CN104395790B - Thin polarizer with excellent optical properties, method for manufacturing same, and polarizing plate and display device comprising thin polarizer - Google Patents

Thin polarizer with excellent optical properties, method for manufacturing same, and polarizing plate and display device comprising thin polarizer Download PDF

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Publication number
CN104395790B
CN104395790B CN201480000908.0A CN201480000908A CN104395790B CN 104395790 B CN104395790 B CN 104395790B CN 201480000908 A CN201480000908 A CN 201480000908A CN 104395790 B CN104395790 B CN 104395790B
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film
pva
laminates
stretched
thickness
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CN104395790A (en
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南星铉
郑棕炫
罗钧日
柳惠珉
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Shanjin Photoelectric Guangzhou Co ltd
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LG Chemical Co Ltd
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    • 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
    • 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
    • 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

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • 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)
  • Nonlinear Science (AREA)
  • Polarising Elements (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)

Abstract

The present invention relates to a thin polarizer with excellent optical properties and a method for manufacturing the same. A method for manufacturing a thin polarizer according to the present invention comprises the steps of: forming a film laminate body by attaching an unstretched polyvinyl alcohol (PVA)-based film onto at least one surface of a thermoplastic polyurethane film by means of an attractive force or an adhesive; stretching the film laminate at a temperature of 45 DEG C to 55 DEG C; and separating the thermoplastic polyurethane film and the PVA-based film.

Description

Film polarizers with excellent optical property, its manufacture method and including described The Polarizer and display device of film polarizers
Technical field
The present invention relates to a kind of film polarizers, its manufacture method and the Polarizer including the film polarizers and display Device, and more particularly, to it is a kind of with the film polarizers that excellent optical property and thickness are 10 μm or less, its Manufacture method and the Polarizer and display device including the film polarizers.
Background technology
Polaroid used in Polarizer is inclined with certain orientation for the light of natural light or random polarization to be converted into The Optical devices of the light for shaking, it has been widely used in display device, for example, liquid crystal display (LCD) and organic light emission two Pole pipe (OLED).As the polaroid being usually used in this display device, it is usually used containing iodine compound or dichroism Dyestuff and the light polarizing film based on polyvinyl alcohol (PVA) with the strand being orientated with predetermined direction.
Light polarizing film based on PVA can be by being dyeed and pre- with iodine or dichroic dye to the film based on PVA Fixed side is pulled up and is crosslinked the film and manufactures.In such a case, it is possible to by solution (such as boric acid aqueous solution or aqueous Iodine solution) in wet tensile, dry tensile in atmosphere etc. carrying out drawing process.In the above-mentioned manufacture work according to correlation technique In skill, based on the film of PVA, before stretching to it, the thickness for having more than 60 μm is needed, during so as to stretching to it Thereon without damaged generation.When being less than in the case of 60 μm based on the thickness of the film of PVA before drawing process, it is based on The swellbility of the film of PVA can increase, and the modulus of the per unit area of this film can increase in drawing process, thus can It is susceptible to the breakage of film.
Meanwhile, according to the trend of the slimming of nearest display device, Polarizer is also required to have the thickness for reducing.But It is, in the case of according to correlation technique using the film based on PVA with the thickness more than 60 μm, in the thickness for reducing polaroid There is restriction in degree aspect.Therefore, have been carried out studying the polaroid that manufacture has the thickness for reducing.
The method that Korean Patent Publication No. 2010-0071998 discloses a kind of thin Polarizer of manufacture, it is used by using Hydrophilic polymer layer applies cloth layer or coextrusion forms the material of basic unit and forms the material of hydrophilic polymer layer and make The layered product made.However, in the case of using coating or coetrusion, after the stretch, PVA layers and basic unit will not be easily It is separated from each other.Because for the peel strength that the separation between them needs high level, may send out in separation process The defect that raw such as PVA layers are damaged or PVA layers deform, causes the deterioration of the optical property (such as degree of polarization) based on the film of PVA. In addition, in the case of using coating or coextrusion method, because being by melting PVA resins then co-extrusion based on the film of PVA Go out PVA layers and basic unit's system and manufacture, or be used as coating solution then by coating solution coating by preparing PVA resins Manufacture in basic unit, so the physical property of manufactured PVA film may easily change, this depends on extrusion condition, applies Cloth condition or membrance casting condition.Therefore, the physical property of resulting PVA film may be deteriorated, and it will not obtain uniformity.
Accordingly, it would be desirable to manufacture the film polarizers with excellent optical property.
The content of the invention
Technical problem
In order to solve the above problems, one aspect of the present invention provide it is a kind of with excellent optical property (particularly, Single light transmittance is 40% to 45% and degree of polarization is more than 99%) and thickness is 10 μm or less based on polyvinyl alcohol (PVA) thin polaroid and its manufacture method.
Technical scheme
According to an aspect of the invention, there is provided a kind of method of manufacture film polarizers, including：By using the two Between gravitation or non-stretched is attached to into thermoplastic polyurethane film based on the film of polyvinyl alcohol (PVA) using adhesive Film laminates are formed at least one surface；The film laminates are stretched at a temperature of 45 DEG C to 55 DEG C；With make the base Separate with the thermoplastic polyurethane film in the film of PVA.
The non-stretched film based on PVA can have 10 μm to 60 μm of thickness.The stretching of film laminates can be Boric acid concentration be 1% to 5%, preferably 1% to 3% boric acid aqueous solution in carry out.
The film based on PVA is separated with the thermoplastic polyurethane film can use 2N/2cm or less stripping strong Spend to carry out.
Methods described may further include：Before stretch film layers laminate, with least in iodine and dichroic dye Plant and film laminates are dyeed, and after stretch film layers laminate, be dried the film laminates of the drawn.
According to another aspect of the disclosure, there is provided a kind of film polarizers, the film polarizers thickness is 10 μm Or it is less, single light transmittance is 40% to 45%, and degree of polarization is more than 99% and 10 etc. on the width of polaroid The standard deviation of the degree of polarization of the point measurement of distance is 0.002% or less.Further it is provided that including that film as above is inclined The Polarizer and display device of mating plate.
Beneficial effect
In the method for the manufacture film polarizers according to disclosure illustrative embodiments, polyurethane film can serve as base Film, and drawing process can be at a predetermined temperature carried out, it is possible thereby to film polarizers are fabricated to by stable technique With excellent optical property.The film polarizers for manufacturing in aforementioned manners can have 10 μm or less thickness, and this is aobvious Write thin, and can have in the excellent optical property of the aspects such as single transmissivity, polarisation, colourity.
Description of the drawings
Fig. 1 is the view for showing the method that bonding strength is measured using texture analyser；With
Fig. 2 is shown in drawing process the damaged photo of the film laminate according to comparative example 3.
Specific embodiment
Hereinafter, with reference to the accompanying drawings to describing embodiments of the present invention in detail.
There is excellent optical property and notable thin (that is, with 10 μm or less thickness) as research manufacture repeatedly Without the result of the polaroid for fracture occur, the inventor of polaroid described herein has found that above-mentioned purpose can be logical Cross using weak gravitation therebetween or using adhesive will be attached on polymer film based on the film of polyvinyl alcohol (PVA) and The film of the after-drawing attachment and realize, and have submitted the korean patent application relevant with this 10-2012-0130576th and No. 10-2012-0130577.
By further research, the inventors discovered that, compared with using different types of film, with significantly improved light The method that the film polarizers of performance can adopt the manufacture film polarizers illustrated in the application submitted to is learned, using thermoplastic Property polyurethane film the film is stretched as polymer film and at a predetermined temperature and is manufactured, and based on the research result invent The polaroid of the present invention set forth herein.
Can be included according to the method for the manufacture film-type polaroid of an exemplary embodiment of the disclosure：Pass through Non-stretched is attached to into thermoplastic polyurethane film extremely based on the film of PVA using gravitation therebetween or using adhesive Film laminates are formed on a few surface；The film laminates are stretched at a temperature of 45 DEG C to 55 DEG C；With make described being based on The film of PVA is separated with the polyurethane film.
Here, the thermoplastic polyurethane film be used to prevent the fracture based on the film of PVA.Carried out according to the present inventor Research, and is compared using different films, and by using polyurethane film as basement membrane, relatively high stretching ratio is to allow , and the heat shrinkability characteristic due to polyurethane film is similar to the heat shrinkability characteristic of the film based on PVA and polyurethane film can The steady contraction on the width based on the film of PVA of drawn is induced in dry run, therefore can be manufactured and had The film polarizers of excellent optical property.
Thermoplastic polyurethane film used in the exemplary embodiment of the disclosure can be in 45 DEG C to 55 DEG C of temperature Under degree, with 5 times or bigger, preferably 8 times or bigger of maximum amplification times yield is stretched, but not limited to this.
Here, the thickness of polyurethane film can be 20 μm to 100 μm, preferably 30 μm to 80 μm.In the thickness of polyurethane film In the case of 20 μm, the possibility of fracture can increase.In the case where the thickness of polyurethane film is more than 100 μm, in film After layered product is formed, draw efficiency can reduce.
Meanwhile, the thickness for being attached to the film based on PVA of the thermoplastic polyurethane film can be 10 μm to 60 μm, preferably 10 μm to 40 μm.In the case where the thickness of the film based on PVA is more than 60 μm, even if making the film for being based on PVA have after the stretch The thickness for having 10 μm or less can be difficult, in the case where the thickness of the film based on PVA is less than 10 μm, in the drawing process phase Between fracture based on the film of PVA occurs.
Meanwhile, the film based on PVA can have about 1,000 to 10,000 degree of polymerization, preferably approximately 1,500 to 5, 000 degree of polymerization, but not limited to this.In the case where the degree of polymerization of film of PVA is based within the above range, molecule can be free It is mobile, and can successfully combine iodine, dichroic dye etc..
Meanwhile, can be commercially available based on PVA according to the film based on PVA of the exemplary embodiment of the disclosure Film, for example, PE20, PE30 or the PE60 manufactured by Kuraray, the M2000 manufactured by Japanese synthetic chemical industry Co., Ltd, M3000 or M6000, etc..
Meanwhile, in the exemplary embodiment of the disclosure, thermoplastic polyurethane film and the film based on PVA can be not Utilized between the surface of thermoplastic polyurethane film and the non-stretched surface based on the film of PVA with the case of single medium The weak gravitation of generation is attached to each other using adhesive.
In the case where thermoplastic polyurethane film being made using gravitation and being attached to each other based on the film of PVA, can be in thermoplasticity Polyurethane film or based on PVA film a surface or two surfaces on be surface-treated so that they have it is suitable degree of Bonding strength.Here, surface treatment can be by known various surface treatment method (for example, electricity in disclosure art It is dizzy process, corona treatment or the surface modification treatment with strong alkaline aqueous solution (such as NaOH or KOH)) carrying out.
Meanwhile, make non-stretched polymer film and the non-stretched feelings being attached to each other based on the film of PVA using adhesive Under condition, the thickness of the adhesive phase before stretch film layers laminate can be 20nm to 4000nm, preferably 20nm to 1, 000nm, more preferably 20nm to 500nm.The thickness of the adhesive phase after stretch film layers laminate can be 10nm to 1, 000nm, more preferably preferred 10nm to 500nm, 10nm to 200nm.Adhesive before and after in stretch film layers laminate Layer thickness within the above range when, stretching and dry run after the film based on PVA separation can without damage Easily carry out in the case of this.
Meanwhile, the material of adhesive has no particular limits, and can without limitation use disclosure art In known various types of adhesives.For example, described adhesive layer can be by the adhesive or ultraviolet hardening based on water Adhesive is formed.
More specifically, adhesive phase can be by comprising selected from based on the resin of PVA, based on acrylic acid resin, based on second At least one in the resin of vinyl acetate is formed based on the adhesive of water.
In addition, adhesive phase can by comprising the resin based on PVA with acrylic acid groups and oh group based on The adhesive of water is formed.Here, the resin based on PVA with acrylic acid groups and oh group can have about 500 to 1,800 degree of polymerization.
In addition, adhesive phase can be by comprising the resin based on PVA containing acetoacetyl and the metallization based on amine Compound crosslinking agent is formed based on the adhesive of water.More specifically, described adhesive can be a kind of aqueous solution, it includes 100 The resin based on PVA containing acetoacetyl of weight portion and the metallic compound crosslinking agent based on amine of 1 to 50 weight portion.
Here, based on PVA resin the degree of polymerization and saponification degree be not particularly limited, as long as should be based on PVA resin contain There is acetoacetyl.The resin of PVA should be based on can have 200 to 4,000 degree of polymerization, and can have 70 moles of % To the saponification degree of 99.9 moles of %.In view of the freedom of the motion of the molecule of the flexible mixing of the material for being included, the degree of polymerization can For 1,500 to 2,500, and saponification degree can be 90 moles of % to 99.9 mole of %.Here, the resin based on PVA can be with Acetoacetyl comprising 0.1 mole of % to 30 mole of %.Within the above range, based on PVA resin and the metal based on amine Reaction between compound crosslink agent can be carried out satisfactorily, and adhesive can have required water resistance.
The metallic compound crosslinking agent based on amine can have predetermined reactivity comprising with the resin based on PVA The water-soluble cross-linker of functional group, and can be the metal complex containing the part based on amine.The metal-complexing Compound can include selected among zirconium (Zr), titanium (Ti), hafnium (Hf), tungsten (W), iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), osmium (Os), the transition metal in rhodium (Rh), iridium (Ir), palladium (Pd) and platinum (Pt).Be coupled to the part of central metal can include to A few amido, such as primary amine, secondary amine (diamines), tertiary amine or ammonium hydroxide.
Additionally, the resin based on PVA containing acetoacetyl can have the solid of 1 weight % to 10 weight % Content.In the case where the solids content of the resin based on PVA is less than 1 weight %, adhesive will not obtain enough water proofing properties Can, therefore, its reduce in drawing process breakage incidence in terms of can be that validity is relatively low.In the resin based on PVA In the case that solids content is more than 10 weight %, the machinability of adhesive may be deteriorated, and base may occur when separating In the damage on the surface of the film of PVA.
Meanwhile, the pH value of adhesive can be 4.5 to 9.Described adhesive pH value within the above range in the case of, The adhesive can be more favourable in terms of bin stability and durability in high humility atmosphere.
Meanwhile, the pH value of the adhesive can be adjusted by providing acid in the aqueous solution.Here, pH adjusting agent can Being strong acid or weak acid.For example, pH adjusting agent can be nitric acid, hydrochloric acid, sulfuric acid, acetic acid etc..
Before stretch film layers laminate, the thickness of the adhesive phase formed by above-mentioned adhesive can be 80nm to 200nm, It is preferred that 80nm to 150nm, and can be 10nm to 100nm, preferred 10nm to 80nm after stretch film layers laminate.Described The thickness of adhesive phase within the above range in the case of, the bonding strength between basement membrane and the film based on PVA can be appropriate Ground continues, and the incidence that ruptures in drawing process may be reduced, while can subtract the breakage on the polaroid surface when separating To minimum.
In the case of adhesive, when adhesive is solidified, in the metallic compound based on amine and the resin based on PVA Reaction is crosslinked between acetoacetyl, the water proofing property after the solidification of described adhesive layer may be significantly improved.Using In the case of this adhesive stacking polymer film and the film based on PVA, when wet tensile is carried out, adhesive is dissolved in water Phenomenon can be minimized.Therefore, adhesive can be used advantageously in during wet tensile.
Meanwhile, adhesive phase can be formed by ultraviolet-curing adhesive.For example, adhesive phase can be consolidated by ultraviolet Change type adhesive is formed, and the ultraviolet-curing adhesive includes that homopolymer glass transition temperature is more than 120 DEG C One epoxide, homopolymer glass transition temperature are that less than 60 DEG C of the second epoxide and cationic photopolymerization cause Agent.Specifically, the homopolymer glass transition temperature that the ultraviolet-curing adhesive can include 100 weight portions is 120 The first epoxide, the second ring that the homopolymer glass transition temperature of 30 to 100 weight portions is less than 60 DEG C more than DEG C The cationic photopolymerization initiator of oxygen compound and 0.5 to 20 weight portion.
Epoxide as herein described may refer to the compound with one or more epoxide groups in the molecule, excellent Elect the compound with two or more epoxide groups in the molecule as, and be construed as including monomer, polymer and The form of resin.Can be in the form of resin according to the epoxide of the illustrative embodiments of the disclosure.
Meanwhile, first epoxide is not particularly limited, as long as it has more than 120 DEG C of homopolymers vitrifying Transition temperature.It is, for example possible to use the alicyclic epoxy compound of the homopolymer glass transition temperature with more than 120 DEG C Thing and/or aromatic epoxy compound are used as the first epoxide in the illustrative embodiments of the disclosure.With 120 The example of the epoxide of the homopolymer glass transition temperature more than DEG C includes 3,4- epoxycyclohexyl-methyl -3,4'- rings Oxygen cyclohexane carboxylate, vinyl cyclohexene dioxide, dicyclopentadiene, double (epoxycyclopentyl) ethers, it is based on The epoxide of bisphenol-A, epoxide based on Bisphenol F etc..Meanwhile, first epoxide can have 120 DEG C To 200 DEG C of homopolymer glass transition temperature.
Then, second epoxide is not particularly limited, as long as it has 60 DEG C or lower of homopolymers glass Change transition temperature.It is, for example possible to use alicyclic epoxide compound, aliphatic epoxy compound etc. are used as in the disclosure The second epoxide in illustrative embodiments.
Here, the alicyclic epoxide compound can be difunctional epoxy compound, it is, having two epoxy radicals The compound of group, wherein, two epoxide groups are cycloaliphatic epoxy groups.But, alicyclic epoxide compound not limited to this.
The aliphatic epoxy compound can be the epoxy with aliphatic epoxy group rather than cycloaliphatic epoxy groups Compound.For example, as aliphatic epoxy compound, it is possible to use the poly epihydric alcohol base ether of aliphatic polyol；Aliphatic The polyglycidyl ether of the alkylene oxide addition products of polyalcohol；Aliphatic polyol and the polyester polyols of aliphatic polycarboxylic acid The poly epihydric alcohol base ether of alcohol；The poly epihydric alcohol base ether of aliphatic polycarboxylic acid；Aliphatic polyol and aliphatic polybasic carboxylic The poly epihydric alcohol base ether of the polyester polycarboxylic acid of acid；By glycidyl acrylate or GMA Vinyl polymerization and obtain dimer, oligomer or polymer；By different from glycidyl acrylate or methacrylic acid The vinyl polymerization based on the monomer of vinyl of ethylene oxidic ester and obtain oligomer or polymer；Etc..Preferably, can be with Bunching water using the alkylene oxide addition products of the poly epihydric alcohol base ether or aliphatic polyol of aliphatic polyol is sweet Oily ether.But, aliphatic epoxy compound not limited to this.
The aliphatic polyol can be with 2-20 carbon atom, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 To 8 carbon atoms or the aliphatic polyol of 2 to 4 carbon atoms.For example, the aliphatic polyol can include：Aliphatic series two Alcohol, such as ethylene glycol, 1,2-PD, 1,3-PD, 2- methyl isophthalic acids, ammediol, 2- butyl -2- ethyl -1,3 propane diols, BDO, neopentyl glycol, 3- methyl -2,4- pentanediols, 2,4- pentanediols, 1,5-PD, 3- methyl isophthalic acids, 5- penta 2 Alcohol, 2- methyl -2,4 pentanediols, 2,4- diethyl -1,5-PD, 1,6- hexylene glycol, 1,7- heptandiol, 3,5- heptandiols, 1, 8- ethohexadiols, 2- methyl isophthalic acids, 8- ethohexadiols, 1,9- nonanediol, 1,10- decanediol etc.；Alicyclic diol, such as hexamethylene diformazan Alcohol, cyclohexane diol, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F；Trimethylolethane, trimethylolpropane, hexitol, pentitol is sweet Oil, polyglycereol, pentaerythrite, dipentaerythritol, tetra methylol propane etc..
Additionally, the epoxyalkane can have 1 to 20 carbon atom, 1 to 16 carbon atom, 1 to 12 carbon atom, The epoxyalkane of 1 to 8 carbon atom or 1 to 4 carbon atom.For example, the epoxyalkane can include oxirane, epoxy third Alkane, epoxy butane etc..
Additionally, the aliphatic polycarboxylic acid can be with, it may for example comprise ethanedioic acid, malonic acid, succinic acid, glutaric acid, oneself two Acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecylic acid, 2- methylsuccinic acids, 2- methyl adipic acids, 3- methyl oneself two Acid, 3 methylvaleric acid, 2- methyloctanoic acids, 3,8- dimethyl capric acid, 3,7- dimethyl capric acid, 1,20- eicosane methylene dicarboxyl Sour (eicosamethylenedicarboxylic acid), 1,2- cyclopentane dicarboxylic acid, 1,3 cyclopentane dicarboxylic acid, 1,2- ring Hexane dicarboxylic acid, 1,3- cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-dicarboxyl methylenecyclohexane, 1,2,3- third Alkane tricarboxylic acids, 1,2,3,4- butane tetracid, 1,2,3,4- cyclobutane tetrabasic carboxylic acid etc., but not limited to this.
Preferably, the second epoxide in the illustrative embodiments of the disclosure can be comprising one or more contractings Water glyceryl ether group.For example, the second epoxide in the illustrative embodiments of the disclosure can be selected from Isosorbide-5-Nitrae- Cyclohexanedimethanodiglycidyl diglycidyl ether, 1,4- butanediol diglycidyl ethers, 1,6 hexanediol diglycidylether, new penta 2 Alcohol diglycidyl ether, resorcinolformaldehyde resin, diethylene glycol diglycidyl glycerin ether, ethylene glycol diglycidylether, Trihydroxymethylpropanyltri diglycidyl ether, normal-butyl diglycidyl ether, 2- hexyl glycidyl ethers, phenyl glycidyl At least one in ether and o-tolyl glycidol ether.
Meanwhile, second epoxide can have the homopolymer glass transition temperature from 0 DEG C to 60 DEG C.
Meanwhile, according to the illustrative embodiments of the disclosure, the first epoxy containing at least one epoxidised alcyl Compound can be preferably used as epoxy with the combination of the second epoxide containing at least one glycidyl ether group Compound, but not limited to this.
Then, the stretching of film laminates can be carried out at a temperature of 45 DEG C to 55 DEG C.As grinding that inventor is carried out It is studying carefully as a result it has been found that the film is stretched as basement membrane and at moderate temperatures by using thermoplastic polyurethane film can be with Improve optical property, such as light transmittance, polarisation, colourity.
Meanwhile, can be to carry out drawing process in 5 to 15 times of stretching ratio, preferably with 5 to 10 times of stretching ratio Carry out drawing process.In view of optical property, particularly preferred can be 6 to 8 times of stretching ratio.
Meanwhile, drawing process, but not limited to this can be carried out by wet tensile or dry tensile.Wet tensile process can be with excellent Select in dry tensile process, reason is, because it is allowed between thermoplastic polyurethane film and the film based on PVA than dry tensile mistake The surface bonding intensity of Cheng Gengqiang, so it can stably be carried out in the case where single medium is not needed.
Meanwhile, drawing process can be dyeed and be crosslinked the Jing with iodine and/or dichroic dye to the film based on PVE At least one of the film based on PVE dyeed by iodine and/or dichroic dye process is carried out together.
For example, drawing process can be carried out in containing iodine and/or dichroic dye and boron aqueous acid, such that it is able to Carry out dyeing course, cross-linking process and drawing process simultaneously.Or, by the way that film laminates are impregnated into containing iodine and/or two In the aqueous solution of color dyestuff to carry out dyeing course after, can be by the way that the film laminates of dyeing be impregnated into into boric acid aqueous solution In and stretch in boric acid aqueous solution the film laminates of the dyeing and come while carrying out cross-linking process and drawing process.
Meanwhile, can be 1% to 5%, preferably 1% to 4% in boric acid concentration, more preferably 1% to 3% boric acid water Drawing process is carried out in solution.In the case of drawing process is carried out in the boric acid aqueous solution in above-mentioned concentration range, The degree of polarization of polaroid can be enhanced.
Meanwhile, drawing process can be carried out and cause the film based on PVA that there is 10 μm or less thickness.For example, based on PVA Film can be drawn into thickness for 1 μm to 10 μm, thickness is 3 μm to 10 μm, or thickness is 1 μm to 5 μm.
Furthermore it is possible to pass through to cause the film for being based on PVA shrinkage factor to be in the width direction 30% to 80%, preferably 60% to 80% carrying out drawing process.When the shrinkage in width rate of film of PVA is based within the above range, can obtain excellent Optical property.
Meanwhile, after this stretching process, can dried film laminate as needed.Here, it is contemplated that the optics of polaroid Performance, can be dried process at 20 DEG C to 100 DEG C at preferably 40 DEG C to 90 DEG C, and drying time can be 1 to 10 points Clock.
Meanwhile, after stretch film layers laminate, between the film based on PVA and the polyurethane film of drawn of drawn Adhesion strength can be 2N/2cm or less, more preferably preferably 0.1 to 2N/2cm, 0.1 to 1N/2cm.When drawn based on Adhesion strength between the film of PVA and the polyurethane film of drawn be within the above range in the case of, it can be separated During will to the damage on its surface minimize.In the manufacture method according to the illustrative embodiments of the disclosure, when When forming adhesive phase between the film and polyurethane film based on PVA, the adhesive layer can be with the film and polyurethane film one based on PVA Rise and be stretched, therefore, the thickness of adhesive phase can be lowered to the 10% to 50% of its original thickness before being stretched.Cause This, the bonding strength between the film and polyurethane film based on PVA can be reduced to 2N/2cm or less, so that they can be with that This is separated freely.Meanwhile, bonding strength refers to the adhesion measured in the case of sample film of the adhesion length for 2cm, and Measuring method is shown in Figure 1.In the illustrative embodiments of the disclosure, intermembranous bonding strength is referred to work as and is using specimen holder By applying force to film layer on the direction of the in-plane of film laminates after the PVA film A of H fixation film laminates The peel strength that the PVA film A of laminate is measured when peeling off from polyurethane film B.Here, measurement apparatus are to stablize micro-system Texture analyser (the model name of (Stable Micro Systems)：TA-XT Plus).
It is then possible to being separated drawn with thermoplastic polyurethane film based on the film of PVA.In separation process, can be with Apply weak peel strength to the film or thermoplastic polyurethane film based on PVA, to allow two films separated from one another.Herein, peel off strong The degree of degree can be 2N/2cm or less.For example, the degree of peel strength can be 0.1 to 2N/2cm, preferably 0.1 to 1N/2cm.In the illustrative embodiments of the disclosure, because compared with the situation using coating or coextrusion method stacked film, The degree of the peel strength required for for separating the film and polymer film based on PVA is significantly weak, so two films can be with that This be easily separated and without the need for single process or equipment.Furthermore, it is possible to reduce the damage to the film based on PVA in separation process It is bad, it is possible thereby to show significantly excellent optical property.
Meanwhile, disclosure institute can be used according to the method for the manufacture film polarizers of the illustrative embodiments of the disclosure State method known to field to carry out, for example, sheet material is to sheet material method (sheet-to-sheet process), sheet material double roll process (sheet-to-roll process), roll-to-roll method (roll-to-roll process) etc..Here, sheet material makes to sheet material method With the single film with preliminary dimension as raw material film (namely be based on the film and polyurethane film of PVA), and sheet material double roll process is used The roll shape film of the length wound on roller uses the single film with preliminary dimension as another kind of raw material as a kind of raw material film Film.Additionally, roll-to-roll method uses roll shape film as raw material film.In view of process continuity and productivity ratio, particularly can use Roll-to-roll method.
For example, can be included according to the method for the manufacture film polarizers of the illustrative embodiments of the disclosure：By Polyurethane film and the film based on PVA is set to make polyurethane film while unwinding from polyurethane deflector roll and the deflector roll based on PVA respectively Film laminates are formed with the film attachment based on PVA；The film laminates are stretched at a temperature of 45 DEG C to 55 DEG C；It is based on separation The film and thermoplastic polyurethane film of PVA.
Meanwhile, after polyurethane film is made and be attached to each other based on the film of PVA, they are recoiled on roller, then film layer Laminate subsequently can unwind and be incorporated in drawing process from the roller of the film laminates recoiled, or be directed into drawing During stretching and without the need for rewinding process.
Additionally, separation process can be by being inserted into polyurethane film and based on PVA's by stripping off device (for example, stripper roll) Between film, separate polyurethane film and the intermembranous interface based on PVA and by detached polyurethane film and detached based on PVA's Film is wound on different rollers and carries out.
The polaroid manufactured using said method can have 10 μm or less thickness.For example, the polaroid can be with With 1 μm to 10 μm, 3 μm to 10 μm or 1 μm to 5 μm of thickness, this is significantly thin.Even if additionally, significantly subtracting as having Little thickness, polaroid can have 40% to 45% single light transmittance, and with 99% or higher, preferably 99.5% or more Height, more preferably 99.7% or higher degree of polarization, this shows significantly excellent optical property.
Additionally, can be with degree of polarization in the direction of the width according to the polaroid of the illustrative embodiments of the disclosure Significantly excellent uniformity.Specifically, the mark of the degree of polarization of 10 equidistant point measurements on the width of polaroid Quasi- deviation can be 0.002% or less.According to the polaroid of the illustrative embodiments of disclosure polarisation in the direction of the width The excellent uniformity of degree is because：Heat shrinkability characteristic due to the polyurethane film as basement membrane is received with the heat of the film based on PVA Contracting characteristic is similar, therefore, it is possible in the whole region of film based on PVA equably carry out drawing process in the direction of the width.
Meanwhile, Polarizer can be formed by being laminated hyaline membrane on a surface or two surfaces of above-mentioned polaroid. Herein, it is possible to use the various types of films as polarizing plate protective film or phase shift films in disclosure art are used as transparent Film, without limiting.For example, it is possible thereby to using based on the film of cellulose, based on acrylic acid film, the film based on cycloolefin Deng.
The stacking of polaroid and hyaline membrane is not particularly limited, and can be using the known bonding of disclosure art Agent, adhesive etc. are carrying out.Here, adhesive or adhesive can be by considering the material of hyaline membrane used etc. come suitably Select.For example, in the case where the hyaline membrane is triacetyl cellulose (TAC) film, it is possible to use the adhesive based on water, example Such as, the adhesive based on PVA.In the case where the hyaline membrane is acrylic film, cyclic olefin polymer (COP) film etc., can be with Using photocuring or Thermocurable adhesive, for example, based on acrylic acid adhesive, the adhesive based on epoxy etc..
Meanwhile, the method for layered polarization piece and hyaline membrane is not particularly limited, and can be by considering that productivity ratio is used Polaroid deflector roll and transparent deflector roll are carried out by roll-to-roll method.Because by using roll-to-roll method layered polarization piece and hyaline membrane Method to manufacture Polarizer is method as known in the art, so detailed description will be omitted.Using roll-to-roll In the case that legal system makes Polarizer, long roll shape Polarizer can be obtained.
Meanwhile, in addition to hyaline membrane, may further include according to the Polarizer of the illustrative embodiments of the disclosure Functional optical layer, such as brightness improving film, prime coat, hard conating, anti-dazzle photosphere, anti-reflection layer, for bonding with liquid crystal panel Adhesive linkage etc..The method for forming such optical layers has no particular limits, and can be known in disclosure art Method.
Because the Polarizer of the illustrative embodiments according to the disclosure, compared with existing Polarizer, be than relatively thin, And with excellent optical property, so it may be advantageously used with display device (for example, liquid crystal display (LCD) panel, organic Electroluminescent device etc.) in.
Embodiment of the present disclosure
Hereinafter, the disclosure will be described in detail with reference to specific embodiment.
Embodiments of the invention 1
Film layer pressure is formed by being laminated the PVA film that thickness is 30 μm on two surfaces of the polyurethane film that thickness is 60 μm Body.By film laminates at 25 DEG C in pure water solution swelling 15 seconds afterwards, by the film laminates at 25 DEG C in iodine concentration To dye 60 seconds in the iodine solution of 0.3 weight %.Then, film laminates are being held in the solution that boric acid concentration is 1 weight % It is continuous to be cleaned after process within 15 seconds, with 7 times of multiplying power stretch film layers in the solution that boric acid concentration is 2 weight % at 45 DEG C Laminate.After this stretching process, film laminates are carried out into complementary color process in the solution that iodate potassium concn is 5 weight %, then It is dried 5 minutes at 80 DEG C in an oven.Hereafter, it is polyurethane film and PVA film is separated from one another, and therefore, it is final to prepare thickness Spend the film polarizers for 7.5 μm.
Embodiments of the invention 2
In addition to carrying out drawing process in the solution that boric acid concentration is 2 weight % at 52 DEG C, use and the present invention The identical method of embodiment 1 manufacture embodiments in accordance with the present invention 2 film polarizers.
Embodiments of the invention 3
In addition to carrying out drawing process in the solution that boric acid concentration is 2 weight % at 55 DEG C, use and the present invention The identical method of embodiment 1 manufacture embodiments in accordance with the present invention 3 film polarizers.
EXPERIMENTAL EXAMPLE 1
The film polarizers prepared by embodiments of the invention 1 to 3 using JASCO V-7100 spectrophotometric determinations Optical characteristics, such as single light transmittance, degree of polarization, monochrome and colour contamination, and its measurement result are shown in Table 1.
【Table 1】
As shown in table 1, in the case where polyurethane film is used as into basement membrane, degree of polarization is 99.5% or higher, is shown excellent Different optical characteristics.Particularly, in the case of 50 DEG C to 55 DEG C of draft temperature, degree of polarization is 99.9% or higher, is shown Go out significantly excellent optical characteristics.
Embodiments of the invention 4
Film layer pressure is formed by being laminated the PVA film that thickness is 30 μm on two surfaces of the polyurethane film that thickness is 60 μm Body.By film laminates at 25 DEG C in pure water solution swelling 15 seconds afterwards, by the film laminates at 25 DEG C in iodine concentration To dye 60 seconds in the iodine solution of 0.27 weight %.Then, film laminates are being held in the solution that boric acid concentration is 1 weight % It is continuous to be cleaned after process within 15 seconds, with 7 times of multiplying power stretch film layers in the solution that boric acid concentration is 2 weight % at 50 DEG C Laminate.After this stretching process, film laminates are carried out into complementary color process in the solution that iodate potassium concn is 5 weight %, then It is dried 5 minutes at 80 DEG C in an oven.Hereafter, it is polyurethane film and PVA film is separated from one another, and therefore, it is final to prepare thickness Spend the film polarizers for 7.5 μm.
Embodiments of the invention 5
In addition to carrying out drawing process in the solution that boric acid concentration is 2.5 weight %, using the enforcement with the present invention The identical method of example 4 manufactures the film polarizers of embodiments in accordance with the present invention 5.
Embodiments of the invention 6
In addition to carrying out drawing process in the solution that boric acid concentration is 3.5 weight %, using the enforcement with the present invention The identical method of example 4 manufactures the film polarizers of embodiments in accordance with the present invention 6.
EXPERIMENTAL EXAMPLE 2
The film polarizers prepared by embodiments of the invention 4 to 6 using JASCO V-7100 spectrophotometric determinations Optical characteristics, such as single light transmittance, degree of polarization, monochrome and colour contamination, and its measurement result are shown in Table 2.
【Table 2】
According to table 2, in the case of using polyurethane film as basement membrane, with the boric acid in embodiments of the invention 4 and 5 Concentration is respectively 2.0 weight % and 2.5 weight % are compared, when boric acid concentration is 3.5 weight %, degree of polarization relative reduction.
Embodiments of the invention 7
Film layer pressure is formed by being laminated the PVA film that thickness is 30 μm on two surfaces of the polyurethane film that thickness is 60 μm Body.By film laminates at 25 DEG C in pure water solution swelling 15 seconds afterwards, by the film laminates at 25 DEG C in iodine concentration To dye 60 seconds in the iodine solution of 0.29 weight %.Then, film laminates are being held in the solution that boric acid concentration is 1 weight % It is continuous to be cleaned after process within 15 seconds, with 6.5 times of multiplying power stretched film in the solution that boric acid concentration is 2 weight % at 50 DEG C Layered product.After this stretching process, film laminates are carried out into complementary color process in the solution that iodate potassium concn is 5 weight %, and It is dry 5 minutes at 80 DEG C in an oven afterwards.Hereafter, it is polyurethane film and PVA film is separated from one another, and therefore, it is final to prepare Thickness is 7.5 μm of film polarizers.
Embodiments of the invention 8
In addition to carrying out drawing process with 7 times of multiplying power, using with the identical method of embodiments of the invention 7 root is manufactured According to the film polarizers of embodiments of the invention 8.
Embodiments of the invention 9
In addition to carrying out drawing process with 7.5 times of multiplying power, use and the manufacture of the identical method of embodiments of the invention 7 The film polarizers of embodiments in accordance with the present invention 9.
EXPERIMENTAL EXAMPLE 3
The film polarizers prepared by embodiments of the invention 7 to 9 using JASCO V-7100 spectrophotometric determinations Single light transmittance and degree of polarization, and its measurement result is shown in Table 3.
【Table 3】
Comparative example 1
In addition to the polyethylene film for using thickness being 90 μm replaces thickness to be 60 μm of polyurethane film, use and the present invention The identical method of embodiment 5 manufacture according to the film polarizers of comparative example 1.
Comparative example 2
In addition to the polypropylene screen for using thickness being 50 μm replaces thickness to be 60 μm of polyurethane film, use and the present invention The identical method of embodiment 8 manufacture according to the film polarizers of comparative example 2.
Comparative example 3
Except using polyethylene terephthalate film that thickness is 40 μm replace polyurethane film that thickness is 60 μm with Outward, film polarizers of the manufacture according to comparative example 3 are attempted using with the identical method of embodiments of the invention 8；But, in stretching During occur damaged, cause that film polarizers can not be manufactured.Fig. 2 be shown in drawing process during according to the film of comparative example 3 The photo of the state of layered product.
Comparative example 4
In addition to carrying out drawing process in the solution that boric acid concentration is 2 weight % at 40 DEG C, use and the present invention The identical method of embodiment 1 manufacture according to the film polarizers of comparative example 4.
Comparative example 5
In addition to carrying out drawing process in the solution that boric acid concentration is 2 weight % at 60 DEG C, use and the present invention The identical method of embodiment 1 manufacture according to the film polarizers of comparative example 4.
EXPERIMENTAL EXAMPLE 4：The measurement of optical property
The film polarisation prepared by embodiments of the invention 1 to 3,4 and 5 using JASCO V-7100 spectrophotometric determinations The optical characteristics of piece, such as single light transmittance, degree of polarization, monochrome and colour contamination, and its measurement result are shown in Table 4.
【Table 4】
With reference to table 1 to table 4, it can be seen that the polaroid phase of the basement membrane manufacture different from the use according to comparative example 1 and 2 Use the film polarizers that polyurethane film is manufactured as basement membrane in single light transmittance, partially than, embodiments in accordance with the present invention 1 to 9 The aspects such as light, colourity show significantly excellent optical property.
EXPERIMENTAL EXAMPLE 5：The evaluation of the uniformity of degree of polarization
For the polaroid manufactured by embodiments in accordance with the present invention 2 and comparative example 1, in the direction of the width in each polaroid 10 equidistant point measurement degree of polarizations, then calculate the standard deviation of measured degree of polarization.Measurement result is shown in table 5 In.
【Table 5】
[description of reference numerals]
H：Frame
A：Polyvinyl alcohol film
B：Polymer film
MD：Longitudinal stretching

Claims (12)

1. it is a kind of manufacture film polarizers method, including：
Non-stretched is attached to into thermoplastic based on the film of polyvinyl alcohol by using gravitation therebetween or using adhesive Property polyurethane film at least one surface on and formed film laminates；
The film laminates are stretched at a temperature of 45 DEG C to 55 DEG C；With
The film based on polyvinyl alcohol is set to separate with the thermoplastic polyurethane film.
2. method according to claim 1, wherein, the drawing of the film laminates is carried out at a temperature of 50 DEG C to 55 DEG C Stretch.
3. method according to claim 1, wherein, with the stretching that 5 to 15 times of multiplying power carries out the film laminates.
4. method according to claim 1, wherein, the non-stretched film based on polyvinyl alcohol has 10 μm to 60 μm Thickness.
5. method according to claim 1, wherein, carry out in the boric acid aqueous solution that boric acid concentration is 1% to 5% described The stretching of film laminates.
6. method according to claim 1, wherein, carry out in the boric acid aqueous solution that boric acid concentration is 1% to 3% described The stretching of film laminates.
7. method according to claim 1, wherein, the stretching of the film laminates is carried out so that described based on polyvinyl alcohol Film have 10 μm or less thickness.
8. method according to claim 1, wherein, the stretching of the film laminates is carried out so that described based on polyvinyl alcohol Film shrinkage factor in the width direction be 30% to 80%.
9. method according to claim 1, wherein, after the film laminates are stretched, in drawn based on poly- second Bonding strength between the film of enol and the polyurethane film of drawn is 2N/2cm or less.
10. method according to claim 1, wherein, carried out using the peel strength of 2N/2cm or less based on poly- second The film of enol and the separation of thermoplastic polyurethane film.
11. methods according to claim 1, further include：Before the film laminates are stretched, with iodine and dichroism At least one in dyestuff is dyeed to film laminates.
12. methods according to claim 1, further include：After the film laminates are stretched, drawn is dried Film laminates.
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JP6105794B1 (en) * 2015-11-27 2017-03-29 住友化学株式会社 Manufacturing method of polarizer
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