CN110446955A - Polarizer and polarizing film - Google Patents
Polarizer and polarizing film Download PDFInfo
- Publication number
- CN110446955A CN110446955A CN201880020354.9A CN201880020354A CN110446955A CN 110446955 A CN110446955 A CN 110446955A CN 201880020354 A CN201880020354 A CN 201880020354A CN 110446955 A CN110446955 A CN 110446955A
- Authority
- CN
- China
- Prior art keywords
- polarizer
- weight
- iodine
- parts
- iodide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Abstract
The purpose of the present invention is to provide a kind of polarizers that content of iodine is high.Polarizer of the invention is made of polyvinyl alcohol resin film.The content of iodine of the polarizer is 12.5 weight % or more.According to the present invention can, provide a kind of content of iodine than existing polarizer compared to high polarizer.
Description
Technical field
The present invention relates to polarizer and polarizing films.
Background technique
Polarizer is used in the image displays such as liquid crystal display.It is by with iodine etc. two that polarizer is representative
Color substance dyes polyvinyl alcohol (PVA) resin film to manufacture (such as patent document 1 and 2).In recent years, image, which is shown, sets
The requirement of standby slimming is increasingly increased.Therefore it also requires further to be thinned for polarizer.But due in dyeing process
The amount for being imported into the iodine of PVA resin film is limited, so if be merely thinned polarizer, ratio of the iodine relative to PVA
Example is constant, but as PVA is thinning, the content of iodine can also be reduced.As a result the transmissivity of polarizer can rise, and cause polarization characteristic
It reduces.Therefore, seek than in the past with the polarizer of higher content of iodine.
Existing technical literature
Patent document
Patent document 1: No. 5048120 bulletins of Japanese Patent No.
Patent document 2: Japanese Unexamined Patent Publication 2013-156391 bulletin
Summary of the invention
Problem to be solved by the invention
The present invention forms in order to solve the above-mentioned existing problems, main to be designed to provide that a kind of content of iodine is high to be polarized
Mirror.
Solution to the problem
Polarizer of the invention is made of polyvinyl alcohol resin film.The content of iodine of the polarizer be 12.5 weight % with
On.
In one embodiment, polarizer with a thickness of 10 μm or less.
In one embodiment, the iron content of polarizer is 500ppm or more.
In one embodiment, the transmissivity of polarizer is 45% hereinafter, and the degree of polarization of polarizer is 99% or more.
In another aspect of the invention, it is provided with a kind of polarizing film.The polarizing film includes above-mentioned polarizer.
The effect of invention
It can provide the content of iodine polarizer higher than existing polarizer according to the present invention.Specifically, polarizer of the invention
It is the polarizer being made of PVA resin film, content of iodine is 12.5 weight % or more.Even if in addition, polarizer of the invention
It is also possible to high content of iodine when thickness thin (such as 10 μm or less).
Specific embodiment
Hereinafter, being illustrated to desirable embodiments of the invention, but the present invention is not limited to these embodiments.
Polarizer of the invention is made of PVA resin film.The content of iodine of the polarizer is 12.5 weight % or more.This hair
Bright polarizer has the content of iodine higher than existing polarizer.
It can illustrate as the PVA resinoid for forming PVA resin film such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer.Poly- second
Enol can be obtained by saponifying polyvinyl acetate.Ethylene-vinyl alcohol copolymer can pass through saponified ethylene-vinyl acetate copolymerization
Object and obtain.The saponification degree of PVA resinoid is usually more than and less than 100 moles % of 85 moles of %, and preferably 95.0 moles of %~
99.99 moles of %, more preferably 99.0 moles of %~99.99 mole %.Saponification degree can be found out according to JIS K 6726-1994.
The polarizer of excellent in te pins of durability can be made by using the PVA resinoid of the saponification degree.
The average degree of polymerization of PVA resinoid can be properly selected according to purpose.Average degree of polymerization is usually 1000~
10000, preferably 1200~4500, more preferably 1500~4300.In addition, average degree of polymerization can be according to JIS K 6726-
1994 find out.
As described above, polarizer of the invention has than previous higher content of iodine.Specifically, polarizer of the invention
Content of iodine be 12.5 weight % or more, preferably 14 weight % or more, more preferably 16 weight % or more.Content of iodine citing comes
It says as 60 weight % or less.In addition, in the present specification, " content of iodine " refers to institute contained in polarizer (PVA resin film)
There is the amount of iodine.More specifically, in polarizer, iodine can be with I-、I2、I3 -、I5 -Etc. forms exist.Content of iodine in this specification
It indicates to contain whole content of iodine of these forms.Especially with a thickness of 2 μm of ultrathin polarizers below,
It can be by providing the content of iodine of polarizer control to the polarizer with excellent degree of polarization in above range.Content of iodine can be according to
The method recorded in embodiment is measured.It specifically, can be glimmering according to being obtained using x-ray fluorescence analysis by following formula
The thickness (μm) of light X-ray intensity (kcps) and film (polarizer) calculates.
(content of iodine)=18.2 × (fluorescent X-ray intensity)/(film thickness)
The fluorescent X-ray intensity of the per unit thickness of polarizer is for example 0.50kcps/ μm or more, preferably
0.65kcps/ μm or more.When the fluorescent X-ray intensity of per unit thickness is above range, polarizer contains for playing conduct
The sufficient iodine of the function of polarizer.
In one embodiment, polarizer of the invention contains ferro element.It can make because polarizer contains ferro element
The humidification durability of polariscope improves.The polarizer high for content of iodine, sometimes the high-temperature humidifying environment as 65 DEG C, 90%RH
Under humidification durability can become problem, it is advantageous to the high polarizers of content of iodine further to contain ferro element.The iron of polarizer
Content is preferably 500ppm or more, more preferably 750ppm or more.By making the iron content of polarizer in above range, can make
The humidification durability of polariscope improves.It is for example 10000ppm or less for the iron content of polarizer.Polarizer be 10 μm with
When lower, by making the iron content of polarizer in above range, transmissivity can be made and degree of polarization is good and humidification durability is also excellent
Different polarizer.The iron content of polarizer can be measured by ICP-MS.
Polarizer of the invention can also contain element sulphur, Zn-ef ficiency, boron element and potassium element etc. other than ferro element.This
A little elements can be contained in polarizer in the manufacturing process of aftermentioned polarizer.These elements can only contain a kind, can also contain
Two or more.In addition, can also contain above-mentioned ferro element and these elements, can also only containing it is therein any one.
The thickness of polarizer of the invention be preferably 10 μm hereinafter, more preferably 5 μm hereinafter, more preferably 2.5 μm hereinafter,
Particularly preferably 2.0 μm or less.Polarizer of the invention is because content of iodine is high, even if being the thickness such as above range,
Excellent optical characteristics can be played.The thickness of polarizer is for example 0.6 μm or more.
The monomer transmissivity of polarizer of the invention is preferably 45% or less.In addition, the monomer transmissivity of polarizer is illustrated
For be 30% or more.In addition, monomer transmissivity (Ts) is to be measured to go forward side by side using 2 degree of visuals field (illuminant-C) of JIS Z8701
Y value obtained from visibility of having gone correction, for example, spectrophotometer (Japan Spectroscopy Corporation's system with integrating sphere of can be used
Make, ProductName: V7100) it is measured.In addition, the degree of polarization of polarizer is preferably 99.0% or more.
Polarizer of the invention can be manufactured by any suitable manufacturing method.In one embodiment, of the invention
Polarizer can by the inclusion of the manufacturing method of following processes be made, the process use containing iodide and to the oxidation of iodide ion
The solution (being also referred to as staining solution below) of agent dyes PVA resin film.It is dyed by using such staining solution, it can be more
Efficiently PVA resin film is dyed, and the high polarizer of content of iodine can be made.
There is no particular restriction for the thickness of PVA resin film, can the thickness of polarizer desirably set.PVA class tree
The thickness of adipose membrane is for example 0.5 μm~200 μm.
In one embodiment, PVA resin film can be formed at the PVA resinoid layer on substrate.Substrate and tree
The laminated body of rouge layer can be made for example, by following methods: the coating fluid containing above-mentioned PVA resinoid is coated on to the side of substrate
Method；The method etc. that PVA resin film is laminated in substrate.Any suitable resin base material can be used as substrate, such as can make
With thermoplastic resin substrate.
Polarizer can for example be manufactured by following manner: by PVA resin film for swelling process, dyeing process,
Cross-linking process step, stretching process, cleaning process, drying process.Each process can carry out at any suitable moment.In addition, according to need
It wants, any process in addition to dyeing process can be omitted, multiple processes can be carried out simultaneously, each process can also be carried out for several times.
Hereinafter, being illustrated to each process.
Swelling process carries out usually before dyeing process.Be swollen process can with dyeing process in same dipping bath together
It carries out.Swelling process can be carried out for example, by PVA resin film to be impregnated in swelling bath.Swelling bath can be used any appropriate
Liquid, such as can be used the water such as distilled water and pure water.Swelling bath contains any suitable other ingredients other than water.As
Other ingredients can enumerate the additives such as alcohol equal solvent, surfactant, iodide etc..As iodide, such as iodate can be used
Potassium, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide and titanium iodide etc..
It is preferable to use potassium iodide.The temperature of swelling bath is, for example, 20 DEG C~45 DEG C.In addition, dip time is, for example, 10 seconds~300 seconds.
In stretching process, according to desired performance and thickness with any suitable stretching ratio to PVA resin film into
Row stretches.Representative is by the simple tension of PVA resin film to relative to 3 times~7 times of original length.Draw direction can be the length of film
It spends in direction (direction MD), can also be the width direction (direction TD) of film.Drawing process can be that dry type stretching is also wet tensile,
Them can also be combined.In addition, PVA resin film can also be stretched when carrying out cross-linking process step, swelling process, dyeing process etc..
In addition, draw direction can be corresponding with the absorption axis direction of obtained polarizer.
Dyeing process is carried out by making PVA class adsorb iodine representatively.Dyeing process for example using iodine aqueous solution into
Row.When using iodine aqueous solution, because iodine is high to the solubility of water, it is advantageous to cooperate iodide in iodine aqueous solution.
In one embodiment, in dyeing process, using containing acting on more iodide ions, iodide and iodide ion
The solution of oxidant etc. dyes PVA resin film.As the oxidant, for example, can be used by cation and anion
The ionic compound of composition.As the ionic compound, it is preferable to use the normal electrode of any one of anion or cation
Current potential is greater than the ionic compound of the standard electrode potential of iodide ion.
In this embodiment, the content of iodide contained in staining solution is preferably 1 relative to 100 parts by weight of solvent
Parts by weight~40 parts by weight, more preferably 3 parts by weight~20 parts by weight.The iodate of above-mentioned act column explanation can be used as iodide
Object.It is preferred that potassium iodide.
When using by cation and the ionic compound that constitutes of anion as above-mentioned oxidant, preferably above-mentioned anion or
The standard electrode potential of cation is greater than the standard electrode potential (0.536V) of iodide ion.The standard of above-mentioned anion or cation
Electrode potential is preferably 0.55V or more, more preferably 0.60V or more.This is because can suitably be functioned as oxidant.Separately
Outside, the standard electrode potential of anion or cation is for example 2.00V or less.
It can illustrate as above-mentioned anion or cation such as Fe3+(0.771V)、Ag+(0.7991V)、Ag2+(1.980V)、Au+(1.83V)、Au3+(1.52V)、Co3+(1.92V)、Cu2+(0.559V)、Mn3+(1.5V)、Pt2+Cations such as (1.188V)；
Br3-(1.0503V)、ClO3 -(0.622V)、ClO2 -(0.681V)、ClO-(0.890V)、Cr2O7 2-(1.36V)、NO3 -
(0.835V、0.94V、0.9557V)、MnO4 -Anion such as (0.56V).It is preferred that ferric ion (Fe3+).Ferric ion exists
It can be present in staining solution as ferrous ion after iodide ion oxidation.Ferric ion and ferrous ion are in dyeing process
In can be taken into PVA resin film.These iron ions have the function of being dehydrated PVA.It therefore, can in subsequent process
The effect for inhibiting more iodide ions to be detached from from PVA resin film.As a result it can provide the polarizer that humidification durability improves.In this explanation
In book, standard electrode potential refers in the case where normal pressure is 1atm, the value in 25 DEG C of aqueous solution.It is 1atm in normal pressure
Under, the standard electrode potential in 25 DEG C of aqueous solution is recorded in for example: " electrochemistry brief guide (electric mood chemistry Bian list) " the 6th edition electricity
Chemistry can compile Maruzen Publishing Co., and Ltd. is published.In the present specification using note in above-mentioned " electrochemistry brief guide "
The value of load.
As above-mentioned oxidant, as long as causing the electrode reaction as desired standard electrode potential in staining solution
Ionic compound, any suitable compound can be used.Can illustrate such as: ferric sulfate, iron chloride, ferric nitrate contain
Fe3+Compound as cation；Potassinm permanganate etc. contains MnO4 -Compound as anion；Copper chloride, copper sulphate etc. contain
There is Cu2+Compound etc. as cation.From containing Fe3+From the viewpoint of, it is preferable to use be selected from ferric sulfate, iron chloride and nitre
At least one kind of compound in sour iron.Oxidant can be used only a kind, can also combine two or more use.
Oxygenate content in staining solution is preferably 0.1 parts by weight~10 parts by weight relative to 100 parts by weight of solvent,
More preferably 0.5 parts by weight~4 parts by weight.Oxygenate content iodide according to contained in staining solution in staining solution
Content determines.
The molar ratio of iodide and oxidant may be set to any suitable value, such as 2/1~50/1, preferably 10/1~
50/1.As long as the molar ratio of iodide and oxidant is within the above range, oxidant can be sufficiently as the oxidation to iodide ion
Agent functions.
Any suitable solvent can be used in solvent as staining solution, usually using water.
Above-mentioned staining solution can also contain any suitable other compounds other than iodide and oxidant.Such as it contaminates
Color solution can further contain iodine.When staining solution further contains iodine, the content of iodine in staining solution for example, relative to
100 parts by weight of solvent are 1 parts by weight or less.
It can illustrate such as colouring method: the method that PVA resin film is impregnated in above-mentioned staining solution；To PVA class tree
The method that adipose membrane is coated with the staining solution；The method etc. of the staining solution is sprayed to PVA resin film.From what can be dyed well
From the point of view of viewpoint, PVA resin film is preferably impregnated in staining solution method.
Liquid temperature when staining solution dyes may be set to any suitable value, such as 20 DEG C~50 DEG C.By PVA resin film
When being impregnated in staining solution, dip time is for example 1 second~1 minute.
In cross-linking process step, usually using boron compound as crosslinking agent.It can illustrate as boron compound such as boric acid, borax
Deng.Preferred boric acid.In cross-linking process step, boron compound uses usually in the form of aqueous solution.
When using boric acid aqueous solution, the boric acid concentration of boric acid aqueous solution is for example the 2 weight % of weight %~15, preferably
For 3 weight of weight %~13 %.It can also be in boric acid aqueous solution further containing iodide, zinc sulfate, zinc chloride such as potassium iodide
Equal zinc compounds.
Cross-linking process step can be carried out by any suitable method.It can illustrate such as: PVA resin film is impregnated in containing boronation
Close the method in the aqueous solution of object；To the method for aqueous solution of the PVA resin film coating containing organic boron compound；To PVA resinoid
The method that film is sprayed the aqueous solution containing organic boron compound.It is preferred that being impregnated in the method in the aqueous solution containing organic boron compound.
The temperature of solution for crosslinking is for example 25 DEG C or more, preferably 30 DEG C~85 DEG C, more preferably 40 DEG C
~70 DEG C.Dip time is for example 5 seconds~800 seconds, preferably 8 seconds~500 seconds.
Aqueous solution of the cleaning process using water or containing above-mentioned iodide carries out.Representative is by by PVA class tree
Adipose membrane is impregnated in potassium iodide aqueous solution to carry out.The temperature of aqueous solution in cleaning process is for example 5 DEG C~50 DEG C.Leaching
The stain time is for example 1 second~300 seconds.
Drying process can be carried out by any suitable method.Can illustrating, dry, decompression is dry as spontaneously dried, blowing
Dry, heat drying etc. is, it is preferable to use heat drying.When being thermally dried, heating temperature is for example 30 DEG C~100 DEG C.
In addition, drying time is for example 10 seconds~10 minutes.
Polarizing film of the invention has above-mentioned polarizer.Polarizing film of the invention is typically at least laminated in one side and protects
Cuticula and use.Forming material as protective film can illustrate such as: diacetyl cellulose (diacetyl cellulose) and three
The olefine kind resins such as the cellulosic resins such as cellulose acetate, (methyl) acrylic resin, cyclenes hydrocarbon resins, polypropylene,
The esters resins such as polyethylene terephthalate resinoid, polyamide-based resin, polycarbonate resin, their copolymer resin
Rouge etc..
The thickness of protective film is for example 10 μm~100 μm.Representative protective film is (specific next across adhesive layer
Say as adhesive layer, adhesive phase) it is laminated in polarizer.Representative adhesive layer is with PVA class bonding agent, active-energy
Line curability bonding agent is formed.Representative adhesive phase is formed with acrylic adhesives.
As described above, the laminated body of substrate and PVA resinoid layer can be used to manufacture in polarizer of the invention.The substrate can
Constituent element as polarizing film uses, without being removed.The protective layer that the substrate for example can be used as polarizer plays
Function.
Embodiment
Hereinafter, specifically describing the present invention by embodiment, but the present invention is not limited to these embodiments.
[embodiment 1]
Polyethylene terephthalate (IPA is copolymerized using water absorption rate 0.75% and Tg75 DEG C of noncrystalline M-phthalic acid
Be copolymerized PET) film (thickness: 100 μm) be used as thermoplastic resin substrate.To substrate single side implement sided corona treatment, and to the corona at
Reason face is coated at 25 DEG C contains polyvinyl alcohol (99.2 moles of degree of polymerization 4200, saponification degree %) and acetyl second with the ratio of 9:1
Acyl modified PVA (degree of polymerization 1200, acetoacetyl modified degree 4.6%, 99.0 moles of % or more of saponification degree, Japanese synthesisization
Learn industrial group's system, trade name " GOHSEFIMER Z200 ") aqueous solution and be dried, form 11 μm of thickness of PVA class tree
Rouge layer, so that laminated body be made.
By obtained laminated body using stenter formula stretching-machine (tenter stretching machine) at 140 DEG C
It carries out stretching (stretch processing) in 4.5 times of atmospheres to the direction orthogonal with the length direction of laminated body.
Then, the insoluble bath that laminated body is impregnated in 30 DEG C of liquid temperature (relative to 100 parts by weight of water, is cooperated into 4 parts by weight
Boric acid aqueous solution obtained from boric acid) 30 seconds (insoluble processing).
Then, the staining solution that laminated body is impregnated in 30 DEG C (relative to 100 parts by weight of water, is added with 6.0 weight of potassium iodide
Measure the aqueous solution of part and 0.8 parts by weight of ferric sulfate n hydrate) 30 seconds, dyed (dyeing processing).Iodine in staining solution
Compound and the molar ratio of oxidant are 23.5/1.In addition, utilizing iodine for the ferric sulfate n hydrate made an addition in staining solution
Average 6.7 hydrates are confirmed as in titration.Therefore, the average molecular weight of ferric sulfate n hydrate is set as 520, calculated and iodide
Molar ratio.
Next, being impregnated in 60 DEG C of liquid temperature of crosslinking bath (relative to 100 parts by weight of water, cooperates the iodate of 3 parts by weight
Potassium simultaneously cooperate 3 parts by weight boric acid obtained from boric acid aqueous solution) in 35 seconds (crosslinking Treatment).
Then, the cleaner bath that laminated body is impregnated in 25 DEG C of liquid temperature (relative to 100 parts by weight of water, is cooperated into 4 weight of potassium iodide
Aqueous solution obtained from part) 10 seconds (cleaning treatment).
Then, it is 60 seconds dry in 60 DEG C of baking oven, and the PVA resinoid layer with 2.5 μm of thickness is made and (rises
Polariscope) laminated body 1.
[embodiment 2]
Laminated body is made in addition to forming 7 μm of thickness of PVA resinoid layer, and staining solution is set as relative to water
Aqueous solution of 100 parts by weight added with 2.0 parts by weight of 15.0 parts by weight of potassium iodide and ferric sulfate n hydrate is (in staining solution
Molar ratio=23.5/1 of iodide and oxidant) other than, the PVA class tree with 1.5 μm of thickness is made similarly to Example 1
The laminated body 2 of rouge layer (polarizer).
[embodiment 3]
In addition to staining solution is set as being hydrated relative to 100 parts by weight of water added with 3.8 parts by weight of potassium iodide and ferric sulfate n
Other than the aqueous solution (molar ratio=23.8/1 of iodide and oxidant in staining solution) of 0.5 parts by weight of object, with embodiment 2
The laminated body 3 of the PVA resinoid layer (polarizer) with 1.5 μm of thickness is similarly made.
[embodiment 4]
Laminated body is made in addition to forming 6 μm of thickness of PVA resinoid layer, and staining solution is set as relative to water
Aqueous solution of 100 parts by weight added with 1.6 parts by weight of 12.0 parts by weight of potassium iodide and ferric sulfate n hydrate is (in staining solution
Molar ratio=23.5/1 of iodide and oxidant) other than, the PVA class tree with 1.2 μm of thickness is made similarly to Example 1
The laminated body 4 of rouge layer (polarizer).
[embodiment 5]
Laminated body is made in addition to forming 5 μm of thickness of PVA resinoid layer, and staining solution is set as relative to water
Aqueous solution of 100 parts by weight added with 2.0 parts by weight of 15.0 parts by weight of potassium iodide and ferric sulfate n hydrate is (in staining solution
Molar ratio=23.5/1 of iodide and oxidant) other than, the PVA class tree with 1.0 μm of thickness is made similarly to Example 1
The laminated body 5 of rouge layer (polarizer).
[embodiment 6]
Other than forming 4 μm of thickness of PVA resinoid layer and laminated body is made, be made has similarly to Example 5
The laminated body 6 of 0.8 μm of thickness of PVA resinoid layer (polarizer).
[embodiment 7]
Laminated body is made in addition to forming 3.6 μm of thickness of PVA resinoid layer, and staining solution is set as relative to water
Aqueous solution of 100 parts by weight added with 3.0 parts by weight of 22.5 parts by weight of potassium iodide and ferric sulfate n hydrate is (in staining solution
Molar ratio=23.5/1 of iodide and oxidant) other than, the PVA class tree with 0.6 μm of thickness is made similarly to Example 1
The laminated body 7 of rouge layer (polarizer).
[embodiment 8]
In addition to formed 13.0 μm of thickness PVA resinoid layers and be made laminated body, and by staining solution be set as relative to
Aqueous solution of 100 parts by weight of water added with 0.7 parts by weight of 5.3 parts by weight of potassium iodide and ferric sulfate n hydrate is (in staining solution
Molar ratio=23.7/1 of iodide and oxidant) other than, the PVA resinoid with 3 μm of thickness is made similarly to Example 1
The laminated body 8 of layer (polarizer).
[embodiment 9]
11 μm of thickness of PVA resinoid layer is formed similarly to Example 1 and laminated body is made.
The laminated body made in 115 DEG C of baking oven is unidirectional towards length direction free end between the different roller of peripheral speed
It is drawn into 2.0 times (stretching in atmosphere).
Then, the insoluble bath that laminated body is impregnated in 30 DEG C of liquid temperature (is cooperated into 3 parts by weight relative to 100 parts by weight of water
Boric acid aqueous solution obtained from boric acid) 30 seconds (insoluble processing).
Then, laminated body is impregnated in 30 DEG C of staining solution (relative to 100 parts by weight of water added with 4.5 weight of potassium iodide
The aqueous solution of amount part and 0.6 parts by weight of ferric sulfate n hydrate) 30 seconds dyed (dyeing processing).In staining solution
The molar ratio of iodide and oxidant is 23.5/1.
Next, being impregnated in 30 DEG C of liquid temperature of crosslinking bath (cooperates the iodate of 3 parts by weight relative to 100 parts by weight of water
Boric acid aqueous solution obtained from potassium and the boric acid of 3 parts by weight) 30 seconds (crosslinking Treatment).
Then, the boric acid aqueous solution that laminated body is impregnated in 70 DEG C of liquid temperature (relative to 100 parts by weight of water, is cooperated into 4 weights on one side
Measure aqueous solution obtained from the boric acid of part and the potassium iodide of 5 parts by weight) in, while towards length side between the different roller of peripheral speed
To progress simple tension at 2.7 times (being stretched in aqueous solution).
Then, the cleaner bath that laminated body is impregnated in 30 DEG C of liquid temperature (is cooperated into the iodine of 4 parts by weight relative to 100 parts by weight of water
Change aqueous solution obtained from potassium) after 10 seconds, it is dried 60 seconds (cleaning-drying operation) with 60 DEG C of warm wind.
So form the laminated body 9 on resin base material with 5 μm of thickness of PVA resinoid layer (polarizer).
[embodiment 10]
In addition to being set as staining solution relative to 100 parts by weight of water added with 12.0 parts by weight of potassium iodide and solid iodine 1.0
Other than the aqueous solution of parts by weight, the layer of the PVA resinoid layer (polarizer) with 1.2 μm of thickness is made similarly to Example 4
Stack 10.
(comparative example 1)
In addition to staining solution is set as being hydrated relative to 100 parts by weight of water added with 3.0 parts by weight of potassium iodide and ferric sulfate n
Other than the aqueous solution (molar ratio=23.5/1 of iodide and oxidant in staining solution) of 0.4 parts by weight of object, with embodiment 2
The laminated body C1 of the PVA resinoid layer (polarizer) with 1.5 μm of thickness is similarly made.
(comparative example 2)
In addition to staining solution is set as being hydrated relative to 100 parts by weight of water added with 3.4 parts by weight of potassium iodide and ferric sulfate n
Other than the aqueous solution (molar ratio=26.6/1 of iodide and oxidant in staining solution) of 0.4 parts by weight of object, with embodiment 2
The laminated body C2 of the PVA resinoid layer (polarizer) with 1.5 μm of thickness is similarly made.
PVA class tree is evaluated using laminated body obtained in Examples 1 to 10 and comparative example 1~2, and by the following method
Monomer transmissivity, content of iodine, iron content, degree of polarization and the humidification durability of rouge layer (polarizer).Show the result in table 1.
1. monomer transmissivity
Use spectrophotometer (Japan Spectroscopy Corporation manufactures, ProductName: V7100) measurement laminated body with integrating sphere
Monomer transmissivity.
2. iodine and iodine compound content
Substrate is obtained to laminated body removing from Examples and Comparative Examples.It is polarized to obtained in Examples and Comparative Examples
Mirror is surveyed using fluorescent X-ray analysis instrument (Rigaku Corporation system, trade name " ZSX100E " measure diameter: ψ 10mm)
Determine fluorescent X-ray intensity (kcps).Determination condition is as described below.
In addition, using spectro-film thickness gauge (Otsuka Electronics Co., Ltd. system, trade name: " MCPD-
3000 ") thickness (μm) of these polarizers is measured.It finds out iodine by following formula, according to obtained fluorescent X-ray intensity and thickness and contains
It measures (weight %).
(content of iodine)=18.2 × (fluorescent X-ray intensity)/(polarizer thickness)
Analytical equipment: Rigaku Corporation fluorescent x-ray analyzer (XRF), ProductName " ZSX100e "
Measure sample: the circular specimen of diameter 10mm
To cathode: rhodium
Light splitting crystallization: lithium fluoride
Exciting light energy: 40kV-90mA
Iodine assay line: I-LA
Sizing technique: FP method
2 θ horns: 103.078deg (iodine), 136.847deg (potassium)
Minute: 40 seconds
3. iron content
The laminated body obtained in the Examples and Comparative Examples removes substrate, is used as sample.Take the sample
In 1.00mg to Teflon (registered trademark) container, nitric acid 10mL is added and covers tightly.Then, using decomposer (Anton
Paar corporation, ProductName: Multiwave 3000), irradiating microwaves, and pressurization acidolysis is carried out at 230 DEG C of highest.Divide completely
Xie Hou is added ultrapure water and is settled to 20mL.After appropriate dilution, iron (Fe) is quantified with ICP-MS.About for analyzing
ICP-MS it is as described below.
ICP-MS:PerkinElmer, Inc. system, ProductName: ELAN DRC II
Analytical element (m/z): Fe (57)
DRC mode: ON
4. the measuring method of degree of polarization
Using UV visible light spectrophotometer (Japan Spectroscopy Corporation manufactures, ProductName " V7100 "), measure thin
Monomer transmissivity (Ts), parallel transmission (Tp) and the orthogonal transmission (Tc) of type light polarizing film simultaneously find out degree of polarization by following formula
(P)。
Degree of polarization (P) (%)={ (Tp-Tc)/(Tp+Tc) }1/2×100
In addition, above-mentioned Ts, Tp and Tc are that be measured and carried out using 2 degree of visuals field (illuminant-C) of JIS Z 8701 can
Y value obtained from the correction of degree of opinion.In addition, investing the meeting such as reflection characteristic, light scattering, adjustment of color to the substrate of slim polarizer
When influencing the function of transmissivity, only the polyvinyl alcohol resin layer containing iodine is measured.
5. humidifying durability evaluation
In the polarizer side for obtaining laminated body obtained in each Examples and Comparative Examples, bonded across 20 μm of thickness of acrylic acid
The alkali-free glass of oxidant layer coating thickness 1.3mm.Then, it is put into the constant temperature and humidity machine of 65 DEG C of 90%RH 500 hours, is commented
Valence humidifies durability.With the polarization with the polarizer before measuring method the same manner of above-mentioned degree of polarization measurement investment and after investment
Degree, and find out variable quantity=(degree of polarization after degree of polarization-investment before investment) of degree of polarization.
[table 1]
Polarizer obtained in embodiment has the high content of iodine of 12.5 weight % or more.In addition, being polarized as ultrathin type
The polarizer of the embodiment 2~7 of mirror also has excellent degree of polarization.In addition, the Examples 1 to 7 containing iron 500ppm or more
Polarizer has excellent humidification durability.
Industrial applicibility
Polarizer of the invention is broadly applicable in LCD TV, liquid crystal display, mobile phone, digital camera, video camera, just
Take the liquid crystal display panel of formula game machine, auto-navigation system, duplicator, printer, facsimile machine, clock and watch, micro-wave oven etc..
Claims (5)
1. a kind of polarizer is made of polyvinyl alcohol resin film, the content of iodine of the polarizer is 12.5 weight % or more.
2. polarizer as described in claim 1, with a thickness of 10 μm or less.
3. polarizer as claimed in claim 1 or 2, the content of ferro element is 500ppm or more.
4. polarizer as claimed any one in claims 1 to 3, transmissivity be 45% or less and degree of polarization be 99% with
On.
5. a kind of polarizing film, it includes polarizers described in any one of Claims 1-4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017073618 | 2017-04-03 | ||
| JP2017-073618 | 2017-04-03 | ||
| PCT/JP2018/012568 WO2018186244A1 (en) | 2017-04-03 | 2018-03-27 | Polarizer and polarizing plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110446955A true CN110446955A (en) | 2019-11-12 |
| CN110446955B CN110446955B (en) | 2022-03-08 |
Family
ID=63712226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880020354.9A Active CN110446955B (en) | 2017-04-03 | 2018-03-27 | Polarizer and polarizing plate |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6857236B2 (en) |
| KR (1) | KR102551170B1 (en) |
| CN (1) | CN110446955B (en) |
| TW (1) | TWI763820B (en) |
| WO (1) | WO2018186244A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112771418B (en) * | 2018-09-28 | 2023-11-21 | 日东电工株式会社 | Method for manufacturing polarizing element |
| WO2021033406A1 (en) * | 2019-08-21 | 2021-02-25 | 日東電工株式会社 | Optical layered body |
| JP2021165809A (en) | 2020-04-08 | 2021-10-14 | 日東電工株式会社 | Polarizing film and polarizing film product |
| JP2021167948A (en) | 2020-04-08 | 2021-10-21 | 日東電工株式会社 | Polarization film |
| JP2021170044A (en) | 2020-04-14 | 2021-10-28 | 日東電工株式会社 | Polarization membrane and polarization film |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1033592A1 (en) * | 1999-03-03 | 2000-09-06 | Konica Corporation | Polarizing plate protective cellulose triacetate film |
| CN101074999A (en) * | 2006-05-18 | 2007-11-21 | 富士胶片株式会社 | Cellulose acylate film and method for producing same, and retardation film, polarizing plate and liquid crystal display device comprising the film |
| CN101101411A (en) * | 2006-07-07 | 2008-01-09 | 日东电工株式会社 | Liquid crystal panel and liquid crystal display |
| JP2010008812A (en) * | 2008-06-27 | 2010-01-14 | Chiba Inst Of Technology | Moisture resistant polarization film |
| CN102150065A (en) * | 2008-09-12 | 2011-08-10 | 日东电工株式会社 | Polarizing film and method for producing the same |
| KR20120111038A (en) * | 2011-03-31 | 2012-10-10 | 동우 화인켐 주식회사 | A polarizing plate and liquid crystal display comprising the same |
| WO2013094435A1 (en) * | 2011-12-19 | 2013-06-27 | コニカミノルタ株式会社 | Polarizing plate and liquid crystal display device using same |
| JP2013156621A (en) * | 2012-01-05 | 2013-08-15 | Nitto Denko Corp | Iodine-based polarizer, polarizing plate, optical film, and image display device |
| CN104169751A (en) * | 2012-11-16 | 2014-11-26 | Lg化学株式会社 | Method for manufacturing thin polarizer, and thin polarizer and polarizing plate manufactured thereby |
| CN104422979A (en) * | 2013-09-09 | 2015-03-18 | 日东电工株式会社 | Pressure-sensitive adhesive layer-bearing polarizing film for transparent conductive coating, laminate, and image display device |
| JP2015114612A (en) * | 2013-12-13 | 2015-06-22 | 三菱製紙株式会社 | Polarizing plate |
| CN105745561A (en) * | 2013-11-19 | 2016-07-06 | 柯尼卡美能达株式会社 | Polarizing plate and liquid crystal display device using same |
| JP2016224469A (en) * | 2010-09-03 | 2016-12-28 | 日東電工株式会社 | Thin polarizing film |
| JP2017004016A (en) * | 2014-07-04 | 2017-01-05 | 住友化学株式会社 | Method for producing polarizing plate with protective films on both surfaces thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01227103A (en) * | 1988-03-08 | 1989-09-11 | Toray Ind Inc | Production of polarizing film |
| JP3410523B2 (en) * | 1993-10-05 | 2003-05-26 | 株式会社クラレ | Manufacturing method of polarizing film |
| CN100473519C (en) * | 2001-11-07 | 2009-04-01 | 富士胶片株式会社 | Polarizing plate, production method thereof and liquid crystal display using the same |
| TW200428040A (en) * | 2003-03-31 | 2004-12-16 | Sumitomo Chemical Co | Polarizer and method for producing the polarizer |
| JP4293543B2 (en) * | 2003-04-21 | 2009-07-08 | 日東電工株式会社 | Polarizer, production method thereof, polarizing plate, optical film, and image display device |
| JP2006047978A (en) * | 2004-06-29 | 2006-02-16 | Nitto Denko Corp | Polarizer, its manufacturing method, polarizing plate, optical film and image display apparatus |
| JP4582704B2 (en) * | 2005-02-01 | 2010-11-17 | 日東電工株式会社 | Adhesive optical film and image display device |
| JP2008040251A (en) * | 2006-08-08 | 2008-02-21 | Nitto Denko Corp | Manufacturing method of polarizer, polarizer, polarizing plate, optical film, and image display device |
| KR100950854B1 (en) * | 2008-04-10 | 2010-03-31 | 주식회사 에이스 디지텍 | Method for manufacturing polyvinyl alcohol polarizer |
| JP5048120B2 (en) | 2010-03-31 | 2012-10-17 | 住友化学株式会社 | Method for producing polarizing laminated film and method for producing polarizing plate |
| JP2013156391A (en) | 2012-01-30 | 2013-08-15 | Konica Minolta Inc | Manufacturing method of roll-shaped circularly polarizing plate, organic electroluminescence display device and lateral electric field type switching mode type liquid crystal display device |
| JP6522289B2 (en) * | 2013-06-28 | 2019-05-29 | 日東電工株式会社 | Polarizing film with adhesive layer, laminate, and image display device |
| JPWO2016104741A1 (en) * | 2014-12-26 | 2017-09-28 | 富士フイルム株式会社 | Polarizer, polarizing plate and image display device |
| JP6604466B2 (en) * | 2015-03-25 | 2019-11-13 | 住友電気工業株式会社 | Copper manufacturing method and copper manufacturing apparatus |
-
2018
- 2018-03-27 KR KR1020197026497A patent/KR102551170B1/en active IP Right Grant
- 2018-03-27 WO PCT/JP2018/012568 patent/WO2018186244A1/en active Application Filing
- 2018-03-27 CN CN201880020354.9A patent/CN110446955B/en active Active
- 2018-03-27 JP JP2019511177A patent/JP6857236B2/en active Active
- 2018-04-02 TW TW107111643A patent/TWI763820B/en active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1033592A1 (en) * | 1999-03-03 | 2000-09-06 | Konica Corporation | Polarizing plate protective cellulose triacetate film |
| CN101074999A (en) * | 2006-05-18 | 2007-11-21 | 富士胶片株式会社 | Cellulose acylate film and method for producing same, and retardation film, polarizing plate and liquid crystal display device comprising the film |
| CN101101411A (en) * | 2006-07-07 | 2008-01-09 | 日东电工株式会社 | Liquid crystal panel and liquid crystal display |
| JP2010008812A (en) * | 2008-06-27 | 2010-01-14 | Chiba Inst Of Technology | Moisture resistant polarization film |
| CN102150065A (en) * | 2008-09-12 | 2011-08-10 | 日东电工株式会社 | Polarizing film and method for producing the same |
| JP2016224469A (en) * | 2010-09-03 | 2016-12-28 | 日東電工株式会社 | Thin polarizing film |
| KR20120111038A (en) * | 2011-03-31 | 2012-10-10 | 동우 화인켐 주식회사 | A polarizing plate and liquid crystal display comprising the same |
| WO2013094435A1 (en) * | 2011-12-19 | 2013-06-27 | コニカミノルタ株式会社 | Polarizing plate and liquid crystal display device using same |
| JP2013156621A (en) * | 2012-01-05 | 2013-08-15 | Nitto Denko Corp | Iodine-based polarizer, polarizing plate, optical film, and image display device |
| CN104169751A (en) * | 2012-11-16 | 2014-11-26 | Lg化学株式会社 | Method for manufacturing thin polarizer, and thin polarizer and polarizing plate manufactured thereby |
| CN104422979A (en) * | 2013-09-09 | 2015-03-18 | 日东电工株式会社 | Pressure-sensitive adhesive layer-bearing polarizing film for transparent conductive coating, laminate, and image display device |
| CN105745561A (en) * | 2013-11-19 | 2016-07-06 | 柯尼卡美能达株式会社 | Polarizing plate and liquid crystal display device using same |
| JP2015114612A (en) * | 2013-12-13 | 2015-06-22 | 三菱製紙株式会社 | Polarizing plate |
| JP2017004016A (en) * | 2014-07-04 | 2017-01-05 | 住友化学株式会社 | Method for producing polarizing plate with protective films on both surfaces thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190128640A (en) | 2019-11-18 |
| TW201841725A (en) | 2018-12-01 |
| CN110446955B (en) | 2022-03-08 |
| TWI763820B (en) | 2022-05-11 |
| WO2018186244A1 (en) | 2018-10-11 |
| JPWO2018186244A1 (en) | 2019-11-21 |
| JP6857236B2 (en) | 2021-04-14 |
| KR102551170B1 (en) | 2023-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110446955A (en) | Polarizer and polarizing film | |
| JP4789925B2 (en) | Iodine polarizing film, method for producing the same, and polarizing plate using the same | |
| CN104737043B (en) | Optical laminates are used before In-cell touch panel liquid crystal cell and use its In-cell touch panel type liquid crystal display device | |
| CN111373294B (en) | Method for manufacturing polarizer | |
| KR20150056044A (en) | Polarizing film and method for manufacturing polarizing film | |
| CN107144907A (en) | Polarizer, Polarizer and image display device | |
| KR20130137657A (en) | Method of manufacturing polarizing plate | |
| KR20200090759A (en) | Polarizer and polarizer | |
| KR20150056045A (en) | Polarizing film and method for manufacturing polarizing film | |
| KR101998093B1 (en) | Method for manufacturing polarizer and polarizer manufactured by the same | |
| CN106896437A (en) | Polarizer, Polarizer and image display device | |
| KR20170068427A (en) | Polarizing film | |
| JPH1149878A (en) | Production of polarized film | |
| CN112771418B (en) | Method for manufacturing polarizing element | |
| JPH1152130A (en) | Production of polarizing film | |
| TW201514555A (en) | Polarizing plate and image display device | |
| JP6817420B2 (en) | Polarizer manufacturing method | |
| JP2895435B2 (en) | Manufacturing method of polarizing film with excellent durability | |
| KR20200103667A (en) | A polyvinyl alcohol-based film for manufacturing a polarizing film, and a polarizing film obtained by using the same, and a polyvinyl alcohol-based resin aqueous solution | |
| JPH0775863B2 (en) | Polarizing film manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |