CN105891930B - Polarizing coating and polarization plates comprising the polarizing coating - Google Patents
Polarizing coating and polarization plates comprising the polarizing coating Download PDFInfo
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- CN105891930B CN105891930B CN201610081182.9A CN201610081182A CN105891930B CN 105891930 B CN105891930 B CN 105891930B CN 201610081182 A CN201610081182 A CN 201610081182A CN 105891930 B CN105891930 B CN 105891930B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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Abstract
A kind of iodine containing ratio W is providedIThe ratio between (weight %) and visual sensitivity correction monomer transmissivity Ty (%) WI/ Ty is in 0.145 or more polarizing coating and the polarization plates for the protective film being laminated comprising the polarizing coating and on its at least one face.WI/ Ty is preferably below 0.5.
Description
Technical field
The present invention relates to a kind of polarizing coating and include the polarization plates of the polarizing coating.
Background technology
Polarization plates are widely used in using liquid crystal display device as image display device of representative etc..As polarization plates, generally
For be polarizing coating made of the dichroism pigments such as iodine are adsorbed and be orientated on polyvinyl alcohol resin film single or double on
It is bonded the structure of protective film.In recent years, develop to mobile device or slim TV etc. with image display device, increasingly want
Ask the polarization plates even filming of polarizing coating.
Japanese Unexamined Patent Publication 2013-182162 bulletins describe polarizing coating (polarizer layer) thickness in 10 μm of polarization plates below
Manufacturing method.
Invention content
It is smaller to polarize film thickness, is influenced by the moisture invaded by surface bigger, when being placed under hygrothermal environment or is exposed to
In warm water or when being immersed in warm water, have the tendency that easy ting produce the deterioration in characteristics such as polarization characteristic reduction or decoloration.It needs
It is bright, in this specification, " humidity resistance " is known as to the patience of the deterioration in characteristics caused by being placed under hygrothermal environment, to because sudden and violent
The patience for being exposed in warm water or being immersed in caused deterioration in characteristics in warm water is known as " heatproof is aqueous ", these is referred to as " resistance to
It is aqueous ".
In invention described in Japanese Unexamined Patent Publication 2013-182162 bulletins, the protective film by fitting in polarizing coating uses
Moisture permeability low film improves the humidity resistance of polarization plates.But under this approach, the protection membrane material to using
Matter, finite thickness system.
The purpose of the present invention is improve the water resistance of polarizing coating itself.Further, it is another object of the present invention to provide resistance to
Aqueous excellent polarization plates.
The present invention provides polarizing coating as follows and polarization plates.
[1] a kind of polarizing coating, which is characterized in that iodine containing ratio WI(weight %) and visual sensitivity correction monomer are saturating
Penetrate the ratio between rate Ty (%) WI/ Ty is 0.145 or more.
[2] polarizing coating as described in [1], wherein the WI/ Ty is below 0.5.
[3] polarizing coating as described in [1] or [2], thickness is at 10 μm or less.
[4] polarizing coating as described in any one of [1]~[3], it includes polyvinyl alcohol resins.
[5] polarizing coating as described in any one of [1]~[4], wherein the Ty is 40~47%.
[6] a kind of polarization plates, which is characterized in that comprising as described in any one of [1]~[5] polarizing coating and described
The protective film being laminated at least one face of polarizing coating.
According to the present invention it is possible to provide the polarizing coating and polarization plates of excellent water resistance.
Description of the drawings
Fig. 1 is the diagrammatic cross-section for an example for indicating polarization layer structure according to the present invention.
Fig. 2 is the diagrammatic cross-section for another example for indicating polarization layer structure according to the present invention.
Fig. 3 is the flow chart for indicating the polarization preferred example of board fabrication method according to the present invention.
Fig. 4 is the diagrammatic cross-section of an example of the stacking film layer structure for indicating to obtain in resin layer formation process.
Fig. 5 is the diagrammatic cross-section of an example of the stretch film layers structure for indicating to obtain in stretching process.
Fig. 6 is the diagrammatic cross-section of an example of the polarizability stacking film layer structure for indicating to obtain in dyeing process.
Fig. 7 is the diagrammatic cross-section of an example of the lamination film layer structure for indicating to obtain in the first bonding process.
Specific implementation mode
＜ polarizing coatings ＞
Polarizing coating according to the present invention is characterized in that, iodine containing ratio WIWith visual sensitivity correction monomer transmission
The ratio between rate Ty WI/ Ty is 0.145 or more.WI/ Ty 0.145 or more the present invention polarizing coating water resistance (humidity resistance and resistance to
Warm water) it is excellent, even if when being placed under hygrothermal environment or when being exposed in warm water or being immersed in warm water, it is also difficult to generate inclined
Characteristic of shaking reduces or the deterioration in characteristics such as decoloration.If using polarizing coating according to the present invention, due to its own excellent water resistance,
Therefore it is excellent water resistance can be provided without being limited by protection membrane material, the thickness of fitting on it using low film of moisture permeability etc.
Different polarization plates.
In the following, to by WIThe technical meaning that/Ty is set as 0.145 or more illustrates.All the time, it is known that in polyvinyl alcohol
Adsorb and be orientated in polarizing coating made of iodine on resin film, polyvinyl alcohol resin and iodine formed complex compound (hereinafter, referred to as
" PVA- iodo-complexes "), dichroism is absorbed by display by shows polarization property.There is also do not formed in polarizing coating
The iodine of PVA- iodo-complexes, such iodine less has absorption in visible light region, therefore is less contributed to polarization property.It is special
It is not with iodide ion (I-) iodine existing for state do not absorb in visible light region, therefore its own is to the inclined of polarizing coating
Performance of shaking is not contributed completely, and is not also contributed completely the appearance of polarizing coating (form and aspect).
If the polarization property to polarizing coating is described in more detail, referred to as " vision generally can be used in polarization property
Susceptibility corrects monomer transmissivity Ty " and two parameters of " visual sensitivity correction degree of polarization Py " are evaluated.These parameters
It is visible light region obtained by being corrected in such a way that the weighting near the highest 550nm of human eye sensitivity becomes maximum respectively
The transmissivity of (380~780nm of wavelength), degree of polarization.Since human eye is not visible less than the light of 380nm to wavelength, in Ty and
Do not consider in Py.Thus, for example there is the iodide ion (I of absorption band in about 200~230nm wave-length coverages-) its own is right
The Ty and Py of polarizing coating, i.e. polarization property do not influence.
Due to the above reasons, evaluation point is carried out to polarizing coating and using the polarization property of the polarization plates of the polarizing coating in the past
When analysis, to not forming the iodine, particularly iodide ion (I of PVA- iodo-complexes-) do not inquire into.But it is although such
Prior art common sense, but the inventors of the present invention conduct in-depth research, as a result, it has been found that in order to improve polarizing coating and use this partially
The water resistance of the polarization plates of vibrating diaphragm, it is important that PVA- iodo-complexes is not only considered, it is also contemplated that not occurring in Ty and Py
Iodide ion (I-), more specifically it is found that the following contents.
A) iodide ion significantly influences the formation of PVA- iodo-complexes in polarizing coating, rule of thumb, in polarizing coating under
The balance for stating formula (1) is set up：
[changing 1]
B) polarizing coating or polarization plates are when being placed under hygrothermal environment or when being exposed to warm water or being immersed in warm water, iodate
Object ion (I-) be easy to ooze out from polarizing coating, as a result because of iodide ion (I-) exudation so that the balance of above-mentioned formula (1) is inclined to the left
Tiltedly, PVA-I3Complex compound easily reduces.As a result, due to the PVA-I of formation short wavelength (blue) side absorption band3Complex compound tails off, because
This polarizing coating or polarization plates are not easy to absorb blue and generate decoloration (de- indigo plant).In addition, if due to PVA-I3Complex compound tail off and
De- indigo plant is generated, then along with this, degree of polarization also reduces.It should be noted that if the balance of above-mentioned formula (1) is tilted to the left,
Form the PVA-I of long wavelength (red) side absorption band5Complex compound has increased trend.
C) in polarizing coating, by the way that " content of iodide ion " was set as relative to " content of PVA- iodo-complexes "
Amount, then can be set as the state being tilted to the right, even if a small amount of iodide ion (I occurs in advance by the balance of above-mentioned formula (1)-)
Exudation, the balance of above-mentioned formula (1) is not easy to simply tilt to the left, so as to by PVA-I3The stable content of complex compound is
Enough amounts.Thus, it is possible to inhibit de- blue and degree of polarization reduction.
According to above result of study export iodine containing ratio WIThe ratio between monomer transmissivity Ty is corrected with visual sensitivity
That is WI/ Ty parameters.That is, first, it is above-mentioned c) described in " content of PVA- iodo-complexes " can correspond to " Ty ".This is because
The content for forming the PVA- iodo-complexes of visible light region absorption band is proportional to Ty.In addition, in order to by it is above-mentioned c) described in
" content of iodide ion " is present in excess relative to " content of PVA- iodo-complexes ", as long as " total by what is contained in polarizing coating
Iodine atom amount " is set as more relative to " content of PVA- iodo-complexes ", and therefore " content of iodide ion " can be with
Corresponding to " total iodine atom amount "." total iodine atom amount " described herein and above-mentioned " iodine containing ratio WI" equivalent in meaning.Cause
This, " content of iodide ion " can be replaced into " iodine containing ratio W relative to " content of PVA- iodo-complexes "I" opposite
In " Ty ", i.e. WI/Ty。
It is not to improve " iodine containing ratio W as described above, in order to improve the water resistance of polarizing coating and polarization platesI" itself,
But it needs to improve WI/Ty.Result of study is found, in order to improve the water resistance of polarizing coating and polarization plates, WI/ Ty needs to improve extremely
0.145 or more.If less than 0.145, it cannot get the improvement effect of water resistance.From the viewpoint of improving water resistance, WI/ Ty is excellent
It is selected in 0.150 or more.
On the other hand, to WIThe upper limit value of/Ty is not particularly limited, but if its is excessive, as a result, iodide ion
(I-) content become excessive, then PVA-I3Complex compound and PVA-I5The amount balance of complex compound occurs crooked (that is, above-mentioned formula (1)
Balance is excessively tilted to the right, and forms the PVA-I of long wavelength (red) side absorption band5The amount of complex compound is insufficient), it cannot be by polarizing coating
And the initial hue of polarization plates is maintained at neutral.Therefore, WI/ Ty is preferably 0.5 hereinafter, more preferably below 0.4.
The iodine containing ratio W of polarizing coatingIIt is defined as the total weight of the iodine contained in the polarizing coating of per unit weight,
Specifically, can be found out according to following formula (2)：
WI(weight %)={ weight (mg) of total weight (mg)/polarizing coating of iodine } × 100
The total weight of the iodine contained in polarizing coating passes through according to JIS K 0127：2013 burning-chromatography of ions
And it finds out.This method is to arrive the gas collection generated by making polarizing coating sample burn in the burning gases containing oxygen
After in absorbing liquid, quantitative method is carried out using the chromatography of ions.The fuel of polarizing coating (measuring sample) is pre-processed according to the JIS
The 6.3.5 of standard.It should be noted that " weight of polarizing coating " in above-mentioned formula is in iodine containing ratio WIAt 1% or more
It is set as 10~20mg, 100mg or more is set as when less than 1%.
In order to by WI/ Ty is set as 0.145~0.5 range, the iodine containing ratio W of polarizing coatingIPreferably 5~15, it is more excellent
It is selected as 6~10.
In addition, the absorbance when wavelength 217nm of aftermentioned polarizing coating is preferably 2.5 or more, more preferably 3.0 or more,
Upper limit value is generally preferably 4.2 hereinafter, more preferably below 4.0.
The visual sensitivity correction monomer transmissivity Ty of polarizing coating can be in the application polarizing coating or comprising the polarizing coating
The image display devices such as the liquid crystal display device of polarization plates in the value that usually finds out, specifically, it is preferable that 40~47%
In range.Ty is more preferably in the range of 41~45%, at this point, the balance of Ty and Py can be more preferable.Ty Py if excessively high are reduced,
The display quality of image display device reduces.When Ty is too low, the brightness reduction of image display device makes display quality reduce, or
It needs to increase input power to fully improve brightness.
It should be noted that as the other methods for improving polarizing coating water resistance, such as, it is contemplated that improve the suction of iodine
Attached amount reduces Ty.But this method can be such that brightness reduces as described above.On the other hand, it can fully kept according to the present invention
While high Ty, the water resistance of polarizing coating is improved.
The visual sensitivity of polarizing coating corrects degree of polarization Py preferably 99.9% or more, more preferably 99.95% or more.
After Water Resistance Test, from the viewpoint of keep image display device display quality, Water Resistance Test (humidity resistance test or
The aqueous experiment of person's heatproof) after Py it is also preferred that 98.0% or more.
Polarizing coating in a manner of single in the presence of (when individualism), will own as measure Specimen Determination polarizing coating Ty
And Py.On the other hand, it in the presence of in a manner of being fitted with polarization plates made of protective film on polarizing coating, removes and protects from polarization plates
Cuticula and adhesive layer isolate the polarizing coating for including in polarization plates, make as measurement sample, or by polarization plates itself
To measure Specimen Determination Ty and Py, as the Ty and Py of polarizing coating.Using polarization plates as the Ty and Py for measuring Specimen Determination
It is substantially the same as the Ty and Py for measuring Specimen Determination with using the polarizing coating detached.
Polarizing coating according to the present invention is to adsorb and be orientated film made of the iodine as dichroism pigment, is preferably comprised poly-
The film of vinyl alcohol resin, more specifically, preferably in the film (polyethylene constituted with the polyvinyl alcohol resin through being uniaxially stretched
Alcohol resin film) on adsorb and be orientated film made of iodine.
The thickness of polarizing coating for example can at 30 μm hereinafter, further at 20 μm hereinafter, but from polarization plates be thinned sight
Point sets out, preferably at 10 μm hereinafter, more preferably at 8 μm or less.The thickness of polarizing coating is generally at 2 μm or more.Thickness is smaller, water-fast
Property is more easily reduced, but according to the present invention, thickness even if at 10 μm hereinafter, be capable of providing the good polarizing coating of water resistance.
As the polyvinyl alcohol resin for constituting polarizing coating, can be used will set made of polyvinyl acetate system resin saponification
Fat.As polyvinyl acetate system resin, other than homopolymer, that is, polyvinyl acetate of vinyl acetate, can also illustrate second
The copolymer of vinyl acetate and the other monomers that can be copolymerized with it.As can with the other monomers of vinyl acetate copolymerization, such as
It can enumerate：Unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class, (methyl) acrylic amide with ammonium
Deng.
Film made of above-mentioned polyvinyl alcohol resin is filmed constitutes polarizing coating.By polyvinyl alcohol resin system
The method of film is not particularly limited, and can be filmed with well known method, but from being easy to get the small polarizing coating of thickness, process
The operability of the polarizing coating of middle film is also excellent to set out, the solution system of pva coating system resin preferably on base material film
The method of film.
The saponification degree of polyvinyl alcohol resin can be in the range of 80.0~100.0 moles of %, preferably 90.0~99.5
The range of mole %, the more preferably range in 94.0~99.0 moles of %.If less than 80.0 moles % of saponification degree, obtain
The water resistance of polarizing coating is easily reduced.When being more than the polyvinyl alcohol resin of 99.5 moles of % using saponification degree, dyeing sometimes
Slow and productivity reduce while, the polarizing coating with abundant polarization property cannot be obtained.
Saponification degree refers to the acetate (second contained in polyvinyl acetate system resin as polyvinyl alcohol resin raw material
Acyloxy：-OCOCH3) ratio that becomes hydroxyl by saponifying process, it is indicated with unit ratio (mole %), is defined by following formula：
Saponification degree (mole %)=100 × (hydroxyl value) ÷ (hydroxyl value+acetic acid radix).
Saponification degree can be acquired according to JIS K 6726 (1994).Saponification degree is higher, indicates that the ratio of hydroxyl is higher, therefore
It indicates to hinder the ratio of the acetate of crystallization lower.
Polyvinyl alcohol resin can also be the modified modified polyvinylalcohol of a part.Such as it can enumerate：With ethylene, propylene
Equal alkene；The unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid；The Arrcostab of unsaturated carboxylic acid, (methyl) acrylamide
Deng the resin being modified to polyvinyl alcohol resin.Modified ratio is preferably less than 30 moles %, more preferably not
To 10%.It when being performed for more than the modification of 30 moles of %, then is difficult to adsorb dichroism pigment, is difficult to obtain with fully polarization
The tendency of the polarizing coating 5 of performance.It should be noted that " (methyl) acrylic acid " in this specification refers to selected from by acrylic acid
With at least one of the group of methacrylic acid composition.It is also the same for " (methyl) acryloyl group " etc..
The average degree of polymerization of polyvinyl alcohol resin is preferably 100~10000, and more preferably 1500~8000, further
Preferably 2000~5000.The average degree of polymerization of polyvinyl alcohol resin can also be found out according to JIS K 6726 (1994).
＜ polarization plates ＞
(1) the layer structure of polarization plates
Fig. 1 shows the diagrammatic cross-sections of an example of polarization layer structure according to the present invention.As shown in Figure 1 is inclined
Vibration plate 1 is in this way, the polarization plates of the present invention can be the polarization plates with single side protective film, with polarizing coating 5 and in one face
First protective film 10 of upper stacking.First protective film 10 can be layered in via first bonding agents layer 15 on polarizing coating 5.
In addition, polarization plates according to the present invention can also further be bonded protective film on another face of polarizing coating 5,
Specifically, polarization plates 2 as shown in Figure 2 in this way, or the polarization plates with two-sided protective film, with polarizing coating,
The first protective film 10 being laminated in one face, the second protective film 20 being laminated on its another face.Second protective film 20 can
It is layered on polarizing coating 5 via second bonding agents layer 25.
When polarization plates according to the present invention are assembled in image display device as liquid crystal display device, can be with
The polarization plates of visual (front) side of the image-displaying member as liquid crystal cells are set, or configuration is carried on the back in image-displaying member
The polarization plates of side (such as backlight side of liquid crystal display device).
(2) polarizing coating
For polarization plates according to the present invention, the polarizing coating as polarizing coating 5, including involved by aforementioned present invention.
Polarizing coating 5 can quote above-mentioned record in detail as a result,.The iodine containing ratio W of the polarizing coating 5 contained in polarization platesIIt can lead to
It crosses and the polarizing coating 5 for removing protective film and adhesive layer from polarization plates and detaching is measured.
(3) first protective films
First protective film 10 can be comprising following (preferably optically transparent) thermoplastic resin with translucency；Or
The film of their mixture, copolymer etc., such as：Chain polyolefin-based resins (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system
Polyolefin-based resins as resin (norbornene resin etc.)；As cellulosic triacetate, cellulose diacetate
Cellulose esters system resin；Polyester based resin；Polycarbonate-based resin；(methyl) acrylic resin；Polystyrene resin.For
The water resistance for further increasing polarization plates, as first protective film 10, it is also preferred that selection includes polyolefin-based resins, Polyester
The relatively low protective film of moisture permeability as the protective film of resin, (methyl) acrylic resin, polystyrene resin etc..
First protective film 10 or the protective film for having both optical function as phase difference film, brightness enhancement film.For example, passing through
The film or liquid crystal layer etc. is formed on the film that (being uniaxially stretched either biaxial stretch-formed etc.) includes above-mentioned thermoplastic resin are stretched, it can
To obtain imparting the phase difference film of arbitrary phase difference.
As chain polyolefin-based resins, except chain olefin as polyvinyl resin, acrylic resin homopolymer with
Outside, the copolymer for including two or more chain olefins can also be enumerated.
Cyclic polyolefin hydrocarbon system resin refers to the general designation for the resin being polymerized as polymerized unit using cyclic olefin.If enumerated
The specific example of cyclic polyolefin hydrocarbon system resin has the open loop (co) polymer of cyclic olefin, the addition polymers of cyclic olefin, cyclic annular alkene
Hydrocarbon is used unsaturated with the copolymer (representative is random copolymer) of chain olefin as ethylene, propylene and by these
The hydride etc. of carboxylic acid or derivatives thereof modified graft polymers and these.Wherein, as cyclic olefin, it is preferable to use using
The norbornene resin that the orbornene-baseds monomers such as norbornene, polycyclic orbornene-based monomer obtain.
Cellulose esters system resin is the ester of cellulose and aliphatic acid.The specific example of cellulose esters system resin includes：Fiber
Plain triacetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate.In addition, being total to for these also can be used
The cellulose esters system resin modified with other substituent groups of a part of polymers, hydroxyl.Wherein, particularly preferred cellulosic triacetate
(triacetyl cellulose：TAC).
Polyester based resin is the resin other than above-mentioned cellulose esters system resin for having ester bond, generally comprises polynary carboxylic
The condensation polymer of acid or derivatives thereof and polyalcohol.As polybasic carboxylic acid or derivatives thereof, dicarboxylic acids or derivatives thereof, example can be used
It can such as enumerate：Terephthalic acid (TPA), M-phthalic acid, dimethyl terephthalate (DMT), naphthalene diformic acid dimethyl ester etc..As polyalcohol,
Glycol can be used, such as can enumerate：Ethylene glycol, propylene glycol, butanediol, neopentyl glycol, cyclohexanedimethanol etc.
The specific example of polyester based resin includes：Polyethylene terephthalate, polybutylene terephthalate, poly- naphthalene two
Formic acid second diester, poly- naphthalenedicarboxylic acid fourth diester, polytrimethylene terephthalate, poly- naphthalenedicarboxylic acid propylene diester, poly terephthalic acid
Cyclohexane dicarboxylates, poly- naphthalenedicarboxylic acid cyclohexane dicarboxylates.
Polymer made of polycarbonate-based resin is bonded comprising monomeric unit by carbonate group.Polycarbonate-based resin
Can also be resin, the copolymerization polycarbonate etc. for being known as modified polycarbonate after modifying polymer backbone.
(methyl) acrylic resin is to have the compound of (methyl) acryloyl group as the resin of main composition monomer.
The specific example of (methyl) acrylic resin, such as including：(methyl) acrylate poly- as polymethyl methacrylate；
Methyl methacrylate-(methyl) acrylic copolymer；Methyl methacrylate-(methyl) acrylate copolymer；Methyl-prop
E pioic acid methyl ester-acrylate-(methyl) acrylic copolymer；(methyl) acrylate-styrene copolymer (MS resins etc.)；
Methyl methacrylate with alicyclic alkyl compound copolymer (for example, methyl methacrylate-methacrylic acid
Hexamethylene ester copolymer, methyl methacrylate-(methyl) acrylic acid norbornyl ester copolymer etc.).It is preferable to use with poly- (methyl)
(methyl) acrylic acid C poly- as methyl acrylate1-6Arrcostab is the polymer of principal component, and more preferable use is with metering system
Sour methyl esters is the methyl methacrylate system resin of principal component (50~100 weight %, preferably 70~100 weight %).
Can also on the surface of the opposite side of the polarizing coating 5 in the first protective film 10, formed as hard conating, antiglare layer,
Anti-reflecting layer, antistatic layer, surface-treated layer (coating layer) as stain-proofing layer.In addition, the first protective film 10 can also contain
It is one or more kinds of lubricants, plasticizer, dispersant, heat stabilizer, ultra-violet absorber, infrared absorbent, antistatic
Additive as agent, antioxidant.
From the viewpoint of polarization plates slimming, the thickness of the first protective film 10 is preferably at 90 μm hereinafter, more preferably in 50 μ
M is hereinafter, further preferably at 30 μm or less.From the viewpoint of intensity and operability, the thickness of the first protective film 10 is generally 5
μm or more.
(4) first bonding agents layer
First bonding agents layer 15 is the layer for first protective film 10 that is adhesively fixed on a face of polarizing coating 5.It is formed
The bonding agent of first bonding agents layer 15 can be containing by the active energy as ultraviolet light, visible light, electron beam, X-ray
Measure ray irradiation and the active energy ray-curable bonding agent of cured curability compound, make polyvinyl alcohol resin this
The bonding agent ingredient of sample dissolve or be dispersed in water and the water system bonding agent that is formed.Wherein, from raising polarization plates water resistance
Viewpoint is set out, it is preferable to use active energy ray-curable bonding agent.The preferred example of active energy ray-curable bonding agent
It is ultra-violet solidified bonding agent.
As the active energy ray-curable bonding agent for forming first bonding agents layer 15, go out from performance good bonding
Hair, preferably curability compound of the use containing cationically polymerizable and/or free-radical polymerised curability compound
Active energy ray-curable adhesive composite.Active energy ray-curable bonding agent, which can further contain, to be useful for causing
The cationic polymerization initiators and/or radical polymerization initiator of the curing reaction of above-mentioned curability compound.
As the curability compound of cationically polymerizable, such as can enumerate：(there are one intramolecular tools for epoxy based compound
Or the compound of more than two epoxy groups), (intramolecular has one or two above oxa-s to oxetanes based compound
The compound of cyclobutane ring) or combination thereof.As free-radical polymerised curability compound, such as can enumerate：
(intramolecular has one or two above (methyl) acryloyl groups or (methyl) acryloyl to (methyl) acrylic compounds
The compound of oxygroup), other vinyl compounds with free-radical polymerised double bond or these combination.It can also
The curability compound of cationically polymerizable and free-radical polymerised curability compound is used in combination.
As needed, active energy ray-curable bonding agent can contain cationic polymerization accelerating agent, ion capturing agent,
Antioxidant, chain-transferring agent, tackifier, thermoplastic resin, filler, flowing regulator, plasticizer, antifoaming agent, antistatic agent,
The additives such as levelling agent, solvent.
The thickness of first bonding agents layer 15 is generally at 0.001~5 μm or so, preferably 0.01~3 μm.
(5) second protective films
Second protective film 20 possessed by polarization plates 2 shown in Fig. 2 with two-sided protective film and the first protective film 10 are same
Sample can be the film for including above-mentioned illustrated thermoplastic resin, can also be while having both as phase difference film, brightness enhancement film
The protective film of optical function.About the thickness etc. of surface-treated layer and film that the second protective film 20 can have, pass can be quoted
In the above-mentioned record described in the first protective film 10.First protective film 10 and the second protective film 20 can be each other include identical type
Resin protective film, can also be the protective film for including different types of resin.In order to further increase the water-fast of polarization plates
Property, as the second protective film 20, it is also preferred that selection comprising polyolefin-based resins, polyester based resin, (methyl) acrylic resin,
The relatively low protective film of the such moisture permeability of protective film of polystyrene resin etc..
(6) second bonding agents layer
Second bonding agents layer 25 is the layer for second protective film 20 that is adhesively fixed on another face of polarizing coating 5.About
Second bonding agents layer 25 it is detailed, the above-mentioned record about first bonding agents layer 15 can be quoted.From raising polarization plates water resistance
From the perspective of, second bonding agents layer 25 is preferably formed by active energy ray-curable bonding agent.Form second bonding agents
The bonding agent of layer 25 can have composition identical with the bonding agent of first bonding agents layer 15 is formed, it is possible to have different groups
At.
(7) adhesive phase
It is on the polarizing coating 5 of polarization plates 1 with single side protective film shown in Fig. 1 or shown in Fig. 2 with two-sided
On the first protective film 10 or the second protective film 20 of the polarization plates 2 of protective film, it can be laminated for making polarization plates fit to it
The adhesive phase of his component (such as liquid crystal cells when applied to liquid crystal display device).The adhesive for forming adhesive phase is general
Including being added using (methyl) acrylic resin, phenylethylene resin series, silicone-based resin etc. as basic polymer and wherein
The adhesive composition of isocyanate compound, epoxide, crosslinking agent as aziridine cpd.Further also may be used
Light scattering adhesive phase is showed to be made containing particle.The thickness of adhesive phase generally at 1~40 μm, preferably 3~
25μm。
(8) other optical layers
Polarization plates according to the present invention can be further contained in its first and/or second protective film 10,20 or polarization
The other optical layers being laminated on film 5.As other optical layers, can enumerate：Transmit certain polarised light and reflect show with
The reflective polarizing film of the polarised light of its opposite nature；Surface has the film of the anti-dazzle function of band of concaveconvex shape；Belt surface anti-reflective
Penetrate the film of function；Surface has the reflectance coating of reflection function；Have both the Transflective film of reflection function and transmission function；Visual field
Angle compensation film etc..
The manufacturing method ＞ of ＜ polarizing coatings and polarization plates
The polarizing coating and polarization plates of the present invention may be adapted to method according to Fig.3, and be manufactured.Manufacturer shown in Fig. 3
Method includes following processes successively：
(1) it after being coated with the coating fluid containing polyvinyl alcohol resin at least one surface of base material film, makes it dry,
Polyvinyl alcohol resin layer is consequently formed and obtains the resin layer formation process S10 of stacked film；
(2) it stretches stacked film and obtains the stretching process S20 of stretched film；
(3) the polyvinyl alcohol resin layer of stretched film is dyed with iodine and forms polarizing coating (polarizer layer), thus obtained
The dyeing process S30 of polarizability stacked film；
(4) it is bonded protective film on the polarizing coating of polarizability stacked film and obtains the first bonding process S40 of laminating film；
(5) stripping removes base material film and obtains the stripping process S50 of the polarization plates with single side protective film from laminating film.
In the manufacture polarization plates 2 with two-sided protective film as shown in Figure 2, after stripping process S50, further wrap
It includes
(6) the second bonding process S60 of protective film is bonded on the polarization film surface of the polarization plates with single side protective film.
In the following, being explained to each process while with reference to 4~Fig. 7 of figure.It should be noted that forming work in resin layer
In sequence S10, mainly the situation formed in single side can be given below in the two-sided formation polyvinyl alcohol resin layer of base material film
Explanation.
(1) resin layer formation process S10
With reference to figure 4, this process is to form polyvinyl alcohol resin layer 6 at least one face of base material film 30 and obtain layer
The process of folded film 100.This polyvinyl alcohol resin layer 6 is stretched process S20 and dyeing process S30 and becomes polarizing coating 5
Layer.Polyvinyl alcohol resin layer 6 can contain polyvinyl alcohol resin by the single or double coating in base material film 30
Coating fluid, and keep coating layer dry and formed.It is easy to get calmly by being so coated with the method to form polyvinyl alcohol resin layer
It is advantageous from the perspective of to the polarizing coating 5 of film.
Base material film 30 can be made of thermoplastic resin, wherein it is preferred that by the transparency, mechanical strength, thermal stability, draftability
It is constituted etc. excellent thermoplastic resin.The specific example of thermoplastic resin so, such as including：Chain polyolefin-based resins,
Polyolefin-based resins as cyclic polyolefin hydrocarbon system resin (norbornene resin etc.)；Polyester based resin；(methyl) acrylic acid
It is resin；Cellulose esters system resin as cellulosic triacetate, cellulose diacetate；Polycarbonate-based resin；Poly- second
Enol system resin；Polyvinyl acetate system resin；Polyarylate system resin；Polystyrene resin；Polyether sulfone system resin；Polysulfones system
Resin；Polyamide series resin；Polyimides system resins；And their mixture, copolymer.
Base material film 30 can be that one layer of resin layer comprising one or more kinds of thermoplastic resins is formed by list
Layer construction can also be the multi-ply construction that laminated multi-layer includes the resin layer of one or more kinds of thermoplastic resins.Base
Material film 30 is preferably made of following resin, can be suitable when the resin stretches stacked film 100 in aftermentioned stretching process S20
Together in being stretched under the draft temperature of stretching polyethylene alcohol resin 6.
Base material film 30 can contain additive.The specific example of additive includes：Ultra-violet absorber, antioxidant, lubrication
Agent, plasticizer, releasing agent, anti-coloring agent, fire retardant, nucleating agent, antistatic agent, pigment and colorant.
Considering from intensity, operability etc., the thickness of base material film 30 is generally 1~500 μm, preferably 1~300 μm,
More preferably 5~200 μm, further preferably 5~150 μm.
Be coated on base material film 30 coating fluid preferably make polyvinyl alcohol resin powder be dissolved in good solvent (such as water) and
Obtained polyvinyl alcohol resin solution.The detailed content of polyvinyl alcohol resin is as described above.As needed, coating fluid also may be used
To contain the additives such as plasticizer, surfactant.
In the method that base material film 30 is coated with above-mentioned coating fluid, it can suitably be selected from following method：Such as bar rubbing method；It is reverse to apply
Roller coating method as cloth, intaglio plate coating；Die head is coated with (die coater) method；Comma rubbing method；Die lip rubbing method；Spin coating
Method；Silk screen rubbing method；Jetting type rubbing method；Infusion process；The methods of spray coating method.
The drying temperature of coating layer (the polyvinyl alcohol resin layer before dry) and drying time can be according to institutes in coating fluid
Solvent-laden type is set.Drying temperature is, for example, 50~200 DEG C, preferably 60~150 DEG C.It is dry when solvent contains water
Temperature is preferably at 80 DEG C or more.
Polyvinyl alcohol resin layer 6 can be formed only on a surface of base material film 30, can also be in two-sided upper formation.
If in two-sided upper formation, can when inhibiting to manufacture polarizability stacked film 300 (with reference to figure 6) issuable film roll song
Meanwhile two panels polarization plates can be obtained from a piece of polarizability stacked film 300, therefore in terms of the production efficiency of polarization plates from the point of view of be also
It is advantageous.
The thickness of polyvinyl alcohol resin layer 6 is preferably 3~30 μm in stacked film 100, more preferably 5~20 μm.If
It is the polyvinyl alcohol resin layer 6 with thickness within the scope of this, then passes through aftermentioned stretching process S20 and dyeing process S30, it can
Dyeability to obtain iodine is good and polarization property is excellent, and the polarizing coating 5 of sufficiently thin (such as thickness is at 10 μm or less).
It, can be at least in order to improve the adaptation of base material film 30 and polyvinyl alcohol resin layer 6 before applied coating solution
To on 30 surface of base material film for forming 6 side of polyvinyl alcohol resin layer, imposing sided corona treatment, corona treatment, flame (fire
It is scorching) processing etc..In addition, for the same reason, polyethenol series tree can also be formed via prime coat etc. on base material film 30
Lipid layer 6.
Prime coat can be by prime coat formation be dried with coating solution after on the surface of base material film 30
It is formed.This coating fluid contains both plays a degree of strong closing force for base material film 30 and polyvinyl alcohol resin layer 6
Ingredient, usually contain the resin component and solvent for assigning such closing force.As resin component, it is preferable to use the transparency,
The excellent thermoplastic resin such as thermal stability, draftability, such as can enumerate：(methyl) acrylic resin, polyethenol series tree
Fat etc..Wherein, it is preferred to use assign the polyvinyl alcohol resin of good closing force.More preferable polyvinyl alcohol resin.As solvent,
Generally using the common organic solvent or water solvent that can dissolve above-mentioned resin component, preferably by using water as the coating of solvent
Liquid forms prime coat.
It, can be in prime coat formation with adding crosslinking agent in coating fluid in order to improve prime coat intensity.Crosslinking agent it is specific
Example includes：Epoxy, isocyanates system, dialdehyde system, metal system (for example, metal salt, metal oxide, metal hydroxides,
Organo-metallic compound), the crosslinking agent of macromolecular.Using polyvinyl alcohol resin as the resin component for forming prime coat
When, preferably use Polyamide Epoxy, methylolated melamine resin, dialdehyde system crosslinking agent, metallo-chelate system to hand over
Join agent etc..
The thickness of prime coat is preferably 0.05~1 μm or so, more preferably 0.1~0.4 μm.If thinner than 0.05 μm,
Then base material film 30 and the closing force improvement effect of polyvinyl alcohol resin layer 6 are small, if thicker than 1 μm, are unfavorable for polarization plates
Filming.
The method of prime coat formation coating solution to base material film 30 can be formed with polyvinyl alcohol resin layer and used
Coating fluid it is identical.Including the drying temperature of the coating layer of prime coat formation coating fluid is, for example, 50~200 DEG C, preferably 60
~150 DEG C.When solvent contains water, drying temperature is preferably at 80 DEG C or more.
(2) stretching process S20
With reference to figure 5, this process is stretched to the stacked film 100 comprising base material film 30 and polyvinyl alcohol resin layer 6,
And the process for obtaining the stretched film 200 of the base material film 30 ' comprising drawn and polyvinyl alcohol resin layer 6 '.Stretch processing is general
It is to be uniaxially stretched.
The stretching ratio of stacked film 100 can as expected polarization characteristic and suitably select, relative to stacked film 100
Raw footage, preferably more than 5 times and 17 times hereinafter, more preferably above 5 times and 8 times or less.If stretching ratio at 5 times hereinafter,
Then polyvinyl alcohol resin layer 6 ' is not orientated fully, therefore be possible to cannot be fully high for the degree of polarization of polarizing coating 5.Another party
Face, stretching ratio is if it exceeds 17 times, it is likely that while easy ting produce the fracture of film when stretching, the thickness of stretched film 200
It spends than required also thin, in subsequent handling processability and operability reduction.
Stretch processing is not limited to the stretching of a step, can also carry out to multistep.At this point it is possible in dyeing process S30
Before continuously carry out multistep whole stretch processings, can also with the dyeing processing and/or crosslinking in dyeing process S30 at
Reason is carried out at the same time the later stretch processing of second step.When carrying out stretch processing like this with multistep, preferably with the whole of stretch processing
A stage adds up to the mode of the stretching ratio more than 5 times to carry out stretch processing.
Stretch processing also may be used other than it can be the longitudinal stretching stretched on the length direction (film conveying direction) of film
To be the cross directional stretch stretched in the width direction of film or oblique extension etc..As longitudinal stretching mode, can enumerate：It uses
Stretching, compression stretching between the roller that roller is stretched can be enumerated using the stretching etc. of fixture (clip) as cross directional stretch mode
Tenter frame process etc..Stretch processing may be used any one in moistening type drawing process, dry-stretch process, but from can be wide
It is preferable to use dry-stretch process from the point of view of selecting to range in terms of draft temperature.
Draft temperature is set to polyvinyl alcohol resin layer 6 and the whole stream for showing stretchable degree of base material film 30
It is more than the temperature of dynamic property, preferably -30 DEG C to+30 DEG C of the phase transition temperature (fusing point or glass transition temperature) of base material film 30
Range, more preferably -30 DEG C to+5 DEG C of range, further preferably -25 DEG C to+0 DEG C of range.Include in base material film 30
When multilayer resin layer, above-mentioned phase transition temperature refers to the highest phase transition temperature in the phase transition temperature shown by the multilayer resin layer.
If making draft temperature less than -30 DEG C of phase transition temperature, stretched in the presence of the high magnification for being difficult to reach more than 5 times,
Or the mobility of base material film 30 is too low and be difficult to carry out the tendency of stretch processing.If draft temperature be more than phase transition temperature+
30 DEG C, then the mobility that there is base material film 30 is excessive and is difficult to the tendency stretched.In order to more easily reach the height more than 5 times
Stretching ratio, draft temperature within the above range, further preferably at 120 DEG C or more.
As the heating means of the stacked film 100 in stretch processing, there is region heating (for example, as by being blown into heat
Wind adjusts the method heated in stretch zones as the heating furnace to set point of temperature)；When being stretched using roller, two pairs of rollers sheet
The method of body heating；Heater heating (infrared heater, halogen heater, baffle heater etc. is arranged in stacked film
100 upper and lower and the method heated with radiant heat) etc..From the viewpoint of the uniformity of draft temperature, drawn between roller
Stretch favored area heating in mode.
It should be noted that draft temperature refers to the gas of (such as in heating furnace) in region in the case of the heating of region
Atmosphere temperature also refers to furnace inner environment temperature in the case of heating in stove in heater heating.In addition, in two pairs of rollers sheet
Refer to the surface temperature of roller in the case of the method for body heating.
Before stretching process S20, the pre-heat treatment process preheated to stacked film 100 may also set up.As preheating
Method identical with the heating means in stretch processing can be used in method.Preheating temperature is preferably -50 DEG C to ± 0 of draft temperature
DEG C range, more preferably-the 40 of draft temperature DEG C to -10 DEG C of range.
In addition, after the stretch processing of stretching process S20, heat fixation treatment process may also set up.Heat fixation is handled
In the state of with clip grab tensile 200 end of film, tense situation is kept on one side, carries out heat more than crystallized temperature on one side
The processing of processing.The crystallization of polyvinyl alcohol resin layer 6 ' can be promoted by being handled by the heat fixation.The temperature of heat fixation processing
The preferably range of -0 DEG C of draft temperature~-80 DEG C, the more preferably range of-the 0 of draft temperature DEG C~-50 DEG C.
(3) dyeing process S30
With reference to figure 6, this process is so that iodine is adsorbed and is taken the dyeing of polyvinyl alcohol resin layer 6 ' of stretched film 200 with iodine
To the process for forming polarizing coating 5.By this process, the single or double that can be obtained in base material film 30 ' is laminated with polarizing coating 5
Polarizability stacked film 300.
Dyeing process can be by carrying out whole immerse of stretched film 200 in the solution (staining solution) containing iodine.As
The solution that iodine is dissolved in solvent can be used in staining solution.As solvent, it is however generally that water can be used, can also further add
Add organic solvent having a miscibility with water.Iodine concentration in staining solution is preferably 0.01~10 weight %, more preferably
0.02~7 weight %.
From staining efficiency can be improved, iodide are preferably further added in staining solution.As iodide, example
It can such as enumerate：Potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, iodate
Tin, titanium iodide etc..Iodide concentration in staining solution is preferably 0.01~20 weight %.Among iodide, iodine is preferably added
Change potassium.When adding potassium iodide, the ratio of iodine and potassium iodide is preferably 1: 5~1: 100 with weight ratio meter, and more preferably 1: 6~1
∶80.The temperature of staining solution is preferably 10~60 DEG C, more preferably 20~40 DEG C.
It should be noted that dyeing process S30 can be carried out before stretching process S20, or these processes are carried out at the same time,
It is preferred that implementing dyeing process S30 again after at least imposing a degree of stretch processing to stacked film 100, so as to be adsorbed in polyethylene
The iodine of alcohol resin is orientated well.
Dyeing process S30 may include the crosslinking Treatment process that immediately tinction processing is implemented.Crosslinking Treatment can be by that will contaminate
The film of color immerses to carry out in the solution (crosslinker solution) that dissolving crosslinking agent is formed in solvent.As crosslinking agent, such as can arrange
It lifts：Boron compound, glyoxal, glutaraldehyde etc. as boric acid, borax.One kind can be used only in crosslinking agent, also can be used in combination
It is two or more.As the solvent of crosslinker solution, water can be used, can also further be contained having a miscibility with water organic molten
Agent.The concentration of crosslinking agent is preferably 0.2~20 weight % in crosslinker solution, more preferably 0.5~10 weight %.
Crosslinker solution can also further contain iodide.By adding iodide, the polarizability in 5 face of polarizing coating can be made
It can more uniformly.The specific example of iodide is same as described above.The concentration of iodide is preferably 0.05~15 weight in crosslinker solution
Measure %, more preferably 0.5~8 weight %.The temperature of crosslinker solution is preferably 1~90 DEG C.
It should be noted that crosslinking Treatment can also by staining solution be incorporated crosslinking agent by with dyeing processing simultaneously into
Row.Further, it is also possible to using different two or more crosslinker solutions are formed, implement 2 times or more the processing for immersing crosslinker solution.
After dyeing process S30, washing procedure and back tender are carried out preferably before aftermentioned first bonding process S40
Sequence.Washing procedure generally comprises water washing process.After water washing can be by the film that will dye that treated or crosslinking Treatment
Film immerse and carried out in ion exchange water, pure water as distilled water.Water washing temperature is generally 3~50 DEG C, preferably 4~
20℃.Washing procedure can also be the combination of water washing process and the washing procedure using iodide solution.As in washers
The arbitrary proper methods such as natural drying, air-supply drying, heat drying may be used in the drying process carried out after sequence.Such as
In heat drying, drying temperature is generally 20~95 DEG C.
(4) first bonding process S40
With reference to figure 7, this process be via adhesive layer on the polarizing coating 5 of polarizability stacked film 300, that is, with polarizing coating 5
30 ' side opposite side of base material film face on be bonded protective film, the process for thus obtaining laminating film 400.It is shown in Fig. 7 via
One adhesive layer 15 is bonded the example of the first protective film 10, but when manufacture carries the polarization plates 2 of two-sided protective film, can also be
The mode of the second protective film 20 is bonded via second bonding agents layer 25.About formation first bonding agents layer 15 or second bonding agents layer
25 bonding agent is as described above.
It should be noted that polarizability stacked film 300 base material film 30 ' it is two-sided have polarizing coating 5 when, generally two-sided
Polarizing coating 5 on be bonded protective film respectively.At this point, these protective films can be the protective film of identical type, can also be difference
The protective film of type.
If to protection for being bonded the situation of the first protective film 10 to use active energy ray-curable bonding agent
The fitting adhering method of film illustrates, then will via the active energy ray-curable bonding agent as first bonding agents layer 15
After first protective film 10 is layered on polarizing coating 5, irradiation ultraviolet light, visible light, electron beam, active-energy is penetrated as X-ray
Line and so that adhesive layer is cured.Wherein preferred ultraviolet light, as the light source in the case of this, can be used low pressure mercury lamp, medium pressure mercury lamp,
High-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp etc..
On polarizing coating 5 be bonded protective film when, in order to improve the cementability with polarizing coating 5, can to protective film and/or partially
The binding face of vibrating diaphragm 5 carries out corona treatment, sided corona treatment, ultraviolet treatment with irradiation, flame (fire is scorching) processing, saponification process
Such surface treatment (easy bonding processing), wherein preferably carry out corona treatment, sided corona treatment or saponification process.
(5) stripping process S50
This process is the process of the stripping removal base material film 30 ' from laminating film 400.By the process, can be obtained and Fig. 1 phases
The same polarization plates with single side protective film.Polarizability stacked film 300 has polarizing coating 5 in the two-sided of base material film 30 ', at them
When being bonded protective film on two polarizing coatings 5, by stripping process S50, two panels can be obtained from a piece of polarizability stacked film 300
Polarization plates with single side protective film.
The method of stripping removal base material film 30 ' is not particularly limited, and can be used and in the general polarization with adhesive
The identical method of stripping process of the partition (stripping film) that plate is carried out is removed.Base material film 30 ' can be in the first bonding process
It is directly removed immediately after S40, can also first be curled into roll and in subsequent process one after the first bonding process S40
Side debatching is removed on one side.
(6) second bonding process S60
This process is on the polarizing coating 5 of the polarization plates with single side protective film, that is, with pass through the first bonding process S40
Further be bonded protective film on the face of the protective film opposite side of fitting, and obtain structure shown in Fig. 2 with two-sided protective film
The process of polarization plates 2.When being bonded the first protective film 10 by the first bonding process S40, the second protective film is bonded by this process
20, when being bonded the second protective film 20 by the first bonding process S40, the first protective film 10 is bonded by this process.Via second
Adhesive layer 25 is bonded the second protective film 20 and can carry out identically as the first protective film 10 of fitting.
More than, polarizing coating is formed to the polyvinyl alcohol resin layer by being coated on base material film, then manufactures polarization plates
Method has been described in detail, and but it is not limited to this, and the first protection can also be bonded on the polarizing coating 5 being made of monomer (independent) film
Film 10 or the first and second protective films 10,20 manufacture polarization plates.
The polarizing coating 5 being made of monomer (independent) film can be manufactured by the method including following process：Such as pass through
The process that well known method makes polyvinyl alcohol resin film as extrusion by melting, solution casting method；By polyethenol series
The process that resin film is uniaxially stretched；The process for dyeing and making it to adsorb to polyvinyl alcohol resin film with iodine；With boric acid water
The process that solution handles the polyvinyl alcohol resin film for being adsorbed with iodine；And it is carried out after being handled using boric acid aqueous solution
The process of washing.Being uniaxially stretched can simultaneously or after dyeing carry out before iodine staining, with dyeing.It carries out after dyeing
When being uniaxially stretched, this, which is uniaxially stretched, to be carried out before boric acid processing or in boric acid processing.In addition it is also possible at these
It is uniaxially stretched in multiple stages.
Both first and second protective films 10,20 are being bonded come when manufacturing the polarization plates with two-sided protective film, these are protected
Cuticula can be successively bonded via adhesive layer, can also be bonded at the same time.
(7)WIThe control of/Ty
For improving the iodine containing ratio W relative to visual sensitivity correction monomer transmissivity TyI, by WI/ Ty is located at
The method stated in prescribed limit is not particularly limited, such as can enumerate following method.
A) in dyeing process, iodide (containing iodine, iodide ion) are largely being contained compared with the amount generally used
The method of film is immersed in staining solution.At this point, by adjusting the concentration of iodide, the temperature of staining solution, film in staining solution
Residence time etc., W can be controlledI/Ty。
B) it in crosslinking Treatment process, is largely soaked in the crosslinker solution containing iodide ion compared with the amount generally used
Enter the method for film.Even in this case, by adjusting the concentration of iodide ion in crosslinker solution, the temperature of crosslinker solution,
The residence time etc. of film, W can be controlledI/Ty。
C) method for making the iodide ion contained by film not ooze out.The iodide ion contained once being washed with water compared with
It is easily washed off.Therefore, as the method for making iodide ion not ooze out, it can enumerate and improve crosslinker concentration in crosslinker solution
Method.If improving crosslinker concentration, the crosslinking quantitative change of crosslinking agent is more, therefore can be difficult to wash off when being washed
Iodide ion.In order to more effectively inhibit the exudation of iodide ion, the temperature of crosslinker solution to be preferably set as low temperature as possible.This
Outside, attached with air knife or air-blaster blowing film surface instead of washing as the other methods for making iodide ion not ooze out
The liquid, or with the method for liquid of the removal film surface attachment such as suction roll be also effective.It can be to avoid by not washing
The exudation of iodide ion.
D) it is above-mentioned a)~c) combination of more than two kinds.
Among the above, b), method c) it is effective, c) method it is most effective.
For obtaining WI/ Ty 0.145 or more one of the preferred embodiment of polarizing coating be include by film immerse be crosslinked
In solution carry out crosslinking Treatment process method, crosslinker solution low temperature as possible and contain crosslinking agent and iodide ion.More
One of preferred embodiment be include by film immerse in following crosslinker solution carry out crosslinking Treatment process method：The crosslinking
The liquid temperature of solution is 3~30 DEG C, preferably 5~15 DEG C, and contains 0.5~10 weight % of crosslinking agent, preferably comprises 1~5 weight
% is measured, and contains excessive iodide ion.The crosslinker solution can implement crosslinking using crosslinker solution more than double flute
At least one kind of crosslinker solution when treatment process.
After crosslinking Treatment process in the preferred embodiment further preferably stated on the implementation, without washing, use
The removals such as air knife or air-blaster, suction roll are attached to the liquid of film surface.It should be noted that subsequent drying process
Condition is not particularly limited, and is difficult to generate the exudation of iodide ion carrying out at a higher temperature.
Embodiment
The present invention is further specifically described in the following, providing embodiment and comparative example, but the present invention is not by these
Example is limited.
1 ＞ of ＜ embodiments
(1) prime coat formation process
By pva powder (" Z-200 ", average degree of polymerization 1100, the soap of the Nippon Synthetic Chemical Industry Co., Ltd
99.5 moles of % of change degree) it is dissolved in 95 DEG C of hot water, it is prepared into the polyvinyl alcohol water solution of a concentration of 3 weight %.Relative to
6 parts by weight of pva powder, with the ratio of 5 parts by weight by the crosslinking agent (" SUMIREZ of field hilllock chemical industry Co. Ltd. system
RESIN 650 ") it is mixed into the aqueous solution of gained, and obtain prime coat formation coating fluid.
Then, prepare un-stretched polypropylene (PP) film (fusing point of 90 μm of thickness：163 DEG C) it is used as base material film, to its single side
After imposing sided corona treatment, using minor diameter gravure coater by above-mentioned prime coat formation coating solution in the sided corona treatment
Face, it is 10 minutes dry at 80 DEG C, the prime coat of 0.2 μm of thickness is consequently formed.
(2) making (resin layer formation process) of stacked film
By pva powder (" PVA124 " of Kuraray Co., Ltd., average degree of polymerization 2400, saponification degree 98.0~
99.0 moles of %) it is dissolved in 95 DEG C of hot water, it is prepared into the polyvinyl alcohol water solution of a concentration of 8 weight %, in this, as poly-
Vinyl alcohol resin layer formation coating fluid.
It is using die applicator, above-mentioned polyvinyl alcohol resin layer formation coating solution is made in above-mentioned (1)
It is 4 minutes dry at 70 DEG C after the base material film primer coat surface with prime coat made, polyethylene is thus formed on prime coat
Alcohol resin, to obtain including the stacked film of base material film/prime coat/polyvinyl alcohol resin layer.
(3) making (stretching process) of stretched film
Using longitudinal uniaxial stretching device of floating, 5.3 are implemented to stacked film made in above-mentioned (2) at 160 DEG C
Free end again is uniaxially stretched, and obtains stretched film.The thickness of polyvinyl alcohol resin layer after stretching is 5.1 μm.
(4) making (dyeing process) of polarizability stacked film
Stretched film made in above-mentioned (3) is immersed in 30 DEG C of dyeing aqueous solution (every 100 weights containing iodine and potassium iodide
Measure part water in containing 0.6 parts by weight of iodine, 10.0 parts by weight of potassium iodide) in about 180 seconds, carry out polyvinyl alcohol resin layer
Dyeing processing after, extra dyeing aqueous solution is washed off with 10 DEG C of pure water.
Then, be immersed in 78 containing boric acid DEG C first crosslinking aqueous solution (water of every 100 parts by weight contains boric acid 10.4
Parts by weight) in 120 seconds, then, be immersed in 70 DEG C containing boric acid and potassium iodide second crosslinking aqueous solution (every 100 weight
Part water contain 5.7 parts by weight of boric acid, 12.0 parts by weight of potassium iodide) in 60 seconds, be further immersed in containing boric acid and iodate
In 10 DEG C of the third crosslinking aqueous solution (water of every 100 parts by weight contains 3.0 parts by weight of boric acid, 15.0 parts by weight of potassium iodide) of potassium
About 10 seconds, to carry out crosslinking Treatment.It is immediately removed using air-blaster and is attached to two-sided liquid, to be wrapped
Polarizability stacked film containing polarizing coating.
(5) making (the first bonding process, stripping process) of the polarization plates of single side protective film is carried
Via the adhesive layer for including ultra-violet solidified bonding agent (" KR-75T " of Asahi Denka Co., Ltd.), upper
It states fitting protective film on the polarizing coating of polarizability stacked film made in (4) and (includes the transparent guarantor of triacetyl cellulose (TAC)
Cuticula (" KC-2UAW " of Konica Minolta Opto Inc)).Then, by using high voltage mercury lamp radiation purple
Outside line cures adhesive layer, to obtain the laminating film of the layer structure comprising protective film/adhesive layer/polarizing coating/base material film
(the first bonding process).Then, the stripping removal base material film from obtained laminating film, it is inclined with single side protective film to obtain
Vibration plate (stripping process).
(6) making of evaluation sample
Sided corona treatment is imposed in the face of the polarizing coating side of the obtained polarization plates with single side protective film on one side, is bonded on one side
The adhesive (" P-3132 " of Lindeke Co., Ltd) of (methyl) acrylic resin.It will obtain with adhesive phase
Polarization plates fit in glass with the adhesive phase, to obtain evaluation sample.
2 ＞ of ＜ embodiments
Content in addition to third to be crosslinked to potassium iodide in aqueous solution is set as relative to the water of 100 parts by weight being 6 parts by weight, this
Outside, it is removed instead of air-blaster and using suction roll other than two-sided liquid, other modes same as Example 1 make band
There are the polarization plates of single side protective film, and then makes evaluation sample.
1 ＞ of ＜ comparative examples
In addition to by third be crosslinked aqueous solution in potassium iodide content be set as relative to 100 parts by weight water be 4 parts by weight with
Outside, other modes same as Example 1 make the polarization plates with single side protective film, and then make evaluation sample.
2 ＞ of ＜ comparative examples
In addition to replacing being immersed in third crosslinking aqueous solution and other than being immersed in 10 DEG C of water, other and 1 phase of embodiment
Same mode makes the polarization plates with single side protective film, and then makes evaluation sample.
(measurement of Ty, Py and monomer form and aspect b)
For the polarization plates of obtained evaluation sample, integrating sphere type spectrophotometer (Japan Spectroscopy Corporation is used
System " V7100 "), to obtain transmissivity, degree of polarization according to 2 degree visuals field (illuminant-C) of JIS Z 8701 progress visual acuity
Degree correction measures visual sensitivity correction monomer transmissivity Ty and visual sensitivity correction degree of polarization Py.In addition, using same point
Light photometric determination monomer form and aspect b.When measurement, evaluation sample is installed in such a way that glass side irradiates incident light.By what is obtained
Visual sensitivity correction monomer transmissivity Ty, visual sensitivity correction degree of polarization Py and monomer form and aspect b are set to polarizing coating
Visual sensitivity corrects monomer transmissivity Ty, visual sensitivity corrects degree of polarization Py and monomer form and aspect b.The results are shown in Table 1.
(iodine containing ratio WIAnd WIThe measurement of/Ty)
Protective film and adhesive layer are removed from the obtained polarization plates with single side protective film to detach polarizing coating, by it
As sample is measured, by according to JIS K 0127：2013 burning-chromatography of ions finds out iodine containing ratio WI(weight
Measure %).In burning-ion chromatography, chlorine/sulphur content analysis apparatus " TOX-100 " of Mitsubishi Chemical's ANALYTECH Co. Ltd. systems is used
As burner, in addition, using " DX-500 " of Thermo Fischer Scient Inc. as ion chromatography apparatus.It uses
The polarizing coating of 12.2mg measures the fuel pretreatment of sample according to the 6.3.5 of same JIS standards as sample is measured.In addition, with
Ty as obtained above calculates WI/Ty.The results are shown in Table 1.
(measuring absorbance when wavelength 217nm)
Protective film and adhesive layer are removed from the obtained polarization plates with single side protective film to detach polarizing coating, by it
As sample is measured, according to spectrophotometer (Shimadzu Scisakusho Ltd's system：UV2450 190~800nm wavelength models) are measured
The absorbance enclosed.In order to avoid leading to the influence to polarization due to device, the absorption axiss for measuring sample are set as relative to device
The horizontal and average value of the absorption spectrum measured and the absorption spectrum for being rotated by 90 ° measurement is employed as the absorption spectrum of polarizing coating.
It is found out by the absorption spectrum and comes from iodide ion (I-) wavelength 217nm at absorbance.The results are shown in Table 1.
In 4 polarizing coatings of Examples 1 to 2 and comparative example 1~2, obtained absorbance is asked with burning-chromatography of ions
The iodine containing ratio W obtainedIWith proportionate relationship.This is because in order to keep Ty identical consistent, the poly- iodine of complex compound is formed with PVA
Amount it is almost equal between 4 polarizing coatings, therefore, it is considered that with the iodine containing ratio W of burning-ion-chromatographic determinationISize
Reflect iodide ion (I-) amount size.It can be seen from this result that the iodine containing ratio found out by burning-chromatography of ions
WIReflect iodide ion (I-) amount.
(water resistance of polarization plates is evaluated)
(1) evaluation of humidity resistance
The evaluation of 4cm square is put into sample in conditioning to the baking oven of 80 DEG C of 90%RH after 48 hours, examination is taken out
Sample after standing about 12 hours in the environment of 23 DEG C, 55%RH, is polarized with visual sensitivity correction is measured with upper identical method
Spend Py.The results are shown in Table 1.
(2) the aqueous evaluation of heatproof
The evaluation of 4cm square is immersed in sample in 60 DEG C of water after 30 points, sample is lifted, in 23 DEG C, 55%RH
After standing about 12 hours under environment, monomer form and aspect b is measured with method same as described above.In addition, sample after visual confirmation experiment
Form and aspect, still keep being evaluated as A when neutral ash after experiment, B be evaluated as when generating de- blue.The results are shown in Table 1.
[table 1]
Claims (6)
1. a kind of polarization plates, which is characterized in that include polarizing coating and protective film,
The iodine containing ratio W of the polarizing coatingI[weight %] is 8.09 hereinafter, light sensitivity correction monomer transmissivity Ty [%] is
40~47, the iodine containing ratio WIThe ratio between [weight %] and light sensitivity correction monomer transmissivity Ty [%] WI/ Ty exists
0.145 or more, it is 99.986% or more that light sensitivity, which corrects degree of polarization, and the absorbance in wavelength 217nm is 2.57 or more,
The protective film is adhesively fixed at least one face of the polarizing coating by active energy ray-curable bonding agent
On.
2. a kind of polarization plates, which is characterized in that include polarizing coating and adhesive phase,
The iodine containing ratio W of the polarizing coatingI[weight %] is 8.09 hereinafter, light sensitivity correction monomer transmissivity Ty [%] is
40~47, the iodine containing ratio WIThe ratio between [weight %] and light sensitivity correction monomer transmissivity Ty [%] WI/ Ty exists
0.145 or more, it is 99.986% or more that light sensitivity, which corrects degree of polarization, and the absorbance in wavelength 217nm is 2.57 or more.
3. polarization plates as claimed in claim 1 or 2, wherein the W of the polarizing coatingI/ Ty is below 0.5.
4. polarization plates as claimed in claim 1 or 2, wherein the thickness of the polarizing coating is at 10 μm or less.
5. polarization plates as claimed in claim 1 or 2, wherein the polarizing coating includes polyvinyl alcohol resin.
6. polarization plates as claimed in claim 2 are also included in the protective film being laminated at least one face of the polarizing coating.
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| JP6794181B2 (en) * | 2016-08-30 | 2020-12-02 | 日東電工株式会社 | Polarizer |
| JP6910931B2 (en) * | 2016-12-02 | 2021-07-28 | 住友化学株式会社 | Method for manufacturing polarizing film and polarizing laminated film |
| KR20240033120A (en) * | 2017-03-06 | 2024-03-12 | 닛토덴코 가부시키가이샤 | Polarizing film with optical functional layer, and liquid crystal display device |
| JP6817420B2 (en) * | 2017-04-03 | 2021-01-20 | 日東電工株式会社 | Polarizer manufacturing method |
| WO2018235461A1 (en) * | 2017-06-23 | 2018-12-27 | 日東電工株式会社 | Polarizing film, polarizing plate including said polarizing film, and vehicle on-board image display device including said polarizing plate |
| TWI762667B (en) * | 2017-09-13 | 2022-05-01 | 日商日東電工股份有限公司 | Polarizing film, polarizing plate, polarizing plate roll, and manufacturing method of polarizing film |
| WO2019168132A1 (en) * | 2018-02-28 | 2019-09-06 | 日東電工株式会社 | Reinforcement-type polarizing optical film laminate for powered vehicle, and optical display panel in which said reinforcement-type polarizing optical film laminate is used |
| KR102536728B1 (en) * | 2018-10-15 | 2023-05-26 | 닛토덴코 가부시키가이샤 | Polarizing plate with phase difference layer, and image display device using this |
| JP7355584B2 (en) * | 2018-10-15 | 2023-10-03 | 日東電工株式会社 | Polarizing plate with retardation layer and image display device using the same |
| JP7355586B2 (en) * | 2018-10-15 | 2023-10-03 | 日東電工株式会社 | Polarizing plate with retardation layer and image display device using the same |
| JP6890162B2 (en) * | 2018-10-15 | 2021-06-18 | 日東電工株式会社 | Polarizing plate with retardation layer and image display device using it |
| JP6890161B2 (en) * | 2018-10-15 | 2021-06-18 | 日東電工株式会社 | Polarizing plate with retardation layer and image display device using it |
| KR102476698B1 (en) * | 2018-10-15 | 2022-12-14 | 닛토덴코 가부시키가이샤 | Polarizing plate with retardation layer and image display using the same |
| JP7355587B2 (en) * | 2018-10-15 | 2023-10-03 | 日東電工株式会社 | Polarizing plate with retardation layer and image display device using the same |
| JP2021165809A (en) * | 2020-04-08 | 2021-10-14 | 日東電工株式会社 | Polarizing film and polarizing film product |
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| TWI614542B (en) | 2018-02-11 |
| TWI604232B (en) | 2017-11-01 |
| KR101839672B1 (en) | 2018-03-16 |
| TW201809762A (en) | 2018-03-16 |
| JP2016153886A (en) | 2016-08-25 |
| KR20160099491A (en) | 2016-08-22 |
| CN105891930A (en) | 2016-08-24 |
| TW201632927A (en) | 2016-09-16 |
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