film is maintained at an appropriate level so that the breakage rate in the stretching process is reduced and the polarizer surface damage during peeling can be minimized. .
  • the said adhesive agent In the case of the said adhesive agent, a crosslinking reaction occurs between the amine type metal compound and the acetacetyl group of polyvinyl alcohol-type resin at the time of hardening, and the water resistance of the adhesive layer after hardening becomes very excellent. Therefore, when the polymer film and the polyvinyl alcohol-based film are laminated using the adhesive, the phenomenon in which the adhesive dissolves in water during wet stretching can be minimized, and thus it can be particularly useful when performing wet stretching. .
  • the adhesive layer may be formed of an ultraviolet curable adhesive, for example, a first epoxy compound having a glass transition temperature of homopolymer of 120 ° C. or more, a second epoxy compound having a glass transition temperature of homopolymer of 60 ° C. or less and It may be formed of an ultraviolet curable adhesive containing a cationic photopolymerization initiator.
  • the UV-curable adhesive is 100 parts by weight of the first epoxy compound having a glass transition temperature of the homopolymer of 120 °C or more, 30 to 100 parts by weight of the second epoxy compound having a glass transition temperature of the homopolymer of 60 °C or less and cationic photopolymerization It may include 0.5 to 20 parts by weight of the initiator.
  • an epoxy compound refers to a compound having one or more epoxy groups in a molecule, preferably a compound having two or more epoxy groups in a molecule, and is in the form of a monomer, a polymer, or a resin.
  • the concept includes all of the compounds.
  • the epoxy compound of the present invention may be in the form of a resin.
  • the glass transition temperature of the homopolymer is an epoxy compound of 120 °C or more can be used without particular limitation, for example, the alicyclic epoxy compound and the glass transition temperature of the homo polymer is 120 °C or more and / Or aromatic epoxy may be used as the first epoxy compound of the present invention.
  • Specific examples of the epoxy compound having a glass transition temperature of homopolymer of 120 ° C. or higher include 3,4-epoxycyclohexylmethyl-3,4′-epoxycyclohexanecarboxylate, vinylcyclohexenedioxide dicyclopentadiene dioxide, and bisepoxycyclo.
  • the first epoxy compound is more preferably the glass transition temperature of the homopolymer is about 120 °C to 200 °C.
  • the second epoxy compound may be used without particular limitation as long as the glass transition temperature of the homopolymer is an epoxy compound of 60 ° C. or less.
  • an alicyclic epoxy compound, an aliphatic epoxy compound, or the like may be used as the second epoxy compound.
  • alicyclic epoxy compound it is preferable to use a bifunctional epoxy compound, that is, a compound having two epoxies, and more preferably use a compound in which the two epoxy groups are both alicyclic epoxy groups. It is not limited.
  • the epoxy compound which has an aliphatic epoxy group which is not an alicyclic epoxy group can be illustrated.
  • polyglycidyl ether of aliphatic polyhydric alcohol Polyglycidyl ethers of alkylene oxide adducts of aliphatic polyhydric alcohols; Polyglycidyl ethers of polyester polyols of aliphatic polyhydric alcohols and aliphatic polyhydric carboxylic acids; Polyglycidyl ethers of aliphatic polyvalent carboxylic acids; Polyglycidyl ethers of polyester polycarboxylic acids of aliphatic polyhydric alcohols and aliphatic polyhydric carboxylic acids; Dimers, oligomers or polymers obtained by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate; Or oligomers or polymers obtained by vinyl polymerization of glycidyl acrylate or glycidyl me
  • aliphatic polyhydric alcohol for example, an aliphatic polyhydric alcohol having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms or 2 to 4 carbon atoms may be exemplified.
  • Ethylene glycol 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neo Pentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8- Aliphatic diols such as octanediol, 1,9-nonane
  • alkylene oxide of 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms can be exemplified, for example, ethylene jade Seeds, propylene oxide or butylene oxide and the like can be used.
  • aliphatic polyhydric carboxylic acid For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sumeric acid, azelaic acid, sebacic acid, dodecane diacid, 2-methyl succinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentaneic acid, 2-methyloctanoic acid, 3,8-dimethyldecanediic acid, 3,7-dimethyldecanediic acid, 1,20-eicosamethylenedica Carboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1,4-dicarboxymethylenecyclohexane, 1,2,3-propylic acid, 1,
  • the second epoxy compound of the present invention may include one or more glycidyl ether groups, for example, 1,4-cyclohexanedimethanol diglycidyl ether, 1,4-butanediol diggle Cydyl ether, 1,6-hexanediol diglycidyl ether, neopentyl diglycidyl ether, resorcinol diglycidyl ether, diethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, One selected from the group consisting of trimethylolpropanetriglycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and o-cresyl glycidyl ether The above can be used as the second epoxy compound of the present invention.
  • the second epoxy compound has a glass transition temperature of about 0 ° C to 60 ° C of the homopolymer.
  • the present invention is not limited thereto, but in the present invention, it is preferable to use a combination of the first epoxy compound including at least one epoxidized aliphatic ring group and the second epoxy compound including at least one glycidyl ether group as the epoxy compound. Particularly preferred.
  • the stretching is performed at a temperature of 45 °C to 55 °C.
  • optical properties such as transmittance, polarization degree, and color are very excellent.
  • the stretching may be performed at a draw ratio of 5 times to 15 times, preferably 5 times to 10 times, and in consideration of optical properties, it is particularly preferable to carry out at a draw ratio of 6 times to 8 times.
  • the stretching may be carried out by wet stretching or dry stretching, but is not particularly limited, because when the wet stretching, the surface adhesion of the thermoplastic polyurethane film and polyvinyl alcohol-based film is stronger than dry stretching. It is more preferable in that stretching can be performed stably without a separate bonding means.
  • the stretching step at least one of the step of dyeing iodine and / or dichroic dye on the polyvinyl alcohol-based film and / or cross-linking the dyed iodine and / or dichroic dye to the polyvinyl alcohol-based film It may be performed together with the above steps.
  • the dyeing, crosslinking and stretching processes can be performed simultaneously.
  • the film laminate with the dyeing completed is immersed in an aqueous solution of boric acid, and stretched in an aqueous solution of boric acid.
  • the crosslinking step and the stretching step may be performed together.
  • the stretching step is particularly preferably carried out in an aqueous boric acid solution having a boric acid concentration of about 1 to 5%, preferably about 1 to 4%, more preferably about 1 to 3%. This is because when the stretching is performed in an aqueous boric acid solution satisfying the concentration range, the polarization degree of the polarizer is improved.
  • the stretching is preferably carried out so that the thickness of the polyvinyl alcohol-based film is less than 10 ⁇ m, for example, the thickness of the polyvinyl alcohol-based film is 1 ⁇ m to 10 ⁇ m, 3 ⁇ m to 10 ⁇ m or 1 ⁇ m It is preferable to carry out so that it becomes about 5 micrometers.
  • the stretching is preferably performed so that the width shrinkage of the polyvinyl alcohol-based film is about 30% to 80%, preferably about 60% to 80%. This is because when the width shrinkage ratio of the polyvinyl alcohol-based film satisfies the numerical range, excellent optical properties can be obtained.
  • the drying is not limited thereto, but considering the optical properties of the polarizer, it is preferable that the drying is performed at a temperature of about 20 ° C. to 100 ° C., more preferably about 40 ° C. to 90 ° C., and the drying time is 1 It is preferable that it is minutes to about 10 minutes.
  • the adhesion between the stretched polyvinyl alcohol-based film and the stretched polyurethane film after stretching of the film laminate is 2N / 2cm or less, preferably, about 0.1 to 2N / 2cm, more preferably 0.1 to 1N / 2cm May be enough.
  • the adhesion between the stretched polyurethane film and the stretched polyvinyl alcohol film satisfies the above range, surface damage can be minimized during the separation process.
  • the adhesive layer is formed between the polyvinyl alcohol-based film and the polyurethane film, the adhesive layer is stretched together by stretching, as well as the polyvinyl alcohol-based film and the polyurethane film.
  • the thickness of the layer is reduced to a level of 10 to 50% compared to before stretching, and as a result, the adhesion force between the polyvinyl alcohol-based film and the polyurethane film is lowered to 2N / 2 cm or less, thereby making it easy to separate.
  • the adhesive force is the adhesive force measured when the sample films of 2cm length is attached, a specific measuring method is shown in FIG.
  • the adhesion between the films as shown in Figure 1, after fixing the polyvinyl alcohol film (A) of the film laminate with a sample holder (H), with respect to the surface direction of the film laminate It refers to the size of the peel strength measured while peeling the polyvinyl alcohol film (A) from the polyurethane film (B) by applying a force in a vertical direction, wherein the measuring instrument is a texture analyzer (Stable Micro Systems, Inc.). : TA-XT Plus) was used.
  • the stretched polyvinyl alcohol-based film is separated from the thermoplastic polyurethane film.
  • the separation step may be performed by applying a weak peel force to the polyvinyl alcohol-based film or thermoplastic polyurethane film to leave both films.
  • the peel force is preferably 2N / 2cm or less, for example, may be 0.1 to 2N / 2cm, 0.1 to 1N / 2cm or so.
  • the peel force required to separate the polyvinyl alcohol-based film and the polymer film is very weak compared to the case of lamination using a coating or co-extrusion, the two films are easily separated without any other process or equipment. Not only that, but also the damage of the polyvinyl alcohol-based film in the separation process is very low, it shows very excellent optical performance.
  • the thin polarizer manufacturing method of the present invention as described above, sheet-to-sheet (sheet-to-sheet) process, sheet-to-roll process or roll well known in the art It may be carried out through a roll-to-roll process or the like.
  • the sheet-to-sheet process is a method of using a sheet-like film cut to a certain size with a raw film (ie, polyvinyl alcohol-based film and polyurethane film), the sheet-to-roll process is a raw film One uses a rolled film in which a long film is wound, and the other is a method of using a sheet-like film cut to a constant size.
  • a roll-to-roll process is a method of using a rolled film as a raw film. In view of the continuity and productivity of the process, it is particularly preferred to use a roll-to-roll process among these.
  • the manufacturing method of this invention adhere
  • the polyurethane film and the polyvinyl alcohol-based film may be rewound in a roll shape, and then the film laminate may be unwound from the rewound film laminate roll and introduced into the stretching process, or may be rewound. It can be added directly to the drawing process without.
  • a peeling means eg, a peeling roll
  • a peeling roll is inserted between the polyurethane film and the polyvinyl alcohol-based film to separate the interface between the polyurethane film and the polyvinyl alcohol-based film, and then the separated poly
  • the urethane film and the polyvinyl alcohol-based film may be carried out by a method of winding up different rolls.
  • the polarizer of the present invention produced by the method as described above is very thin, about 10 ⁇ m or less, for example, 1 ⁇ m to 10 ⁇ m, 3 ⁇ m to 10 ⁇ m, or 1 ⁇ m to 5 ⁇ m.
  • the unitary transmittance is about 40 to 45%, and the polarization degree is 99.0% or more, preferably 99.5% or more, and more preferably 99.7% or more.
  • the polarizer of this invention is very excellent in the uniformity of the polarization degree to the width direction.
  • the polarizer of the present invention has a standard deviation of the degree of polarization measured at ten points located at equal intervals along the width direction of the polarizer at 0.002% or less.
  • the uniformity in the polarization degree of the polarizer of the present invention is excellent in the uniformity in the heat shrinkage characteristics of the polyurethane film used as the base film is similar to the polyvinyl alcohol-based film is stretched over the entire width-direction region of the polyvinyl alcohol-based film This is because it can be made uniform.
  • a polarizing plate can be formed by laminating a transparent film on one side or both sides on the polarizer of the present invention as described above.
  • the transparent film various films used as a polarizer protective film or a retardation film in the art may be used without limitation.
  • a cellulose film, an acrylic film, a cycloolefin film, or the like may be used.
  • Lamination of the polarizer and the transparent film is not particularly limited, and may be performed using an adhesive or an adhesive well known in the art.
  • the pressure-sensitive adhesive or adhesive may be appropriately selected in consideration of the material of the transparent film to be used, for example, when using a TAC as a transparent film, an aqueous adhesive such as a polyvinyl alcohol-based adhesive may be used, When using an acrylic film, a COP film, etc. as a transparent film, photocuring or thermosetting adhesives, such as an acrylic adhesive and an epoxy adhesive, can be used.
  • the lamination method of the polarizer and the transparent film is not particularly limited, but is preferably made of a roll-to-roll method using a polarizer film roll and a transparent film roll in terms of productivity. Since a method of manufacturing a polarizing plate by laminating a polarizer and a transparent film in a roll-to-roll manner is well known in the art, a detailed description thereof will be omitted. Thus, when manufacturing a polarizing plate by a roll-to-roll system, a long rolled polarizing plate can be obtained.
  • the polarizing plate of the present invention in addition to the transparent film may further include another functional optical layer, such as a brightness enhancement film, a primer layer, a hard coating layer, an antiglare layer, an antireflection layer or an adhesive layer for adhesion with a liquid crystal panel.
  • another functional optical layer such as a brightness enhancement film, a primer layer, a hard coating layer, an antiglare layer, an antireflection layer or an adhesive layer for adhesion with a liquid crystal panel.
  • the formation method of these optical layers is not specifically limited, The well-known method well known in the art can be used.
  • the polarizing plate of the present invention has a very thin thickness compared to the conventional polarizing plate and has excellent optical properties, and thus may be usefully used in display devices such as liquid crystal display panels and organic light emitting display devices.
  • a 30-micrometer-thick polyvinyl alcohol film was attached to both sides of a 60-micrometer-thick polyurethane film to prepare a film laminate. Then, the film laminate was swelled for 15 seconds in a 25 ° C. pure solution, followed by a dyeing process for 60 seconds in a 0.3 wt% concentration and an iodine solution at 25 ° C. Then, the film laminate was washed for 15 seconds in a 1 wt% solution of boric acid, and then stretched 7 times in a 2 wt% solution of boric acid at 45 ° C. After stretching, after the complementary color process in a 5 wt% KI solution, the drying process was performed for 5 minutes in an 80 °C oven. Then, the polyurethane film and the polyvinyl alcohol film were separated to finally produce a thin polarizer having a thickness of 7.5 ⁇ m.
  • a thin polarizer was prepared in the same manner as in Example 1 except that the stretching process was performed in a 2 wt% solution of boric acid at 50 ° C.
  • a thin polarizer was prepared in the same manner as in Example 1 except that the stretching process was performed in a 2 wt% solution of boric acid at 55 ° C.
  • Optical properties such as the single transmittance, polarization degree, single color, and orthogonal color of the thin polarizers prepared in Examples 1 to 3 were measured with a JASCO V-7100 Spectrophotometer. The measurement results are shown in [Table 1].
  • the polarization degree is 99.5% or more, and the optical properties are excellent.
  • the stretching temperature is 50 ° C to 55 ° C
  • the polarization degree is 99.9. It can be seen that the optical properties are particularly excellent at more than%.
  • a 30-micrometer-thick polyvinyl alcohol film was attached to both sides of a 60-micrometer-thick polyurethane film to prepare a film laminate. Then, the film laminate was swelled for 15 seconds in a 25 ° C. pure solution, followed by a dyeing process for 60 seconds in a 0.27 wt% concentration and an iodine solution at 25 ° C. Then, the film laminate was washed for 15 seconds in a 1 wt% solution of boric acid, and then stretched 7 times in a 2 wt% solution of boric acid at 50 ° C. After stretching, after the complementary color process in a 5 wt% KI solution, the drying process was performed for 5 minutes in an 80 °C oven. Then, the polyurethane film and the polyvinyl alcohol film were separated to finally produce a thin polarizer having a thickness of 7.5 ⁇ m.
  • a thin polarizer was prepared in the same manner as in Example 4, except that the stretching process was performed in a 2.5 wt% solution of boric acid.
  • a thin polarizer was prepared in the same manner as in Example 4 except that the stretching process was performed in a 3.5 wt% solution of boric acid.
  • Optical properties such as the single transmittance, polarization degree, single color, and orthogonal color of the thin polarizers prepared in Examples 4 to 6 were measured with a JASCO V-7100 Spectrophotometer. The measurement results are shown in [Table 2].
  • a 30-micrometer-thick polyvinyl alcohol film was attached to both sides of a 60-micrometer-thick polyurethane film to prepare a film laminate. Then, the film laminate was swelled for 15 seconds in a 25 ° C. pure solution, followed by a dyeing process for 60 seconds in a 0.29 wt% concentration and an iodine solution at 25 ° C. Then, the film laminate was washed in a 1 wt% solution of boric acid for 15 seconds, and then a 6.5-fold stretching process was performed in a 2 wt% solution of boric acid at 50 ° C.
  • a thin polarizer was produced in the same manner as in Example 7, except that the draw ratio was increased to 7 times.
  • a thin polarizer was produced in the same manner as in Example 7 except that the draw ratio was 7.5 times.
  • a thin polarizer was prepared in the same manner as in Example 5 except that a polyethylene film having a thickness of 90 ⁇ m was used instead of a polyurethane film having a thickness of 60 ⁇ m.
  • a thin polarizer was prepared in the same manner as in Example 8 except that a polypropylene film having a thickness of 50 ⁇ m was used instead of a polyurethane film having a thickness of 60 ⁇ m.
  • a thin polarizer was prepared in the same manner as in Example 8 except that a polyethylene terephthalate film having a thickness of 40 ⁇ m was used instead of a polyurethane film having a thickness of 60 ⁇ m, but breakage occurred during stretching, and thus, the thin polarizer could not be manufactured.
  • Figure 2 is a photograph showing the state of the film laminate in the stretching process of the present Comparative Example 3.
  • a thin polarizer was prepared in the same manner as in Example 1 except that the stretching process was performed in a 40 wt% solution of boric acid at 2 wt%.
  • a thin polarizer was prepared in the same manner as in Example 1, except that the stretching process was performed in a 2 wt% solution of boric acid at 60 ° C.
  • Optical properties such as single transmittance, polarization degree, single color, and orthogonal color of the thin polarizers prepared by Comparative Examples 1 to 3, 4, and 5 were measured by a JASCO V-7100 Spectrophotometer. The measurement results are shown in [Table 4].

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  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)

Abstract

La présente invention concerne un polariseur mince ayant d'excellentes propriétés optiques et son procédé de fabrication. Un procédé de fabrication d'un polariseur mince selon la présente invention comprend les étapes de: formation d'un corps de film laminaire par la fixation d'un film à base d'alcool polyvinylique non étiré sur au moins une surface d'un film de polyuréthane thermoplastique au moyen d'une force d'attraction ou d'un adhésif; étirement du film laminaire à une température de 45°C à 55°C; et séparation du film de polyuréthane thermoplastique et du film à base d'alcool polyvinylique.
PCT/KR2014/005184 2013-06-18 2014-06-12 Polariseur mince ayant d'excellente propriétés optiques, procédé pour sa fabrication, et plaque de polarisation et dispositif d'affichage comprenant le polariseur mince WO2014204132A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US14/386,296 US9684104B2 (en) 2013-06-18 2014-06-12 Thin film polarizer having superior optical properties, manufacturing method thereof, and polarizing plate and display device including the same
CN201480000908.0A CN104395790B (zh) 2013-06-18 2014-06-12 具有优异的光学性能的薄膜偏光片、其制造方法和包括所述薄膜偏光片的偏光板和显示装置
JP2016518280A JP6302053B2 (ja) 2013-06-18 2014-06-12 光学物性に優れた薄型偏光子、その製造方法、これを含む偏光板及びディスプレイ装置

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KR20130069634 2013-06-18
KR10-2013-0069634 2013-06-18
KR10-2014-0067776 2014-06-03
KR1020140067776A KR20140147009A (ko) 2013-06-18 2014-06-03 광학 물성이 우수한 박형 편광자, 그 제조 방법, 이를 포함하는 편광판 및 디스플레이 장치

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JP2017107238A (ja) * 2015-11-27 2017-06-15 住友化学株式会社 偏光子の製造方法
JP2017107239A (ja) * 2015-11-27 2017-06-15 住友化学株式会社 偏光子の製造方法及びポリビニルアルコールの検出方法
JP2017107237A (ja) * 2015-11-27 2017-06-15 住友化学株式会社 偏光子の製造方法

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KR102183981B1 (ko) * 2019-06-28 2020-11-27 에스케이씨 주식회사 폴리에스테르 필름 및 이를 이용한 유기 발광 표시 장치
KR102415828B1 (ko) * 2019-09-30 2022-06-30 코오롱인더스트리 주식회사 폴리에스테르 다층 필름 및 그 제조방법

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JP2010145866A (ja) * 2008-12-19 2010-07-01 Fujifilm Corp 偏光フィルム及び偏光フィルムの製造方法、偏光板及び偏光板の製造方法、並びに乗り物用映り込み防止フィルム
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JP2017107239A (ja) * 2015-11-27 2017-06-15 住友化学株式会社 偏光子の製造方法及びポリビニルアルコールの検出方法
JP2017107237A (ja) * 2015-11-27 2017-06-15 住友化学株式会社 偏光子の製造方法

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