CN106461843A - Polarizing film, polarizing plate and liquid crystal panel - Google Patents
Polarizing film, polarizing plate and liquid crystal panel Download PDFInfo
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- CN106461843A CN106461843A CN201580026971.6A CN201580026971A CN106461843A CN 106461843 A CN106461843 A CN 106461843A CN 201580026971 A CN201580026971 A CN 201580026971A CN 106461843 A CN106461843 A CN 106461843A
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- Prior art keywords
- polarizing coating
- liquid crystal
- film
- polarization plates
- warpage
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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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Abstract
Provided are: a polarizing film which has a contraction force of 1.5 N or less per 2 mm width in the absorption axis direction after being held at 80 DEG C for 4 hours; a polarizing plate which comprises the polarizing film that has a contraction force of 1.5 N or less per 2 mm width in the absorption axis direction after being held at 80 DEG C for 4 hours and a protection film that is arranged on at least one surface of the polarizing film; and a liquid crystal panel which uses this polarizing plate.
Description
Technical field
The present invention relates to being applied to the polarizing coating of liquid crystal indicator, polarization plates and liquid crystal panel.
Background technology
Polarization plates are widely used as the polarization feed element in the image display devices such as liquid crystal indicator.As polarization
Plate, typically uses structure (the such as Japanese Unexamined Patent Publication 2013-148806 publication that protecting film is fitted to polarizing coating by bonding agent
(patent documentation 1)).
Widely available using the various mobile machine of liquid crystal indicator, slim liquid crystal TV set etc., it is accompanied by this,
In recent years, increasingly require to constitute the polarization plates of liquid crystal panel of liquid crystal indicator and the slimming of liquid crystal cells.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2013-148806 publication
Content of the invention
Invent problem to be solved
On the whole, for polarization plates, particularly for slim polarization plates, the polarizing coating that it has is typically
Stretched operation manufactures, therefore the absorption direction of principal axis (MD) of its polarizing coating and then transmission direction of principal axis (with absorb direction of principal axis
Vertical direction, TD) on, easily produce warpage under such as hot environment, under high humidity environment.If such polarization plates are fitted
Manufacture liquid crystal panel to liquid crystal cells, then liquid crystal cells are thin, rigidity low in the case of, the liquid crystal panel of particularly gained
Warpage can be produced.There is the visual confirmatory to liquid crystal indicator and bring dysgenic possibility in the warpage of liquid crystal panel.
Therefore, it is an object of the invention to, provide polarizing coating and using its polarization plates and liquid crystal panel, wherein institute
Stating polarizing coating can provide：Improve the polarization plates of warpage under the degree of warpage that liquid crystal panel can fully be suppressed.
Method for solving problem
The present invention provides following polarizing coating, polarization plates and liquid crystal panel.
[1] a kind of polarizing coating, it keeps the 4 little contractions with respect to the axial width 2mm of absorption constantly at 80 DEG C
Power is below 1.5N.
[2] polarizing coating according to [1], it is stretched film.
[3] polarizing coating according to [1] or [2], its thickness is less than 20 μm.
[4] polarizing coating according to any one of [1]～[3], its boron containing ratio is the model of 0.5～2.0 weight %
Enclose.
[5] according to the polarizing coating any one of [1]～[4], wherein it is seen that degree revise monomer absorbance be 40% with
Upper, visibility correction degree of polarization is more than 90%.
[6] a kind of polarization plates, it includes：
The 4 little contractilitys with respect to the axial width 2mm of absorption constantly are kept to be the inclined of below 1.5N at 80 DEG C
Vibrating diaphragm；And
The protecting film at least one face of described polarizing coating for the configuration.
[7] polarization plates according to [6], wherein, the thickness of described protecting film is less than 50 μm.
[8] polarization plates according to [6] or [7], it includes configuring the protecting film on the two sides of described polarizing coating,
With respect to a side protective film another side protective film thickness than for more than 1.5.
[9] polarization plates according to any one of [6]～[8], it has long more than side 8cm and more than minor face 5cm
Square configuration.
[10] a kind of liquid crystal panel, it includes：Liquid crystal cells；And configuration in [6]～[9] in its at least one face appoint
Polarization plates described in one.
[11] according to the liquid crystal panel described in [10], wherein, constitute described liquid crystal cells substrate thickness be 0.5mm with
Under.
Invention effect
, it is provided that polarization plates, it is in the journey of the warpage that can fully suppress liquid crystal panel for polarizing coating according to the present invention
Improve warpage under degree.The liquid crystal panel employing the polarization plates of the present invention can suppress warpage, be suitable for slim liquid crystal
Showing device.
Specific embodiment
<Polarizing coating>
Polarizing coating is the blooming having the following properties that, described property is to absorb to have the vibration plane parallel with its absorption axis
Linear polarization and through have vertical with absorption axiss (parallel with the axis of homology) vibration plane linear polarization, the present invention's is inclined
Vibrating diaphragm is it is characterised in that it is below 1.5N with respect to the contractility absorbing axial width 2mm.Hereinafter, by absorption axiss side
It is referred to as " TD " to referred to as " MD ", by transmission direction of principal axis (direction vertical with absorption axiss).
(1) contractility of polarizing coating
The warpage of the polarization plates for the one or two sides laminating protecting film in polarizing coating for the present inventor has been carried out respectively
Plant research, find：If ask will using the severing sample of polarization plates and according to the assay method recorded in detail in [embodiment] project
The amount of warpage (the axial amount of warpage of transmission) with TD for the amount of warpage (absorbing axial amount of warpage) of the MD in the polarization plates obtaining
Ratio (hereinafter referred to as " MD/TD warpage ratio ".) be adjusted to 1.0 or its near, then can effectively suppress using this polarization plates to make
The warpage of the liquid crystal panel made.
And studied by further, find：As for by the MD/TD warpage ratio of polarization plates be adjusted to 1.0 or its
Neighbouring concrete grammar, extremely effective be, by polarizing coating with respect to absorb axial width 2mm contractility (below
Referred to as " MD contractility ".) it is adjusted to below 1.5N.
As described above, polarizing coating is generally manufactured by stretching process, result tensile axis now are usually MD and (absorb
Axle is also MD).Therefore, the MD/TD warpage ratio of existing polarization plates is than 1.0 or it is bigger nearby.If in contrast, using MD
Contractility is the polarizing coating of the present invention of below 1.5N, then the MD/TD warpage ratio of polarization plates can be adjusted to 1.0 or it is attached
Closely.
Here so-called MD contractility refers to, laminating protecting film and make the MD contractility of the polarizing coating before polarization plates,
At 80 DEG C, keep the 4 little contractilitys with respect to the axial width 2mm of absorption constantly.MD contractility is using this polarization
Detailed description that the severing sample of film is measured and its assay method is as described in the project of [embodiment].From for will be inclined
The MD/TD warpage of vibration plate is that effective angle is set out than close to 1.0, and MD contractility is preferably 0.1～1.3N, is more preferably 0.3
～1.1N.
On the other hand, in the polarizing coating of the present invention, at 80 DEG C keep 4 little constantly with respect to the axial width of transmission
The contractility of 2mm is (hereinafter referred to as " TD contractility ".) it is usually 0.1～1.0N.The detailed description of the assay method of TD contractility
As described in the project of [embodiment].Here so-called TD contractility refers to, laminating protecting film and make the polarization before polarization plates
The TD contractility of film.
(2) material of polarizing coating, thickness etc.
The polarizing coating of the present invention can for monomer (monolayer) film comprising thermoplastic resin film that is stretched it is typical that
Make the polyvinyl alcohol resin film gas absorption quantity dichroism pigment through uniaxial tension.
As the polyvinyl alcohol resin constituting polyvinyl alcohol resin film, it is possible to use by polyvinyl acetate system resin
Carry out the material after saponification.As polyvinyl acetate system resin, except the homopolymer of vinylacetate is polyvinyl acetate
In addition, also can illustrate vinylacetate with can be with the copolymer of the other monomers of its copolymerization.As can be with vinylacetate
The other monomers of copolymerization, can include for example, unsaturated carboxylic acid class, olefines, ethylene ethers, unsaturated sulfonic acid class, have ammonia
(methyl) acrylic amide of base etc..The saponification degree of polyvinyl alcohol resin can be the scope, excellent of 80.0～100.0 moles of %
Elect the scope of 90.0～99.5 moles of % as, the more preferably scope of 94.0～99.0 moles of %.
In addition, " (methyl) acrylic acid " refers to, at least one party in acrylic acid and methacrylic acid in this specification.
For when " (methyl) acryloyl group " etc. similarly.
The average degree of polymerization of polyvinyl alcohol resin is preferably 100～10000, more preferably 1500～8000, further
It is preferably 2000～5000.The average degree of polymerization of polyvinyl alcohol resin can be tried to achieve based on JIS K 6726 (1994).If flat
All degree of polymerization less than 100, then are difficult to obtain polarization property, if more than 10000, film processability is deteriorated sometimes.
The dichroism pigment of adsorbed orientation to polarizing coating can be iodine or dichroic organic dye.Dichroic organic dye
Concrete example include red BR, red LR, red R, powder LB, rubine BL, purplish red GS, sky blue LG, lemon yellow, blue BR, blue 2R, purplish blue RY,
Green LG, purple LB, purple B, black H, black B, black GSP, yellow 3G, yellow R, orange LR, orange 3R, scarlet GL, scarlet KGL, Congo red, brilliant violet BK,
Super indigo plant (Supra Blue) G, super indigo plant (Supra Blue) GL, super orange (Supra Orange) GL, direct sky blue, directly
Everbright fast orange S, forever solid black.Dichroism pigment can individually only be used, or two or more may be used.
The thickness of polarizing coating is usually 5～40 μm about, from the viewpoint of the slimming of polarization plates and liquid crystal panel,
It is able to ensure that the scope of sufficient treatability and durability, preferred thickness gets over Bao Yuehao.Therefore, the thickness of polarizing coating is preferably 20
Below μm, it is more preferably less than 15 μm.Wherein, thickness more thin then MD/TD warpage is more than 1 than easier, thus in order that MD/TD
Warpage ratio, close to 1, preferably reduces MD contractility.
(3) polarization characteristic of polarizing coating
The polarization property of polarizing coating can mainly be represented by the numerical value being referred to as monomer absorbance and degree of polarization, respectively such as
Following formula defines：
Monomer absorbance (λ)=0.5 × (Tp (λ)+Tc (λ))
Degree of polarization (λ)=100 × (Tp (λ)-Tc (λ))/(Tp (λ)+Tc (λ))
Here, Tp (λ) is the polarizing coating being measured with the relation of parallel-nicol by the linear polarization of incident wavelength X nm
Absorbance (%), Tc (λ) is the polarizing coating being measured by the relation of linear polarization and the crossed Nicol of incident wavelength X nm
Absorbance (%), and be the mensure of gained during the polarized UV visible absorption spectra being recorded using spectrophotometer is measured
Value.In addition, applying to be referred to as the spirit of visibility correction for the monomer absorbance (λ) tried to achieve according to each wavelength and degree of polarization (λ)
Sensitivity correction, is referred to as visibility correction monomer absorbance (Ty) and visibility correction degree of polarization (Py).These Ty, Py
Value such as spectrophotometer etc. can be used to be measured.
In order to ensure being applied to the good clarity of image during liquid crystal indicator, the visibility correction monomer of polarizing coating
Absorbance (Ty) is preferably more than 40% and visibility correction degree of polarization (Py) is more than 90%.Ty more preferably more than 42%,
Py more preferably more than 99%.Further preferably Ty is more than 42.8%, Py is more than 99.99%.
In order to improve Ty and Py, it usually needs improve stretching ratio, in this case, there is MD contractility and become big inclining
To.Therefore, in the case of obtaining the high polarizing coating of Ty and Py, particularly preferably MD is fully reduced by method described later and shrink
Power.
(4) the boron containing ratio in polarizing coating
In order to reduce the MD contractility of polarizing coating, effectively reduce the boron containing ratio in polarizing coating, for example, it is preferable to will partially
Boron containing ratio in vibrating diaphragm is set as 0.5～2.0 weight %.Boron containing ratio in polarizing coating can calculate as described below.First
First, measure the weight of polarizing coating, then, polarizing coating is immersed in 95 DEG C of hot water 60 minutes so as to be completely dissolved.Then,
Titration is neutralized to the aqueous solution of dissolving polarizing coating, is calculated the boron in polarizing coating and contained by the weight and titer of polarizing coating
Rate.
<Polarization plates>
The polarization plates of the present invention include the polarizing coating and configuration protecting film in its at least one face.
(1) polarizing coating
In order to by the MD/TD warpage ratio of polarization plates be adjusted to 1.0 or its near, as described above, the MD of this polarizing coating
Contractility is set to below 1.5N, is preferably 0.1～1.3N, more preferably 0.3～1.1N.In addition, the polarization plates institute of the present invention
The TD contractility of the polarizing coating having is usually 0.1～1.0N.
Here so-called MD and TD contractility be by polarization plates remove protecting film obtained by polarizing coating contractility, except this with
Outward, represent with above-mentioned<Polarizing coating>Project in explanation contractility identical the meaning.The detailed description of assay method is as [implemented
Example] project in record shown in.Before and after protecting film laminating, thermal history can be different, thus above-mentioned<Polarizing coating>Project
In the value of the value of contractility and so-called contractility here can how much different.
The material of the polarizing coating having for the polarization plates of the present invention, thickness, polarization characteristic, boron containing ratio etc., quote
Above-mentioned<Polarizing coating>Project in description.
(2) protecting film
The protecting film fitted, configuring in the one or two sides of polarizing coating can be for comprising thermoplastic resin for example, chain
Polyolefin-based resins (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system resin (norbornene resin etc.) such polyolefin
Resin；Cellulosic triacetate, cellulose diacetate such cellulose esters system resin；Polyethylene terephthalate,
The such polyester based resin of PEN, polybutylene terephthalate (PBT)；Polycarbonate-based resin；Poly- methyl
Acrylic acid methyl ester. system resin such (methyl) acrylic resin；Or they mixture, the transparent resin film of copolymer etc..
Protecting film is generally laminated in polarizing coating via bond layer.
Protecting film can also improve the such protecting film having optical function concurrently of film for phase retardation film, brightness.For example, pass through
The transparent resin film comprising above-mentioned material is stretched (being stretched uniaxially or biaxially), or liquid crystal is formed on this film
Layer etc., is obtained in that the phase retardation film giving arbitrary phase difference value.
The surface with polarizing coating opposition side in protecting film, can also form hard conating, antiglare layer, anti-reflection layer, resist
Electrostatic layer, stain-proofing layer such surface-treated layer (coating).The method forming surface-treated layer on protecting film surface is not special
Limit, it is possible to use known method.
In the case of the two sides of polarizing coating laminating protecting film, these protecting film can make to comprise resinoid film of the same race,
It can also be the film comprising variety classes resin.Go out than the more effectively viewpoint close to 1.0 from the MD/TD warpage making polarization plates
Send out, the protecting film on two sides preferably comprises resinoid film of the same race, but even in the case of comprising variety classes resin, according to
The present invention is it is also possible to make MD/TD warpage ratio be substantial access to 1.0.
From the viewpoint of the slimming of polarization plates, the thickness of protecting film is preferably thin, if excessively thin, intensity decreases, and processing
Property be deteriorated.Therefore, the thickness of protecting film is preferably 5～150 μm, more preferably 5～100 μm, more preferably 10～50 μm.
As make MD/TD warpage than close to 1.0 additive method it is considered to be improved the reinforced effects using protecting film, for example improve protect
The thickness of cuticula.However, the method is not favourable for the slimming of polarization plates.According to the present invention, even if by protecting film
Thickness reduce until less than 50 μm it is also possible to make MD/TD warpage ratio close to 1.0.
In the case of the two sides of polarizing coating laminating protecting film, these protecting film can have same thickness, can also have
There is mutually different thickness.Fit it is considered to have on the two sides of polarizing coating than the additive method close to 1.0 as making MD/TD warpage
Protecting film, using the method for the reinforced effects of these protecting film.However, in the case of the method, creating the protection on two sides
The necessary identical or essentially identical such restriction of the thickness of film.According to the present invention, even the thickness ratio of the protecting film on two sides is
More than 1.5, it is also possible to make MD/TD warpage ratio close to 1.0 in the case of being more than 2.0 further.
In addition, as making MD/TD warpage than the additive method close to 1.0 it is also contemplated that there being the single-sided lamination only in polarizing coating
Protecting film, using the reinforced effects of this protecting film, but in this case, for the abundant thickness obtaining reinforced effects, material
Rigidity etc. is limited by the protecting film that can use.According to the present invention, it is stacked in one side with protection film layer or is layered in two sides
Unrelated, MD/TD warpage can be made than close to 1.0.Thus, the polarization plates of the present invention are in the fitted protecting film of wide scope maintenance
While the degree of freedom of number, material, thickness etc., MD/TD warpage can be made to be also advantageous than on 1.0 this aspect.
(3) structure of polarization plates
Polarization plates (polarizing coating) can have the suitable geomery sought by applicable liquid crystal indicator, for example
Can be the square configuration (such as rectangle, square) of long more than side 8cm and more than minor face 5cm.In such as existing polarization plates
In the case that such MD/TD warpage ratio is big, the size that there are polarization plates is more big, and the warpage of liquid crystal panel is more significantly inclined to,
According to the present invention, even if making, size increases up to for example long more than side 200cm and more than minor face 100cm is it is also possible to press down well
The warpage of liquid crystal panel processed.
As described above, MD/TD warpage in the polarization plates of the present invention is than near for 1.0 or its, more particularly, it is 1.0
± 0.4, it is preferably 1.0 ± 0.3, more preferably 1.0 ± 0.2.If in this scope, can effectively suppress sticking up of liquid crystal panel
Bent.
Polarization plates can have the adhesive layer for fitting to liquid crystal cells.Adhesive layer can be laminated in protecting film
(for example the one side in polarizing coating is laminated for outside (for example the two sides in polarizing coating is laminated with the situation of protecting film) or polarization face
There is the situation of protecting film).
The binding agent forming adhesive layer generally comprises adhesive composition, and described adhesive composition is by (methyl) propylene
Acid is polymer based on resin, phenylethylene resin series, silicone-based resin etc., is added thereto to isocyanate compound, ring
The such cross-linking agent of oxygen compound, aziridine cpd.The thickness of adhesive layer can be 1～40 μm about.
<Polarizing coating and the manufacture method of polarization plates>
Make, by the polarizing coating of the polyvinyl alcohol resin film gas absorption quantity dichroism pigment of uniaxial tension, can pass through
Following operation manufacture, i.e. polyvinyl alcohol resin film is carried out with the operation of uniaxial tension；By with dichroism pigment to polyethylene
Alcohol resin film is dyeed, thus adsorbing the operation of dichroism pigment；Processed with boric acid aqueous solution and be adsorbed with dichroism pigment
Polyvinyl alcohol resin film operation；And, the operation being carried out after the process using boric acid aqueous solution.As raw material
Polyvinyl alcohol resin film for example, 10～150 μm about of thickness.Make the polarization that thickness is less than 20 μm due to easy
Film, thus the thickness of polyvinyl alcohol resin film is preferably less than 40 μm.
The uniaxial tension of polyvinyl alcohol resin film or can be dyeed with dyeing before the dyeing of dichroism pigment simultaneously
After carry out.In the case of carrying out uniaxial tension after dyeing, this uniaxial tension can enter in boric acid before processing or boric acid are processed
OK.In addition, uniaxial tension can be carried out in these multiple stages.
In uniaxial tension, uniaxial tension can be carried out it is also possible to carry out single shaft using hot-rolling between the different roller of peripheral speed
Stretching.In addition, uniaxial tension can be the dry type stretching being stretched in an atmosphere or using solvent, make poly- second
The wet tensile being stretched under enol resin film swelling state.Stretching ratio is usually 3～8 times about.Good in order to give
Good polarization characteristic, stretching ratio is preferably more than 4 times, more preferably more than 5 times.
In addition, for the MD contractility reducing polarizing coating, preferably by uniaxial tension in boric acid before processing and boric acid are processed
Carry out respectively.In this case, total stretching ratio of boric acid before processing is more than 1.0 times, preferably 1.01～2.5 times.This always draws
Stretch more preferably 1.01～2.1 times of multiplying power, be more preferably 1.01～1.7 times.
Method as being dyeed to polyvinyl alcohol resin film with dichroism pigment, using for example, by polyvinyl alcohol
The method that resin film impregnated in the aqueous solution containing dichroism pigment (staining solution).Polyvinyl alcohol resin film is preferably in dye
Color before processing is implemented in the impregnation process (swelling process) in water in advance.
In the case of using iodine as dichroism pigment, it is typically employed in dipping in the aqueous solution containing iodine and potassium iodide
The method that polyvinyl alcohol resin film is dyeed.The content of the iodine in this dyeing aqueous solution is commonly angled relative to water 100 weight portion
About 0.01～1 weight portion.In addition, it is that 0.5～20 weight portion is left that the content of potassium iodide is commonly angled relative to water 100 weight portion
Right.The temperature of dyeing aqueous solution is usually 20～40 DEG C about.
On the other hand, in the case of using dichroic organic dye as dichroism pigment, following methods are generally adopted：
The method that dipping polyvinyl alcohol resin film is dyeed in the dyeing aqueous solution comprising dichroic organic dye.Dyeing is water-soluble
It is 1 × 10 that the content of the dichroic organic dye in liquid is commonly angled relative to water 100 weight portion-4About～10 weight portions, preferably 1
×10-3About～1 weight portion.This dyeing aqueous solution can contain the inorganic salts such as sodium sulfate as dyeing assistant.Dyeing aqueous solution
Temperature be usually 20～80 DEG C about.
Being processed using the boric acid after the dyeing of dichroism pigment can be by soaking the polyvinyl alcohol resin film after dyeing
Stain to be carried out in containing boron aqueous acid.It is commonly angled relative to water 100 weight in the amount containing the boric acid in boron aqueous acid
Amount part is about 0.1～15 weight portion.As described above, for the MD contractility reducing polarizing coating, effectively reducing polarizing coating
In boron containing ratio, for example, it is preferable to the boron containing ratio in polarizing coating is set as 0.5～2.0 weight %.Therefore, in order to reduce
The MD contractility of polarizing coating, the amount containing the boric acid in boron aqueous acid preferably with respect to water 100 weight portion be 0.1～3
Weight portion, more preferably 0.1～1.3 weight portion.In order to more effectively reduce the MD contractility of polarizing coating, preferably in this boron applicable
While acid concentration, using above-mentioned preferred stretching form.
In the case of using iodine as dichroism pigment, potassium iodide should be preferably comprised containing boron aqueous acid.Contain
The amount of the potassium iodide in boron aqueous acid be commonly angled relative to water 100 weight portion be 0.1～15 weight portion about, be preferably 5～
About 12 weight portions.Temperature containing boron aqueous acid is usually 50～85 DEG C about.
Polyvinyl alcohol resin film after boric acid is processed generally is carried out by impregnated in water or potassium iodide aqueous solution
Process.The temperature of the water in cleaning treatment or potassium iodide aqueous solution is usually 5～40 DEG C about.
Implement dried after cleaning, obtain polarizing coating.Dried can be added using air drier or far infrared
Hot device, hot-rolling etc. are carried out.The temperature of dried is usually 30～100 DEG C about, is preferably 50～80 DEG C.From drying efficiency
Viewpoint is set out, and the film moisture rate before dried is preferably 25～55 weight %.In addition, the film moisture rate after drying process is usual
For 5～35 weight %, from the viewpoint of conveyance property, preferably 6～33 weight %.
Polarization plates can pass through via bond layer the one or two sides in polarizing coating (monomer film) obtained as above
Laminating protecting film is obtaining.As the bonding agent forming bond layer, it is possible to use water system bonding agent or Photocurable adhesive agent.
In the case of two sides laminating protecting film, the bonding agent forming two bond layers can be with identical type or not of the same race
Class.For example, in the case of two sides laminating protecting film, one side can be fitted using water system bonding agent, and one side in addition can
To be fitted using Photocurable adhesive agent.
As water system bonding agent, the bonding agent comprising polyvinyl alcohol resin aqueous solution, water system two-liquid type ammonia can be included
Carbamate system emulsion adhesive etc..Wherein, preferably use the water system bonding agent comprising polyvinyl alcohol resin aqueous solution.
As polyvinyl alcohol resin, it is possible to use be that polyvinyl acetate carries out saponification by the homopolymer of vinylacetate
Alcotex obtained by process, in addition, it is possible to use by vinylacetate with can be with the other monomers of its copolymerization
Copolymer carries out polyvinyl alcohol based copolymer obtained by saponification process or their hydroxyl is carried out partially modified modification
Vinol series polymer etc..Water system bonding agent can comprise polyaldehyde, soluble epoxide compound, melamine based compound, oxygen
Change the additives such as zirconium compoundss, zinc compound.
In the case of using water system bonding agent, preferably implement contained in water system bonding agent for removing after laminating
Water and the drying process that is dried.Baking temperature is preferably 30～100 DEG C.If baking temperature is less than 30 DEG C, protecting film holds
Easily peel off from polarizing coating.If in addition, baking temperature is more than 100 DEG C, exist by the polarization property deterioration of thermal conductivity deflection vibrating diaphragm
May.After drying process, following culture processes can be set, i.e. in room temperature or such as 20～45 DEG C of the temperature more slightly higher than it
Carry out the culture of 12～600 hours about at a temperature of left and right.
Above-mentioned Photocurable adhesive agent refers to, the bonding agent being solidified by irradiation ultraviolet radiation isoreactivity energy-ray, can
Include for example, comprise the bonding agent of polymerizable compound and Photoepolymerizationinitiater initiater, the bonding agent comprising light reactive resin, bag
Bonding agent containing adhesive resin and photoreactivity cross-linking agent etc..As polymerizable compound, photo-curable epoxy can be included
It is the photopolymerization monomers such as monomer, light-curable acrylic system monomer, photo-curable carbamate system monomer or poly- from light
Oligomer of conjunction property monomer etc..As Photoepolymerizationinitiater initiater, the photograph comprising by ultraviolet isoreactivity energy-ray can be included
Penetrate and produce Neutral radical, radical anion, the material of the such spike of radical cation.As comprising polymerism
Compound and the Photocurable adhesive agent of Photoepolymerizationinitiater initiater, preferably comprise photo-curable epoxy monomer and light cation is gathered
Close the material of initiator.
In the case of using Photocurable adhesive agent, after laminating, make photocuring by irradiating active energy beam
Property bonding agent solidification.The light source of active energy beam is not particularly limited, and preferably has luminous distribution in below wavelength 400nm
Active energy beam, specifically, preferably uses low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, chemical lamp, black
Light lamp, microwave-excited mercury lamp, metal halide lamp etc..
Before polarizing coating is fitted with protecting film, in the binding face of polarizing coating and/or protecting film, in order to improve cementability,
Corona treatment can be carried out, halation process, ultraviolet treatment with irradiation, flame (flame) are processed, saponification process is such easily
Bonding is processed.
The polarization plates of the present invention are not limited to said method, can pass through such as Japanese Unexamined Patent Publication 2009-98653 publication
Described in, base material film formed polyvinyl alcohol resin layer, using this resin bed as polarizer layer (being equivalent to polarizing coating)
Method is making.The method is favourable for the polarizer layer of acquisition thin film.
Specifically, the method can include in the following order：
So as to be dried after the coating fluid containing polyvinyl alcohol resin at least one face of base material film coating, by this shape
Polyvinyl alcohol resin layer is become to obtain the resin bed formation process of stacked film；
Stretch stacked film and obtain the stretching process of stretched film；
With dichroism pigment, the polyvinyl alcohol resin layer of stretched film is dyeed, form polarizer layer and (be equivalent to partially
Vibrating diaphragm), it is derived from the dyeing process of polarizability stacked film；
Using bonding agent, protecting film is fitted in the 1st laminating that laminating film is obtained on the polarizer layer of polarizability stacked film
Operation；And
Peel off removing base material film from laminating film and obtain the stripping process of the polarization plates with one side protecting film.
In the case of the two sides stacked guard film of polarizer layer, further include：Using bonding agent in band one side protection
2nd bonding process of the polarization single-sided lamination protecting film of the polarization plates of film.
<Liquid crystal panel>
The liquid crystal panel of the present invention comprise liquid crystal cells and its at least one face laminating, configuration and the invention described above
Related polarization plates.Just for the laminating of the polarization plates of liquid crystal cells, generally to carry out via adhesive layer.Liquid crystal panel can
Only there are the polarization plates related to the invention described above, can also have on two sides in one side.Warpage from suppression liquid crystal panel
From the viewpoint of, preferably the two sides in liquid crystal cells configures the related polarization plates of the invention described above.
Liquid crystal cells have and separate predetermined distance and a pair of substrate (such as glass substrate of opposite configuration by distance piece
Such transparency carrier) and between this pair of substrate enclose liquid crystal liquid crystal layer, can be TN (Twisted
Nematic, twisted-nematic) type, STN (Super-Twisted Nematic, super twisted nematic) type, VA (Vertical
Alignment, vertical alignment) the arbitrary type of drive such as type, IPS (In-Plane Switching, plane conversion) type.
The thickness constituting the substrate of liquid crystal cells is any, in MD/TD warpage as existing polarization plates than big
In the case of, have that substrate is more thin, the warpage of liquid crystal panel is more significantly inclined to.According to the present invention, even if making the thickness of substrate subtract
Little until such as below 0.5mm, further be below 0.3mm it is also possible to well suppress liquid crystal panel warpage.
Liquid crystal panel can have the suitable geomery sought by applicable liquid crystal indicator, can be for for example
The square configuration (such as rectangle, square) of long more than side 8cm and more than minor face 5cm.As existing polarization plates
In the case that MD/TD warpage ratio is big, there is the warpage of the more big then liquid crystal panel of size of liquid crystal panel (corresponding polarization plates) more
Significantly it is inclined to, according to the present invention, even if making the size of liquid crystal panel increase up to for example long more than side 200cm and minor face
More than 100cm, can suppress the warpage of liquid crystal panel well.
Embodiment
Hereinafter, illustrate that embodiment is further elaborated with the present invention, but the present invention is not exposed to these restriction.Separately
Outward, in following embodiment comparative examples, the boron containing ratio in polarizing coating, the polarization characteristic of polarizing coating, MD and TD contractility (are protected
Before cuticula laminating and after laminating), MD/TD warpage ratio is measured in accordance with the following methods.
Boron containing ratio in (a) polarizing coating
Measure the weight of the polarizing coating of gained, then, so that polarizing coating impregnate 60 minutes in 95 DEG C of hot water so as to complete
Dissolving.Then, acid-base titration dissolves the aqueous solution of polarizing coating, is calculated the boron in polarizing coating and is contained by the weight and titer of polarizing coating
There is rate.
The polarization characteristic of (b) polarizing coating
For the polarizing coating of gained, using spectrophotometer (" V-7100 " that Japanese light splitting (strain) is made), measure visibility
Revise monomer absorbance (Ty) and visibility correction degree of polarization (Py).
MD the and TD contractility of the polarizing coating before the laminating of (c) protecting film
Cut out and will be absorbed the width 2mm as long side for the direction of principal axis (MD, draw direction), length 10mm by the polarizing coating of gained
MD contractility measurement sample.This sample is installed to the thermo-mechanical analysis device that SII Nano Technology (strain) makes
(TMA) " EXSTAR-6000 ", in the state of making size keep fixing, measures and keeps the 4 little long side sides constantly producing at 80 DEG C
Contractility (MD contractility) to (absorbing direction of principal axis, MD).In addition, except (hanging down with absorbing direction of principal axis using by transmission direction of principal axis
Straight direction, TD) it is set to the width 2mm on long side, beyond the sample of length 10mm, as described above, measure TD contractility.
MD the and TD contractility of the polarizing coating after the laminating of (d) protecting film
The polarization plates of gained are cut out the small pieces of 10cm × 5cm so as to impregnated in dichloromethane 600mL, enters at room temperature
30 minutes ultrasonic Treatment of row, dissolving removes fitted protecting film.Cut out absorption axiss by the polarizing coating eliminating protecting film
Direction (MD, draw direction) is set to the MD contractility measurement sample of the width 2mm on long side, length 10mm.Except using this examination
Beyond sample, same with above-mentioned (c), measure MD contractility.In addition, being cut out transmission direction of principal axis by the polarizing coating eliminating protecting film
(with absorbing the vertical direction of direction of principal axis, TD) is set to the width 2mm on long side, the polarization plate of length 10mm, in addition, with MD
Contractility similarly, measures TD contractility.
The MD/TD warpage ratio of (e) polarization plates
By the polarization plates of gained, cut out and be set to the width 40mm on long side, length by absorbing direction of principal axis (MD, draw direction)
The MD amount of warpage measurement sample of 150mm.Using acrylic binder, this sample is fitted to flat glass substrate (width
51mm, length 156mm, thickness 0.5mm) face center.In this condition, measure in the following order and absorb axial sticking up
Qu Liang.Using a side of sample minor face as place 0mm, with two-dimensional determinator along long side direction measure place 5mm,
The height of 5 points (being respectively positioned on the center of short side direction) of 40mm, 75mm, 110mm, 145mm, as maximum height and minimum constructive height
Difference, obtain the MD amount of warpage (mm) before heating.Then, at 85 DEG C, sample is heated 250 hours.For the examination after heating
Sample, a side of sample minor face is set to place 0mm, two-dimensional determinator along long side direction measure place 5mm, 40mm,
The height of 5 points (being respectively positioned on the center of short side direction) of 75mm, 110mm, 145mm, as the difference of maximum height and minimum constructive height,
Obtain the MD amount of warpage (mm) after heating.Using the difference being deducted the MD amount of warpage before heating by the MD amount of warpage after heating as MD
Amount of warpage.In addition, except using the width that transmission direction of principal axis (with absorbing the vertical direction of direction of principal axis, TD) is set to long side
Beyond 40mm, the sample of length 150mm, as described above, measure the axial amount of warpage of transmission (TD amount of warpage, mm), press
Obtain MD/TD warpage ratio according to following formula.
MD/TD warpage ratio=MD amount of warpage/TD amount of warpage
<Embodiment 1>
(A) making of polarizing coating
Continuously transport polyvinyl alcohol raw material film (width 450cm, 30 μm of thickness, the average polymerization of polyvinyl alcohol of strip
Degree about 2400,99.9 moles of more than % of saponification degree) while so as to carry out swelling within 97 seconds in impregnated in 30 DEG C of pure water after,
Make it impregnated in the weight of potassium iodide/water than 123 seconds in the aqueous solution comprising iodine of 30 DEG C for 2/100, dyeed.So
Afterwards so as to impregnate 81 seconds in the weight of potassium iodide/boric acid/water is than the aqueous solution of 56 DEG C for 12/1.0/100, carry out boron
Acid treatment.Then, by filling impregnated membranes 2 seconds in 5 DEG C of the rinsing bowl of pure water, thus washing to film, then, lead to
Cross and make film pass through hot-air drying stove, thus carrying out 160 seconds dried at 60 DEG C, obtaining makes polyvinyl alcohol gas absorption quantity iodine
Strip polarizing coating.During this period, mainly carry out longitudinal uniaxial tension process using dyeing process and boric acid treatment process, until
Total stretching ratio before boric acid treatment process is 2.1 times, be 5.5 times from total stretching ratio of raw material film.The thickness of polarizing coating
It is 1.5 weight % for the boron containing ratio in 12.5 μm, polarizing coating.
(B) making of polarization plates
While the strip polarizing coating obtaining in continuous conveyance above-mentioned (A), by doubling roller, triacetyl cellulose will be comprised
Protecting film (40 μm of thickness) fit to behind the two sides of polarizing coating via water system bonding agent, by being passed to hot-air drying stove,
Carry out 98 seconds dried at 60 DEG C, obtain being fitted with the strip polarization plates of protecting film on the two sides of polarizing coating.Water system is glued
Connect agent and use following water system bonding agent：By acetoacetyl modified polyvinyl alcohol resin (trade name " GOHSEFIMER Z-
200 ", Japanese synthetic chemical industry (strain) system) it is dissolved in pure water, the aqueous solution of preparation 10% concentration, mixing conduct thereto is handed over
The sodiam glyoxlate of connection agent, and according to the former: the solids by weight of the latter is mixed than the mode for 1: 0.1, presses further
Photograph for water 100 weight portion, acetoacetyl modified polyvinyl alcohol resin be 1 weight portion mode carried out with pure water dilute
Release, be derived from water system bonding agent.
<Embodiment 2～4>
In the thickness of raw material film that comprises polyvinyl alcohol, the dried operation of (protecting film laminating after) when making polarization plates
Baking temperature and gained polarizing coating thickness as shown in table 1, in addition, similarly to Example 1, make polarization
Film and polarization plates.
<Comparative example 1>
(A) making of polarizing coating
Continuous conveyance strip polyvinyl alcohol raw material film (width 450cm, 30 μm of thickness, polyvinyl alcohol average degree of polymerization about
2400th, 99.9 moles of more than % of saponification degree) while so as to impregnated in 24 seconds in 20 DEG C of pure water, after carrying out swelling so as to
The weight that impregnated in potassium iodide/water, than 74 seconds in the aqueous solution comprising iodine of 30 DEG C for 2/100, is dyeed.Then, make
It impregnates 64 seconds in the weight of potassium iodide/boric acid/water is than the aqueous solution of 56 DEG C for 12/1.5/100, carries out at boric acid
Reason.Then, by impregnated membranes 2 seconds in the rinsing bowl full of 5 DEG C of pure water, film is washed.Then, led to by making film
Cross hot-air drying stove, carry out 160 seconds dried at 60 DEG C, obtaining makes the strip of polyvinyl alcohol gas absorption quantity iodine polarize
Film.During this period, mainly carry out longitudinal uniaxial tension process using dyeing process and boric acid treatment process, until science and engineering at boric acid
Total stretching ratio before sequence is 3.7 times, be 5.5 times from total stretching ratio of raw material film.The thickness of polarizing coating is 13.2 μm, partially
Boron containing ratio in vibrating diaphragm is 2.4 weight %.
(B) making of polarization plates
Using the strip polarizing coating obtaining in above-mentioned (A), make polarization plates according to method same as Example 1.
<Comparative example 2>
Except by the baking temperature in the dried operation of (protecting film laminating after) when making polarization plates be set to 90 DEG C with
Outward, in the same manner as comparative example 1, polarizing coating and polarization plates are made.
Boron containing ratio in the polarizing coating of gained in each embodiment and comparative example, the polarization characteristic of polarizing coating, protecting film patch
MD the and TD contractility of polarizing coating before closing and after laminating, the MD amount of warpage of polarization plates, TD amount of warpage and MD/TD warpage ratio are in the lump
It is shown in table 1." the boric acid amount " of table 1 represents the boric acid content with respect to water 100 weight portion in the aqueous solution processing for boric acid.
[table 1]
Claims (11)
1. a kind of polarizing coating, its keep at 80 DEG C 4 little constantly with respect to absorb axial width 2mm contractilitys be
1.5N it is following.
2. polarizing coating according to claim 1, it is stretched film.
3. polarizing coating according to claim 1 and 2, its thickness is less than 20 μm.
4. the polarizing coating according to any one of claims 1 to 3, its boron containing ratio is the scope of 0.5～2.0 weight %.
5. the polarizing coating according to any one of Claims 1 to 4, wherein,
Visibility correction monomer absorbance is more than 40%, visibility correction degree of polarization is more than 90%.
6. a kind of polarization plates, it includes：
The 4 little polarizing coatings being below 1.5N with respect to the contractility absorbing axial width 2mm constantly are kept at 80 DEG C；
And
The protecting film at least one face of described polarizing coating for the configuration.
7. polarization plates according to claim 6, wherein,
The thickness of described protecting film is less than 50 μm.
8. the polarization plates according to claim 6 or 7, it includes configuring the protecting film on the two sides of described polarizing coating,
With respect to a side protective film another side protective film thickness than for more than 1.5.
9. the polarization plates according to any one of claim 6～8, it has the side of long more than side 8cm and more than minor face 5cm
Shape shape.
10. a kind of liquid crystal panel, it includes：
Liquid crystal cells；And
The polarization plates any one of claim 6～9 at least one face of described liquid crystal cells for the configuration.
11. liquid crystal panels according to claim 10, wherein,
The thickness constituting the substrate of described liquid crystal cells is below 0.5mm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014107225A JP6219781B2 (en) | 2014-05-23 | 2014-05-23 | Polarizing film, polarizing plate and liquid crystal panel |
| JP2014-107225 | 2014-05-23 | ||
| PCT/JP2015/062191 WO2015178150A1 (en) | 2014-05-23 | 2015-04-22 | Polarizing film, polarizing plate and liquid crystal panel |
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| CN106461843A true CN106461843A (en) | 2017-02-22 |
| CN106461843B CN106461843B (en) | 2019-08-02 |
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| JP (1) | JP6219781B2 (en) |
| KR (1) | KR101949003B1 (en) |
| CN (1) | CN106461843B (en) |
| TW (1) | TWI629157B (en) |
| WO (1) | WO2015178150A1 (en) |
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| CN107132606A (en) * | 2016-02-29 | 2017-09-05 | 住友化学株式会社 | Polarization plates group and liquid crystal panel |
| CN109581569A (en) * | 2017-09-28 | 2019-04-05 | 住友化学株式会社 | Polarization plates and its manufacturing method and display device |
| CN109782478A (en) * | 2019-03-21 | 2019-05-21 | 南京汉旗新材料股份有限公司 | A kind of TN/STN polarizing film form and aspect regulation method |
| CN110462500A (en) * | 2017-03-31 | 2019-11-15 | 夏普株式会社 | The manufacturing method of liquid crystal display panel and liquid crystal display panel |
| CN110869840A (en) * | 2017-07-14 | 2020-03-06 | 株式会社Lg化学 | Liquid crystal panel and method for manufacturing same |
| CN111316144A (en) * | 2017-11-10 | 2020-06-19 | 住友化学株式会社 | Circular polarizing plate and display device |
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| JP2018062377A (en) * | 2016-10-14 | 2018-04-19 | 昭和電工パッケージング株式会社 | Sealing material and container sealed by sealing material |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2015222368A (en) | 2015-12-10 |
| KR101949003B1 (en) | 2019-02-15 |
| CN106461843B (en) | 2019-08-02 |
| KR20170012280A (en) | 2017-02-02 |
| JP6219781B2 (en) | 2017-10-25 |
| TWI629157B (en) | 2018-07-11 |
| WO2015178150A1 (en) | 2015-11-26 |
| TW201601895A (en) | 2016-01-16 |
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