CN106842403B - The manufacture method of polarizer - Google Patents
The manufacture method of polarizer Download PDFInfo
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- CN106842403B CN106842403B CN201611052849.9A CN201611052849A CN106842403B CN 106842403 B CN106842403 B CN 106842403B CN 201611052849 A CN201611052849 A CN 201611052849A CN 106842403 B CN106842403 B CN 106842403B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67316—Acids
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
- D06P1/67358—Halides or oxyhalides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polarising Elements (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention provides a kind of manufacture method of polarizer, it can further improve productivity by removing the PVA being dissolved in dyeing liquor.The manufacture method includes dyeing process, in the dyeing process, polyvinyl alcohol (PVA) resin film is immersed in the dyeing liquor containing dichroism pigment (iodine), thus PVA resin films are dyed, dyeing liquor contains crosslinking agent (boric acid), and above-mentioned dyeing liquor is filtered using filter material.
Description
Technical field
The present invention relates to the manufacture method of polarizer.
Background technology
Back and forth, the feed element as the polarised light in the display devices such as liquid crystal display device, and as polarization
The detecting element of light, widely uses polarization plates.Polarization plates are usually the single side or double in polarizing coating (polarizer) using bonding agent
Face paste closes the element of the composition of protective film.
Polarizer is by implementing non-stretched polyvinyl alcohol (PVA) resin film (reel film) swelling treatment, at dyeing
It is dried after reason, stretch processing, crosslinking Treatment, carrying out washing treatment etc. to manufacture.
In recent years, with the high performance of liquid crystal display device, slimming, also require to be thinned for polarizer.Example
Such as, thickness be less than 10 μm polarizer by thermoplastic resin base material be coated with PVA system's resin solutions and make its drying and
Formed after the layered product with PVA resins and to implement above-mentioned reason everywhere using the layered product as reel film this is manufactured.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2008-292935 publications
The content of the invention
Problem to be solved by the invention
But in the above-mentioned dyeing process dyed to PVA resin films (PVA resins), into being about to reel
In the dyeing liquor containing iodine (dichroism pigment) of the film immersion in dye bath.At this time, sometimes a part of PVA from PVA systems tree
Adipose membrane is dissolved in dyeing liquor.Particularly dissolubility of the filming to thickness for less than 10 μm of polarizer (PVA resin films)
It is high.
In this case, if carrying out the continuous production of polarizer, the PVA dissolved is accumulated in dye bath, dyeing liquor
In PVA concentration rise so that the PVA of precipitation is attached on PVA resin films, causes the dyeing of polarizer unequal.In addition,
When reel film is taken out out of dye bath, the de- liquid (dehydration) of dyeing liquor is deteriorated.The result is that produce the yield drop so that polarizer
The problem of low such.In addition, in addition to the above problems, due to the PVA concentration rise in dyeing liquor, iodine can be also produced in PVA
The problem of adsorption rate (dyeing kinetics) on resin film reduces, infringement productivity is such.
As its countermeasure, disclose by the foreign matter comprising PVA for making to produce in crosslinking is bathed contacted with activated carbon so that
Adsorb the method (referring to above patent document 1) removed.But activated carbon also adsorbs iodine, therefore, for needing to protect iodine concentration
Hold not preferred for constant dye bath.
It is thus impossible to the PVA being dissolved in dyeing liquor is removed, thus, as elevated for the PVA concentration in dye bath
Countermeasure, is generally updated periodically (replacement) treatment fluid before the above problem is produced.But in existing dyeing process, it is more
Dyeing liquor is used as using iodine, potassium iodide etc..Therefore, the environmental problem caused by the discharge from halogen, it is of high cost the problems such as,
Also the renewal (replacement) of dyeing liquor is not preferably carried out continually.
The present invention be in view of above-mentioned present situation and propose, its purpose is to provide a kind of manufacture method of polarizer, it is logical
Productivity can be further improved by crossing the PVA for removing and being dissolved in dyeing liquor.
The means used to solve the problem
As the means for solving the above problems, mode according to the present invention, there is provided a kind of manufacture method of polarizer,
It includes dyeing process, and in the dyeing process, polyvinyl alcohol (PVA) resin film is immersed in the dyeing comprising dichroism pigment
In liquid, thus above-mentioned PVA resin films are dyed, above-mentioned dyeing liquor contains crosslinking agent, using filter material to above-mentioned dyeing liquor
Filtered.
In addition, the manufacture method of the polarizer of aforesaid way can be following manufacture method：Make above-mentioned dyeing liquor via upper
State filter material circulation.
In addition, the manufacture method of the polarizer of aforesaid way can be following manufacture method：Above-mentioned dyeing liquor is stirred
Mix.
Can be following manufacture method in addition, in the manufacture method of the polarizer of aforesaid way：Above-mentioned crosslinking agent is boron
Compound.
Can be following manufacture method in addition, in the manufacture method of the polarizer of aforesaid way：Above-mentioned boron compound is
Boric acid.
Can be following manufacture method in addition, in the manufacture method of the polarizer of aforesaid way：Above-mentioned PVA systems resin
Its thickness of film is less than 10 μm, is formed on thermoplastic resin base material.
Can be following manufacture method in addition, in the manufacture method of the polarizer of aforesaid way：Above-mentioned crosslinking agent it is dense
Spend for 0.01~0.1 parts by weight.
Can be following manufacture method in addition, in the manufacture method of the polarizer of aforesaid way：Above-mentioned dichroism pigment
For iodine.
Can be following manufacture method in addition, in the manufacture method of the polarizer of aforesaid way：Above-mentioned dichroism pigment
Concentration be 0.01~10 parts by weight.
Can be following manufacture method in addition, in the manufacture method of the polarizer of aforesaid way：Above-mentioned dyeing liquor contains
Potassium iodide.
Invention effect
As described above, mode according to the present invention, using the teaching of the invention it is possible to provide a kind of manufacture method of polarizer, it is dissolved by removing
PVA in dyeing liquor can further improve productivity.
Embodiment
In the present embodiment, the manufacture method as the polarizer for applying the present invention, enumerate exemplified by following situations into
Row explanation：PVA system's resin solutions are coated with thermoplastic resin base material and make its drying, so as to be formed with PVA resins
The layered product of (film), then implements each processing using the layered product as reel film, thus manufactures the polarizer below 10 μm of thickness.
<Thermoplastic resin base material>
First, the thermoplastic resin base material used in the manufacture method to applying the polarizer of the present invention illustrates.
As thermoplastic resin base material, the thermoplastic resin base material for the transparent protective film for being used as polarizer back and forth can be used.
As the material for forming thermoplastic resin base material, such as the transparency, mechanical strength, heat endurance, water can be used
Divide the excellent thermoplastic resins such as block, isotropism, draftability., can be with as the concrete example of such thermoplastic resin
Enumerate：The celluosic resins such as tri acetyl cellulose；The polyester such as polyethylene terephthalate, polyethylene naphthalate
Resin；Polyethersulfone resin；Polysulfone resin；Polycarbonate resin；The polyamides such as nylon, aromatic polyamide；Polyimides
Resin；The vistanexes such as polyethylene, polypropylene, ethylene-propylene copolymer；Ring with ring system structure or norbornene structure
Shape vistanex (norbornene resin)；(methyl) acrylic resin；Polyarylate resin；Polystyrene resin；Poly- second
Enol resin；And their mixture.
In addition, in order to improve the adaptation with PVA resins, thermoplastic resin base material can be implemented to be surface-treated (example
Such as sided corona treatment), the thin layers such as priming coat (prime coat) can also be formed.
Thermoplastic resin can be roughly divided into：Macromolecule is in the thermoplastic resin and height of the crystalline state of ordered arrangement
Molecule is in without ordered arrangement or an only few part has amorphous or noncrystalline state the thermoplastic of ordered arrangement
Property resin.The former is known as crystalline state, the latter is known as amorphous or noncrystalline state.Correspondingly, crystalloid is formed
The thermoplastic resin of the property of state is referred to as crystalline resin, and the thermoplastic resin without such property is referred to as amorphism tree
Fat.
On the other hand, either crystalline resin or amorphous resin, do not reach the resin for being not at crystalline state or
To the resin referred to as amorphous (ァ モ Le Off ァ ス) or amorphous (non-Jing Quality of crystalline state) resin.Here, amorphous or amorphous
The amorphous resin difference of property of the resin with not forming crystalline state uses.
As crystalline resin, for example there is have：Olefin-based resin including polyethylene (PE), polypropylene (PP)；Including
The ester system resin of polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT).The spy of crystalline resin
One of sign is general with the property for arranging and being crystallized by heating, stretching orientation macromolecule.The physical property of resin
Various change occurs according to the degree of crystallization.
On the other hand, such as crystalline resin as polypropylene (PP), polyethylene terephthalate (PET)
For, can also hinder by heat, stretch orientation caused by high molecular arrangement, can suppress to crystallize.It will suppress
Such polypropylene (PP) of crystallization, polyethylene terephthalate (PET) is known as amorphism polypropylene, amorphism is gathered
They, are referred to as amorphism olefin-based resin, amorphism ester system resin by ethylene glycol terephthalate respectively.
Such as in the case of polypropylene (PP), by forming atactic (the ァ sunset Network チ Star Network Agencies without stereoregularity
Make), the amorphism polypropylene (PP) for inhibiting crystallization can be produced.In addition, for example, polyethylene terephthalate
(PET) in the case of, by being copolymerized M-phthalic acid, modified group is used as polymerized monomer as 1,4-CHDM,
I.e. by being copolymerized the molecule for the crystallization for hindering polyethylene terephthalate (PET), it can make and inhibit crystallization
Amorphism polyethylene terephthalate (PET).
The thickness of thermoplastic resin base material (before stretching) can determine suitably, but workability generally from intensity, operability etc.,
The viewpoints such as thin layer are set out, and are 10~500 μm.In particular it is preferred that for 20~300 μm, more preferably 30~200 μm.Thermoplasticity
The thickness of resin base material is particularly preferred in the case of being 50~150 μm.
<Polyvinyl alcohol (PVA) resin (film)>
In the manufacture method of polarizer of the present invention is applied, formed and included on above-mentioned thermoplastic resin base material
The layered product of PVA resins (film).As PVA systems resin, can use without particular limitation has thoroughly in visible region
The scattered adsorption of photosensitiveness has the PVA systems resin of the dichroic substances such as iodine, dichroic dye.
As PVA systems resin, preferably using the PVA systems resin of polarizer is used as back and forth.As PVA systems resin,
PVA or derivatives thereof can be enumerated.As the derivative of PVA, polyvinyl formal, polyvinyl acetal can be enumerated
Deng.In addition, can also enumerate：The alkene such as ethene, propylene；The unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and
Its Arrcostab；Material after being modified using acrylamide etc..
The degree of polymerization of PVA is preferably 100~10000, and more preferably 1000~10000.On saponification degree, generally using soap
Change degree is the PVA of 80~100 moles of %.
The additives such as plasticizer, surfactant can also be contained in PVA systems resin.As plasticizer, can enumerate
Polyalcohol and its condensation product etc..Specifically, such as can enumerate：It is glycerine, two glycerine, triglycerin, ethylene glycol, propane diols, poly-
Ethylene glycol etc..The usage amount of plasticizer etc. is not particularly limited, in preferably every 100 parts by weight PVA systems resin for 20 parts by weight with
Under.
<Layered product (reel film)>
Can be by being coated with the aqueous solution containing PVA systems resin on thermoplastic resin base material as the layered product of reel film
After be dried so as to forming PVA resins to obtain.In addition, layered product can be thermoplastic resin base material and PVA systems tree
The structure that lipid layer is built up across base coat layer.In addition, layered product can also be that thermoplastic resin base material and PVA resins are direct
The structure that is laminated into or be substrate layer and the layered product of the integrated state of hydrophilic macromolecule layer.
Aqueous solution such as can by by the powder of PVA systems resin or crushed material, cut-out thing be dissolved in appropriate heating after
Water (hot water) in prepare.The concentration of aqueous solution is preferably set to 2~20 parts by weight relative to 100 parts by weight of water, more preferably
For 4~10 parts by weight.
Painting solution can be selected suitably using such as bar rubbing method, reversion coating on thermoplastic resin base material
The rolling methods such as method, intaglio plate coating, spin-coating method, silk screen rubbing method, jetting type rubbing method, dip coating, spraying process, die coating method, comma
It is coated with (one ト of カ Application マ Us) method, lip rubbing method, spin-coating method etc..
In the case where thermoplastic resin base material has priming coat, the direct painting solution on the priming coat.The opposing party
Face, in the case where thermoplastic resin base material does not have priming coat, the direct painting solution on substrate layer.Need what is illustrated
It is that drying temperature is preferably set to 50~200 DEG C, more preferably 60~150 DEG C.Drying time is preferably set to 5~30 minutes.
According to obtaining in the case of the stretching ratio of PVA resins in the stretch processing for considering to implement layered product
The thickness of polarizer is formed for less than 10 μm of thickness.The thickness of non-stretched PVA resins is preferably set to 3~20 μ
M, more preferably 5~15 μm.
<Treatment process>
Apply the present invention polarizer manufacture method in, to layered product (reel film) at least implements dyeing processing with
Stretch processing.In addition, in the manufacture method of polarizer of the present invention is applied, it is possible to implement crosslinking Treatment.Dyeing handle,
In crosslinking Treatment and stretch processing bath is respectively handled using dye bath, crosslinking bath and stretch bath respectively.In the situation using processing bath
Under, it can use and each corresponding treatment fluid (aqueous solution etc.) of processing.
<Dyeing process>
In dyeing process, by make iodine or PVA resins that dichroic dye is adsorbed in layered product and be orientated come
Carry out dyeing processing.In dyeing process, dyeing processing can be carried out together with stretch processing.
Dyeing processing is carried out by the way that layered product is immersed in the dyeing liquor in dye bath (dye bath).As dyeing
Liquid, generally iodine solution.Iodine aqueous solution as iodine solution can be used by the use of iodine and contained as the iodide of dissolution aids
There is aqueous solution of iodide ion etc..
As iodide, can use for example：Potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, iodine
Change copper, barium iodide, calcium iodide, stannic iodide, titanium iodide etc..As iodide, preferably potassium iodide.In addition, in the present embodiment
The iodide used are also same with above-mentioned iodide in the case of being used in other process.
Iodine concentration in iodine solution is preferably set to 0.01~10 parts by weight relative to 100 parts by weight of solvent, more preferably
0.02~5 parts by weight, more preferably 0.1~1.0 parts by weight.Iodide concentration is preferably set relative to 100 parts by weight of solvent
It is set to 0.1~10 parts by weight, more preferably 0.2~8 parts by weight.During iodine staining, the temperature of iodine solution is preferably set to 20~50
DEG C, more preferably 25~40 DEG C.Dip time is preferably set to 10~300 seconds, more preferably 20~240 seconds.Need to illustrate
, dyeing time can be soaked in the way of it can reach the degree of polarization specified or transmissivity within the optional time
Stain.
<Stretching process>
In stretching process, dry type stretching processing and wet tensile processing can be used.In stretching process, by layer
Stack implements uniaxial tension to carry out stretch processing.Uniaxial tension can be the longitudinal direction carried out relative to the length direction of layered product
Stretching and any of the cross directional stretch that carries out of width relative to layered product.
, can also be while carrying out stretching in width while being shunk in length direction in cross directional stretch.As transverse direction
Stretching mode, can enumerate for example：The fixing end monoaxial stretching method of one end is fixed via stenter, is not fixed the freedom of one end
Hold monoaxial stretching method etc..
On the other hand, in longitudinal stretching, can use for example：Drawing process, compression stretching method between roller, use tentering
Drawing process of machine etc..In addition, stretch processing can also be carried out with multistage.In addition, stretch processing can be drawn by using twin shaft
Stretch, oblique extension etc. carries out.
Dry type stretching processing can widely set temperature range during stretching layered product, in this respect preferably.In dry type
In stretch processing, preferably by layered product be heated to 50~200 DEG C, more preferably 80~180 DEG C, more preferably 100~
Stretch processing is carried out in the state of 160 DEG C.In stretching process, including in the case of dry type stretching processing, preferably in dyeing process
Preceding implementation dry type stretching processing.
In the treatment fluid used in wet tensile processing, iodide can be contained.Contain iodide in treatment fluid
In the case of, iodide concentration is preferably set to 0.1~10 parts by weight relative to 100 parts by weight of solvent, more preferably 0.2~5 weight
Measure part.Treatment temperature in wet tensile method is preferably set to more than 25 DEG C, more preferably 30~85 DEG C, further for 50~
70℃.Dip time is preferably set to 10~800 seconds, more preferably 30~500 seconds.Furthermore it is possible to at dyeing processing, crosslinking
Reason implements stretch processing together.
In stretching process, relative to layered product the original length, in a manner of being calculated as 4~8 times by total stretching ratio
Carry out stretch processing.Total stretching ratio is preferably 5~7 times.It should be noted that total stretching ratio refers to beyond stretching process
Process etc. in stretching in the case of include the accumulation stretching ratio of stretching in other process.Total stretching ratio is being examined
Suitably determined in the case of considering the stretching ratio in other process etc..
When always stretching ratio is low, orientation deficiency, it is difficult to obtain the polarizer of high optical characteristics (degree of polarization).On the other hand,
When always stretching ratio is excessive, tension failure easily occurs.In addition, polarizer becomes too thin, the processability in subsequent handling has can
It can reduce.
In stretching process, such as " No. 4751481 publications of Japanese Patent No. " are described, can be in the auxiliary in atmosphere
Implement wet tensile processing after stretch processing.The draft temperature in assisting tension processing in atmosphere is preferably preset
For 60~180 DEG C, be further 95~150 DEG C of so high temperature.In addition, in atmosphere assisting tension processing in drawing
Stretch multiplying power and be preferably set to 1.3~4 times, be more preferably set as 1.5~3 times.In addition, the assisting tension in atmosphere handles it
Treatment temperature in the wet tensile processing implemented afterwards is preferably set to 50~80 DEG C, more preferably 60~70 DEG C.Dip time
It is preferably set to 5~120 seconds, more preferably 10~60 seconds.In addition, the stretching ratio preferably always stretching times in wet tensile processing
Rate is set as 4~7 times, more preferably 5~6 times.
In stretching process, including in atmosphere assisting tension processing and wet tensile processing in the case of, preferably
Implement the assisting tension processing in atmosphere before dyeing processing, implement wet tensile processing after dyeing processing.It is this
In the case of, the processing bath for wet tensile processing is also used as crosslinking bath, preferably implements with together with wet tensile processing at crosslinking
Reason.
<Cross-linking process step>
In cross-linking process step, crosslinking Treatment is carried out using boron compound as crosslinking agent.Crosslinking Treatment can with dyeing
Reason, stretch processing carry out together.In addition, crosslinking Treatment can be divided into multiple progress.As boron compound, such as boron can be used
Acid, borax etc..Boron compound uses generally in the form of aqueous solution or water-organic solvent mixed solution.
In the case of using boric acid aqueous solution, heat resistance, therefore, the boric acid concentration of boric acid aqueous solution are assigned by the degree of cross linking
1~10 parts by weight are preferably set to relative to 100 parts by weight of solvent, more preferably 2~7 parts by weight.In boric acid aqueous solution etc.
The iodide such as potassium iodide can be contained.In the case of containing iodide in boric acid aqueous solution, iodide concentration is relative to water 100
Parts by weight are preferably set to 0.1~10 parts by weight, more preferably 0.5~8 parts by weight.
Crosslinking Treatment can be carried out by the way that layered product is immersed in boric acid aqueous solution etc..Processing temperature in crosslinking Treatment
Degree is preferably set to more than 25 DEG C, and more preferably 30~85 DEG C, be further 30~60 DEG C.Processing time is preferably set to 5~
800 seconds, more preferably 8~500 seconds.
<Insoluble process>
Apply the present invention polarizer manufacture method in, to layered product implement dyeing processing or crosslinking Treatment it
Before can implement insoluble processing.The purpose of insoluble process is to implement to be used to make PVA resins undissolved insoluble
Processing.
, can be by making the PVA resins in layered product be immersed in such as boric acid or containing boron in insoluble process
Insoluble processing is carried out in the solution of the boron compounds such as sand.Solution is generally with the shape of aqueous solution or water-organic solvent mixed solution
State uses.
In the case of using boric acid aqueous solution, the boric acid concentration of boric acid aqueous solution is preferably set relative to 100 parts by weight of solvent
It is set to 1~4 parts by weight.Treatment temperature in insoluble process is preferably set to more than 25 DEG C, more preferably 30~85 DEG C, into one
Walk as 30~60 DEG C.Processing time is preferably set to 5~800 seconds, more preferably 8~500 seconds.
<Washing procedure>
In the manufacture method of polarizer of the present invention is applied, dyeing processing, stretch processing can be implemented to layered product
And further implement crosslinking Treatment, but carrying out washing treatment can be implemented after these processing are implemented.
In washing procedure, liquor kalii iodide can be used to carry out carrying out washing treatment.Iodate potassium concn in liquor kalii iodide
0.5~10 parts by weight are preferably set to relative to 100 parts by weight of solvent, more preferably 0.5~8 parts by weight, more preferably 1
~6 parts by weight.
In the carrying out washing treatment using liquor kalii iodide, its treatment temperature is preferably set to 5~60 DEG C, more preferably 10~
40℃.Dip time is preferably set to 1~120 second, more preferably 3~90 seconds.Utilize the rank of the carrying out washing treatment of liquor kalii iodide
As long as just it is not particularly limited before section drying process.
In addition, as carrying out washing treatment, it is possible to implement water washing.Water washing is by the way that PVA systems resin is immersed in
Carried out in the pure water such as ion exchange water, distilled water.Water washing temperature is preferably set to 5~50 DEG C, more preferably 10~45 DEG C,
More preferably 15~40 DEG C.Dip time is preferably set to 5~300 seconds, more preferably 10~240 seconds.
In washing procedure, it will can be combined using the carrying out washing treatment of liquor kalii iodide and water washing, such as also may be used
To use the solution for being suitably combined with the liquid alcohols such as methanol, ethanol, isopropanol, butanol, propyl alcohol.
<Drying process>
In addition, in the manufacture method of polarizer of the present invention is applied, after implementing above-mentioned each processing, final implementation is dry
Dry processing, so as to manufacture polarizer.In drying process, corresponding to the moisture rate needed for obtained polarizer (film), setting
Optimal drying time and drying temperature.Specifically, drying temperature is preferably set to 20~150 DEG C, and more preferably 40~100
℃.When drying temperature is too low, drying time is elongated, it is impossible to efficiently manufactured, therefore it is not preferred.On the other hand, dry temperature
When spending high, obtained polarizer deteriorates, and is deteriorated in terms of optical characteristics and tone.Heat drying time is preferably set to 1~
10 minutes.
<Water soluble antioxidant>
, can be at least one work after above-mentioned dyeing process in the manufacture method of polarizer of the present invention is applied
Carry out utilizing the processing of the treatment fluid containing at least one water soluble antioxidant in sequence.
In processing using the treatment fluid containing water soluble antioxidant, layered product is implemented after dyeing processing each
Contain water soluble antioxidant in any at least one in each bath used in processing.Alternatively, in addition individually implement to utilize
The processing for the treatment of fluid containing water soluble antioxidant.Using the treatment fluid containing water soluble antioxidant processing preferably with friendship
Connection processing and/or stretch processing carry out together.
It should be noted that crosslinking Treatment, stretch processing can by be carried out at the same time multiple processing be uniformly processed come into
OK.Carry out at the same time in being uniformly processed of multiple processing, contain water soluble antioxidant in the bath used during this is uniformly processed.
In addition, in the multistage processing of crosslinking Treatment and stretch processing is in addition individually carried out, in any of crosslinking Treatment and stretch processing
Contain water soluble antioxidant at least one processing.
As water soluble antioxidant, can enumerate for example：Ascorbic acid (vitamin C), arabo-ascorbic acid, thio sulphur
Acid, sulfurous acid, chlorogenic acid, citric acid, Rosmarinic acid and their salt etc..
As salt, alkali metal salts such as sodium salt, sylvite etc. can be enumerated.
Wherein, preferably using ascorbic acid, erythorbate, thiosulfate, sulphite.These water-soluble antioxygens
Agent can be used alone or be applied in combination two or more.
Dichroic substance (iodine of the additive amount of water soluble antioxidant according to contained by each treatment fluid after dyeing process
Or dichroic dye) pollution concentration determine.The pollution concentration caused by dichroic substance in the treatment fluid of pollution is higher,
The additive amount of the water soluble antioxidant then added is also more.
Throughout manage in liquid, preferably according to water soluble antioxidant concentration relative to 100 parts by weight of solvent for 0.005~
The mode of 1 parts by weight adds water soluble antioxidant, more preferably 0.005~0.5 parts by weight.The concentration of water soluble antioxidant
In the case of less than 0.005 parts by weight, the ratio of the water soluble antioxidant in treatment fluid after pollution reduces, it is impossible to fully suppression
Make the reduction of the characteristic (monomer transmissivity, degree of polarization) of obtained polarizer.On the other hand, the concentration of water soluble antioxidant
In the case of more than 1 parts by weight, the ratio increase of the water soluble antioxidant in bath, therefore, obtained polarizer decoloration, thoroughly
Penetrate rate rise.Accompany with this, it is possible to need to improve the iodine concentration of dye bath, but reduction etc. is not present to ask in terms of optical characteristics
Topic.
<Polarizer>
The polarizer manufactured by the manufacture method for the polarizer for applying the present invention is formed on thermoplastic resin base material,
But above-mentioned thermoplastic resin base material can not also be used and implemented using non-stretched PVA resins film as reel film above-mentioned each
Handle to manufacture.In this case, the thickness of polarizer can be more than 10 μm, be preferably 5~50 μm.
Thermoplastic resin base material can directly be used as the transparent protective film of polarization plates described later.Furthermore it is possible to inclined
Shake piece side opposite with thermoplastic resin base material face on be bonded transparent protective film.On the other hand, without using thermoplastic resin
In the case of base material, transparent protective film can be bonded in the both sides of polarizer.In addition, thermoplastic resin base material is shelled from polarizer
From rear, transparent protective film can be bonded in the both sides of the polarizer.
As the material for forming transparent protective film, such as the transparency, mechanical strength, heat endurance, moisture can be used to hinder
The excellent thermoplastic resins such as gear property, isotropism.As the concrete example of such thermoplastic resin, tri acetyl cellulose etc.
Celluosic resin, polyester resin, polyethersulfone resin, polysulfone resin, polycarbonate resin, polyamide, polyimide resin,
Vistanex, (methyl) acrylic resin, cyclic polyolefin resin (norbornene resin), polyarylate resin, polyphenyl
Vinyl, polyvinyl alcohol resin and their mixture.
<Dyeing liquor containing crosslinking agent>
The PVA systems resin used in above-mentioned dyeing process is preferably to be unstained.In addition, applying the polarization of the present invention
In the manufacture method of piece, the dyeing liquor used in above-mentioned dyeing process contains crosslinking agent.As crosslinking agent, such as can be from boron
Using at least one or two or more uses are shared in the boron compounds such as acid, borax, glyoxal, glutaraldehyde etc..Wherein, preferably make
With boron compound, further preferably using boric acid.
In above-mentioned dyeing process, by making dyeing liquor contain micro boric acid (crosslinking agent), which makes from PVA systems tree
Lipid layer is dissolved in the PVA crosslinkings (complexing materialization) in dyeing liquor.Thus, the PVA and dyeing liquor being dissolved in dyeing liquor are generated
In iodine and boric acid bonding gelatinous iodine/PVA/ boric acid complex (hereinafter referred to as complex compounds).
(complexing materialization) is crosslinked in order to make to be dissolved in the PVA in dyeing liquor, the concentration of the boric acid (crosslinking agent) in dyeing liquor
0.01~0.1 parts by weight are preferably set to relative to 100 parts by weight of solvent, more preferably 0.02~0.1 parts by weight.Boric acid it is dense
When spending to be more than 0.01 parts by weight, the PVA being dissolved in dyeing liquor can be made to be crosslinked (complexing materialization).On the other hand, boric acid
When concentration is more than 0.2 parts by weight, boric acid is in the surface of layered product (reel film), the table for the roller for transporting layered product (reel film) sometimes
Face etc. separates out, the defects of causing polarizer etc..
Can be the boric acid that ormal weight is added into dyeing liquor as the method for the concentration for adjusting the boric acid in dyeing liquor
Method.In addition, in the case of there is the processing bath containing boric acid before dyeing processing, can use from the processing bath and layered product
The boric acid brought into together.
In the manufacture method of polarizer of the present invention is applied, above-mentioned dyeing liquor contains micro boric acid (crosslinking agent),
The boric acid makes to be dissolved in the PVA crosslinkings (complexing materialization) in dyeing liquor, thus, it is possible to avoid the attachment of PVA as conventional,
The problems such as dyeing kinetics reduce.That is, the PVA being dissolved in dyeing liquor crosslinks (complexing materialization), is thus not easy to be attached to PVA
Resin (reel film).In addition, de- liquid (dehydration) property of dyeing liquor when reel film is taken out out of dye bath improves.Thus,
It can obtain the polarizer of dye-free inequality.
<The filtering of dyeing liquor>
In addition, in the manufacture method of polarizer of the present invention is applied, dyeing liquor is filtered using filter material.
Thereby, it is possible to by make to be dissolved in dyeing liquor PVA crosslinking (complexing materialization) and generate complex compounds from
Separated in dyeing liquor.For example, adjust the film forming condition for the flat membrane for forming film or carry out surface treatment for being separated into film,
So as to which the organic matters such as PVA are separated with the heterogeneity of dyeing liquor.As filter material, for example, can use polypropylene filter material,
Polyester filter material, nylon filter etc..Module is not particularly limited, it is however preferred to have filter material is accommodated in sealable container and can
Handling ground sets the filter cartridge type of structure in a device.
More specifically, by the inside aperture of the flat membrane inside adjusting film (for example, be adjusted to not make molecular weight 300 with
On material pass through) or formed according to the difference of ionic charge repulsive force come determine material whether the function that can be passed through on film
Property coated film or Surface Treated Films, thus, it is possible to which the organic matters such as PVA are separated with other components in dyeing liquor.
As filter membrane, such as ultrafiltration (UF) film, fine filtering (MF) film, nanofiltration (NF) film, reverse osmosis can be used
(RO) film etc. thoroughly, wherein preferably using UF films, MF films.In addition, in filter membrane, PVA etc. can be had preferably using that can set
The mistake for multiple separation benchmark (for example, molecular weight and ionic charge repulsive force) that machine thing is isolated from the different component of dyeing liquor
Filter membrane.
In addition, the dyeing liquor in dye bath is circulated preferably via filter material.Thereby, it is possible to efficiently remove (to catch using filter material
Collection) complex compounds in dye bath.In addition, dyeing liquor can be recycled.
In addition, the dyeing liquor in dye bath is preferably stirred.Thereby, it is possible to promote to be dissolved in the PVA's in dyeing liquor
It is crosslinked (complexing materialization), efficiently can removes complex compounds from dyeing liquor.
As the method for stirring dyeing liquor, it can use and set the agitating units such as agitating vane dyeing in dye bath
The method for stirring dyeing liquor in bath.It in addition, by the circulation of above-mentioned dyeing liquor, also can stir the dyeing liquor in dye bath
Mix.In addition, by the reel film for transporting (discrepancy) in dye bath the dyeing liquor in dye bath can also stirred.
As described above, in the manufacture method of polarizer of the present invention is applied, it can remove and be dissolved in dyeing liquor
PVA.Thereby, it is possible to can also extend dyeing liquor more while avoiding being dissolved in influence caused by the PVA in dyeing liquor
Period newly (is replaced), therefore, it is possible to further improve the productivity of polarizer.
Embodiment
In the following, make the effect of the present invention clearer by embodiment.It should be noted that the present invention is not limited to down
Embodiment is stated, implementation can be suitably changed in the scope for not changing its purport.
(embodiment 1)
In embodiment 1, using the manufacture method for the polarizer for applying the present invention, produce in thermoplastic resin base material
On the polarizability stacked film formed with polarizer.
Specifically, first, as thermoplastic resin base material, amorphous polyethylene terephthalate (A-PET) is prepared
Film (Mitsubishi chemical Co., Ltd's system, trade name " ノ バ Network リ ァ mono- (registration mark) ", thickness：200μm).
Then, sided corona treatment (treatment conditions are implemented to the single side of the thermoplastic resin base material：90W minutes/m2), at this
Implement on the face of sided corona treatment 65 DEG C be coated with the degree of polymerization 4000,99.0 moles of more than % of saponification degree PVA aqueous solution, so
After make its drying.Thus, as reel film, the PVA systems of single side in thermoplastic resin base material formed with 8.3 μm of thickness have been obtained
The layered product of resin bed.
Then, obtained reel film is subjected to uniaxial tension (stretch processing) in 90 DEG C of baking oven with 1.8 times.
Then, insoluble bath of the reel film after stretching in 30 DEG C of liquid temperature (is dissolved with boric acid relative to 100 parts by weight of water
The boric acid aqueous solution of 3 parts by weight) in dipping 30 seconds (insoluble processing).
Then, in a manner of the transmissivity of polarizer is about 42.0%, while iodine concentration, dip time are adjusted, while will
Reel film immersion (dyeing processing) in dye bath.
In embodiment 1, prepared to have dissolved 0.18 parts by weight of iodine, 1.26 weight of potassium iodide relative to 100 parts by weight of water
Part, the dyeing liquor of 0.02 parts by weight of boric acid.Then, the liquid temperature of the dyeing liquor is set as 30 DEG C, by reel film immersion 13 seconds.
In addition, adding PVA0.05 parts by weight in the dyeing liquor, using magnetic stirrer 15 minutes, while make profit
Liquor circulation after being filtered with polypropylene filter material.
Then, by reel film 40 DEG C of liquid temperature crosslinking bath (relative to 100 parts by weight of water dissolved with 3 parts by weight of potassium iodide,
The boric acid aqueous solution of 3 parts by weight of boric acid) in dipping 30 seconds (crosslinking Treatment).
Then, while (boric acid aqueous solution of the reel film immersion in 70 DEG C of liquid temperature has been dissolved boron relative to 100 parts by weight of water
Sour 4 parts by weight, the aqueous solution of 5 parts by weight of potassium iodide) while carrying out uniaxial tension in longitudinal direction (length direction) (in liquid longitudinally
Stretching).At this time, the maximum tension multiplying power of layered product is 5.94 times.
Then, washing bath of the reel film in 30 DEG C of liquid temperature (4 parts by weight of potassium iodide have been dissolved into relative to 100 parts by weight of water
Aqueous solution) in dipping 5 seconds, be then dried (carrying out washing treatment and drying process) using 60 DEG C of warm wind.
By by above-mentioned operation, having made the inclined of on the thermoplastic resin base material polarizer formed with 4.5 μm of thickness
Shaking property stacked film.
(embodiment 2)
In example 2, it is 0.05 parts by weight to make boric acid, is prepared for dyeing liquor similarly to Example 1 in addition.So
Afterwards, using the dyeing liquor, polarizer has been made by method similarly to Example 1.
(embodiment 3)
In embodiment 3, it is 0.1 parts by weight to make boric acid, is prepared for dyeing liquor similarly to Example 1 in addition.So
Afterwards, using the dyeing liquor, polarizer has been made by method similarly to Example 1.
(embodiment 4)
In example 4, it is 0.2 parts by weight to make boric acid, is prepared for dyeing liquor similarly to Example 1 in addition.So
Afterwards, using the dyeing liquor, polarizer has been made by method similarly to Example 1.
(embodiment 5)
In embodiment 5, it is 0.01 parts by weight to make boric acid, is prepared for dyeing liquor similarly to Example 1 in addition.So
Afterwards, using the dyeing liquor, carry out to dyeing handling by method similarly to Example 1.
(comparative example 1)
In comparative example 1, boric acid is not contained, is prepared for dyeing liquor similarly to Example 1 in addition.
Then, using the dyeing liquor, polarizer has been made by method similarly to Example 1.
Then, each polarizer made for these embodiments 1~5 and comparative example 1, by visual observation observation whether there is generation
" dyeing is uneven ".In addition, the level of residue of the complex compounds to being trapped using filter material is measured, " the filtering to dyeing liquor
Property " evaluated.Wherein, " ◎ " is set to, it is set to "○" by good by very good, difference is set to "×".Further,
Observe and be attached to when dyeing and handling the presence or absence of " pollution caused by boric acid " of device etc. by visual observation.They are collected and is shown in down
State in table 1.
[table 1]
As shown in table 1, it is known that：Compared with the embodiment 1~5 containing boric acid in dyeing liquor, boron is not contained in dyeing liquor
In the comparative example 1 of acid, filterability is poor, and it is uneven to generate dyeing.
On the other hand, compared with embodiment 1~3,5, in example 4, the amount of the boric acid contained in dyeing liquor is excessive, sees
Pollution caused by having observed the precipitation of boric acid.
On the other hand, in embodiment 1~3,5, filterability is good, does not dye inequality, and boric acid is also not observed and leads
The pollution of cause.
Claims (9)
1. a kind of manufacture method of polarizer, it includes dyeing process, in the dyeing process, by undyed polyethenol series tree
Adipose membrane is immersed in the dyeing liquor comprising dichroism pigment, and thus the polyvinyl alcohol resin film is dyed,
The dyeing liquor contains crosslinking agent,
The concentration of the crosslinking agent is 0.01~0.1 parts by weight relative to 100 parts by weight of solvent contained in the dyeing liquor,
In the dyeing liquor, from polyvinyl alcohol, the dichroism pigment and the institute of polyvinyl alcohol resin film dissolving
Crosslinking agent is stated bonding occurs and produces complex compounds,
The dyeing liquor containing the complex compounds is filtered using filter material, the network is separated from the dyeing liquor
Chelate compound.
2. the manufacture method of polarizer as claimed in claim 1, wherein, the dyeing liquor is circulated via the filter material.
3. the manufacture method of polarizer as claimed in claim 1 or 2, wherein, the dyeing liquor is stirred.
4. the manufacture method of polarizer as claimed in claim 1 or 2, wherein, the crosslinking agent is boron compound.
5. the manufacture method of polarizer as claimed in claim 4, wherein, the boron compound is boric acid.
6. the manufacture method of polarizer as claimed in claim 1 or 2, described its thickness of polyvinyl alcohol resin film for 10 μm with
Under, it is formed on thermoplastic resin base material.
7. the manufacture method of polarizer as claimed in claim 1 or 2, wherein, the dichroism pigment is iodine.
8. the manufacture method of polarizer as claimed in claim 1 or 2, wherein, the concentration of the dichroism pigment is relative to institute
It is 0.01~10 parts by weight to state 100 parts by weight of solvent.
9. the manufacture method of polarizer as claimed in claim 1 or 2, wherein, the dyeing liquor contains potassium iodide.
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| JP2015-231961 | 2015-11-27 | ||
| JP2015231961 | 2015-11-27 | ||
| JP2016-138720 | 2016-07-13 | ||
| JP2016138720A JP6105795B1 (en) | 2015-11-27 | 2016-07-13 | Manufacturing method of polarizer |
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| CN106842403B true CN106842403B (en) | 2018-04-24 |
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| JP6713372B2 (en) * | 2016-08-02 | 2020-06-24 | 日東電工株式会社 | Film processing method and polarizing film manufacturing method |
| TWI640556B (en) * | 2017-09-13 | 2018-11-11 | 日商住友化學股份有限公司 | Method and system for forming polarizer sheet |
| JP7014559B2 (en) * | 2017-10-02 | 2022-02-01 | 住友化学株式会社 | Method for manufacturing polarizing film |
| JP7260266B2 (en) * | 2017-10-02 | 2023-04-18 | 住友化学株式会社 | Polarizing film manufacturing equipment |
| CN107619566B (en) * | 2017-10-18 | 2020-06-05 | 中国石油化工集团公司 | Preparation method of polyvinyl alcohol polarizer |
| CN111045139B (en) * | 2019-12-26 | 2022-02-01 | 东华大学 | Preparation method of raincoat brim polaroid |
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| JP2001108827A (en) * | 1999-10-06 | 2001-04-20 | Nitto Denko Corp | Polarizing film and its manufacturing method |
| JP3898416B2 (en) * | 2000-04-04 | 2007-03-28 | 日東電工株式会社 | Manufacturing method of polarizing plate |
| JP4362211B2 (en) * | 2000-06-28 | 2009-11-11 | 株式会社クラレ | Manufacturing method of polarizing film |
| CN100489572C (en) * | 2001-10-03 | 2009-05-20 | 日东电工株式会社 | Polarized plate and its producing method and liquid crystal display |
| JP4394431B2 (en) * | 2003-12-11 | 2010-01-06 | 住友化学株式会社 | Manufacturing method of polarizing film and manufacturing method of polarizing plate |
| KR20090109264A (en) * | 2008-04-15 | 2009-10-20 | 동우 화인켐 주식회사 | Method for recovering of dyeing solution from waste solution for polarizing film and method for preparing polarizing film using the recovered dyeing solution |
| JP5414738B2 (en) * | 2010-09-03 | 2014-02-12 | 日東電工株式会社 | Manufacturing method of thin polarizing film |
| KR20120047499A (en) * | 2010-11-04 | 2012-05-14 | 동우 화인켐 주식회사 | Method of preparing polarizer |
| JP6191197B2 (en) * | 2013-03-29 | 2017-09-06 | 住友化学株式会社 | Manufacturing method of polarizing film |
| KR20140147009A (en) * | 2013-06-18 | 2014-12-29 | 주식회사 엘지화학 | Thin polarizer having good optical properties, manufacturing method thereof, polarizing plate and display device comprising the same |
| WO2014204132A1 (en) * | 2013-06-18 | 2014-12-24 | 주식회사 엘지화학 | Thin polarizer with excellent optical properties, method for manufacturing same, and polarizing plate and display device comprising thin polarizer |
| WO2015065075A1 (en) * | 2013-10-31 | 2015-05-07 | 주식회사 엘지화학 | Apparatus and method for recycling polarizing plate manufacturing solution |
| JP5860448B2 (en) * | 2013-11-14 | 2016-02-16 | 日東電工株式会社 | Polarizing film and manufacturing method of polarizing film |
| JP5943444B2 (en) * | 2015-05-21 | 2016-07-05 | 日東電工株式会社 | Polarizing film and manufacturing method of polarizing film |
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| TWI606253B (en) | 2017-11-21 |
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