CN105467496A - Polarizing plate and process for producing the same - Google Patents
Polarizing plate and process for producing the same Download PDFInfo
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- CN105467496A CN105467496A CN201510640110.9A CN201510640110A CN105467496A CN 105467496 A CN105467496 A CN 105467496A CN 201510640110 A CN201510640110 A CN 201510640110A CN 105467496 A CN105467496 A CN 105467496A
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Abstract
The invention provides a polarizing plate and a process for producing the same; the polarizing plate comprises a polarizing sheet, a bonding agent layer and a brightness enhancing film in sequence; the bonding agent layer side of the brightness enhancing film is processed by surface activate treatment; the surface activate treatment preferably uses corona treatment.
Description
Technical field
The present invention relates to the polarization plates and manufacture method thereof that comprise polaroid and stacked brightness enhancement film thereon.
Background technology
In recent years, along with the maximization of the liquid crystal mobile terminal representated by smart mobile phone, realizing to utilize limited battery capacity driving for a long time, taking, using brightness enhancement film to improve the utilization ratio of backlight.And from design, portability aspect, the requirement of the slimming of liquid crystal mobile terminal is improved day by day, for wherein used polarization plates, also requires further slim lightweight.
Brightness enhancement film is the film with following character: when backlight, its reflected light incidence of liquid crystal indicator, the linear polarization of reflection specification polarization axle or the rotatory polarization of prescribed direction, and makes other light generation transmissions.Such as, by be configured at liquid crystal cells backlight side polaroid (absorptive-type linear polarizer) backlight side configuration brightness enhancement film, can when making backlight be incident in brightness enhancement film, only make the light generation transmission of the regulation polarization state that polarization state of transmission-polarizing sheet (can) and be supplied to polaroid, on the other hand, the light beyond regulation polarization state is made reflection to occur and transmission can not occur.If strengthen film at specific luminance to be provided with reflection horizon etc. closer to backlight side, reflection horizon then can be utilized to make the light reverse direction of travel reflected in this brightness enhancement film face, and re-shoot in brightness enhancement film, now, part or all that can make the light re-shoot, as the Transmission light brightness enhancement film of regulation polarization state, is supplied to polaroid.
Like this, if use brightness enhancement film, then can make to be polarized that polarisation that sheet absorbs and reflection occur and not to the transmission of polaroid side, and by the interreflection between brightness enhancement film-reflection horizon and reversion, this polarisation light is changed into can that polarisation light of transmission-polarizing sheet, be supplied to polaroid.The utilization ratio of backlight can be improved thus, so can electricity consumption be reduced, in addition, with when using compared with identical electricity consumption (amount of backlight), compared with when can make picture and not use brightness enhancement film brighter (such as Japanese Unexamined Patent Publication 11-248941 publication, Japanese Unexamined Patent Publication 11-248942 publication, Japanese Unexamined Patent Publication 11-64840 publication and Japanese Unexamined Patent Publication 11-64841 publication).
The polarization plates via adhesive phase (pressure sensitive bond layer) brightness enhancement film of stacked thickness 40 ~ 100 μm on polaroid is disclosed in Jap.P. No. 5332599 instructions.
Summary of the invention
When requiring to tolerate the permanance of hygrothermal environment to the polarization plates of brightness enhancement film of fitting on polaroid via adhesive phase, there is following problems in polarization plates in the past: such as, if implement the wet heat durability test of 60 DEG C of 90%RH, then in the end of polarization plates, can peel off in the interface of brightness enhancement film and adhesive phase.Less then this problem of thickness of brightness enhancement film is more remarkable.
The object of the present invention is to provide a kind of polarization plates and manufacture method thereof, described polarization plates is the polarization plates comprising polaroid, adhesive phase and brightness enhancement film successively, be difficult to the stripping between adhesive phase and brightness enhancement film occurs under hygrothermal environment, wet heat durability is excellent.
The invention provides polarization plates shown below and manufacture method thereof and liquid crystal indicator.
[1] polarization plates, it comprises polaroid, adhesive phase and brightness enhancement film successively,
The surface of the above-mentioned adhesive phase side in above-mentioned brightness enhancement film implements surface activation process.
[2] polarization plates Gen Ju [1], above-mentioned adhesive phase connects with above-mentioned brightness enhancement film.
[3] according to [1] or the polarization plates described in [2], above-mentioned polaroid connects with above-mentioned adhesive phase.
[4] according to the polarization plates according to any one of [1] ~ [3], above-mentioned surface activation process is corona treatment.
[5] according to the polarization plates according to any one of [1] ~ [4], the thickness of above-mentioned brightness enhancement film is 10 ~ 30 μm.
[6] according to the polarization plates according to any one of [1] ~ [5], the thickness of above-mentioned polaroid is less than 15 μm.
[7] according to the polarization plates according to any one of [1] ~ [6], the storage elastic modulus of above-mentioned adhesive phase in the temperature range of 23 ~ 80 DEG C is 0.15 ~ 1MPa, thickness is 3 ~ 20 μm.
[8] according to polarization plates according to any one of [1] ~ [7], its comprise further be laminated in above-mentioned polaroid with the diaphragm on the face of above-mentioned adhesive phase opposite side.
[9] polarization plates Gen Ju [8], said protection film is made up of polyolefin-based resins or cellulose-based resin.
[10] liquid crystal indicator, it comprises liquid crystal cells and the polarization plates according to any one of [1] ~ [9].
[11] manufacture method, it is the manufacture method of the polarization plates comprising polaroid, adhesive phase and brightness enhancement film successively, comprises
The surface of the above-mentioned adhesive phase side in above-mentioned brightness enhancement film is implemented to the operation of surface activation process, and
The operation of stacked above-mentioned adhesive phase on the above-mentioned surface implementing above-mentioned surface activation process.
According to the present invention, can provide a kind of polarization plates, even if when the thickness of brightness enhancement film is little, described polarization plates is also difficult to the stripping between adhesive phase and brightness enhancement film occurs under hygrothermal environment, and wet heat durability is excellent.Polarization plates of the present invention can preferably be applicable to liquid crystal indicator be the image display device of representative, the liquid crystal indicator of especially middle-size and small-size mobile terminal (flat board, smart mobile phone etc.).
Accompanying drawing explanation
Fig. 1 is the summary section of the example that the layer showing polarization plates of the present invention is formed.
Fig. 2 is the summary section of an example of the manufacture method showing polarization plates of the present invention.
Fig. 3 is the summary section of another example of the manufacture method showing polarization plates of the present invention.
Embodiment
Below, embodiment is shown, the present invention will be described in detail.
< polarization plates >
(1) formation of polarization plates
Fig. 1 is the summary section of the example that the layer showing polarization plates of the present invention is formed.Polarization plates 1 is as shown in Figure 1 such, and polarization plates of the present invention comprises polaroid 10, the 1st adhesive phase 20 and brightness enhancement film 30 successively.Polarization plates of the present invention can comprise other films, layer further; such as; polarization plates 1 shown in Fig. 1 comprises: be laminated in polaroid 10 with the diaphragm 40 on the face of the 1st adhesive phase 20 opposite side; be laminated in the 2nd adhesive phase 50 on the outside surface of diaphragm 40, be laminated in the barrier film 60 on the outside surface of the 2nd adhesive phase 50.2nd adhesive phase 50 is for being pasted on miscellaneous part (such as liquid crystal cells, other bloomings) by polarization plates.Barrier film 60 is the films temporarily pasted to protect its surface before the 2nd adhesive phase 50 is fitted in miscellaneous part.
The surface of the 1st adhesive phase 20 side in brightness enhancement film 30 implements surface activation process.Thereby, it is possible to be difficult to the polarization plates of stripping between generation the 1st adhesive phase 20 and brightness enhancement film 30, wet heat durability excellence under being formed in hygrothermal environment.Surface activation process is preferably corona treatment.
(2) polaroid
Polaroid 10 absorbs the absorptive-type polaroid of the linear polarization with the vibration plane parallel with its absorption axle, the character making the linear polarization transmission with (with light transmission shaft parallel) vibration plane orthogonal with absorption axle for having, can preferably use dichromatism pigment to be adsorbed in polyvinyl alcohol resin film and the polarizing coating of orientation occur.Such as, polaroid 10 can be manufactured by the method comprising following operation: the operation of polyvinyl alcohol resin film being carried out to uniaxial tension; By dyeing the operation making it adsorb dichromatism pigment to polyvinyl alcohol resin film with dichromatism pigment; By the operation that boric acid aqueous solution processes the polyvinyl alcohol resin film being adsorbed with dichromatism pigment; And carry out the operation of washing after with boric acid aqueous solution process.
As polyvinyl alcohol resin, can use and saponification be carried out to polyvinyl acetate system resin and the resin obtained.As polyvinyl acetate system resin, except the polyvinyl acetate of the homopolymer as vinyl acetate, can also enumerate with can with the multipolymer etc. of other monomers of vinyl acetate copolymerization.Can unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class be comprised with the example of other monomers of vinyl acetate copolymerization and there is (methyl) acrylic amide etc. of ammonium.In this instructions, " (methyl) acrylic acid " be meant at least one party being selected from acrylic acid and methacrylic acid.
The saponification degree of polyvinyl alcohol resin is generally about 85 ~ 100mol%, is preferably more than 98mol%.Polyvinyl alcohol resin through modification, such as, can use the polyvinyl formal or polyvinyl acetal etc. through aldehydes modification.The average degree of polymerization of polyvinyl alcohol resin is generally about 1000 ~ 10000, is preferably about 1500 ~ 5000.The average degree of polymerization of polyvinyl alcohol resin can be obtained according to JISK6726.
Such polyvinyl alcohol resin is filmed and former material film that the film that obtains can be used as polaroid 10 (polarizing coating) uses.The method that polyvinyl alcohol resin is filmed is not particularly limited, known method can be adopted.The thickness of the former material film of polyethenol series is not particularly limited, and in order to the thickness of polaroid 10 is made less than 15 μm, preferably uses the former material film of about 5 ~ 35 μm.Be more preferably less than 20 μm.If stretch to the former material film of the polyethenol series of thickness more than 35 μm the polaroid 10 obtaining thickness less than 15 μm, then need to improve stretching ratio, even if when being made below 15 μm by the thickness of polaroid 10, the dimensional contraction under hot environment also can increase.In addition, when thickness is less than 5 μm, operability during stretching reduces, and when manufacturing polaroid, easily occurs to cut off such undesirable condition.
The uniaxial tension of polyvinyl alcohol resin film can before dichromatism pigment dyeing, with dyeing simultaneously or carry out after dyeing.When carrying out uniaxial tension after dyeing, this uniaxial tension can carry out before boric acid process or in boric acid process.In addition, also uniaxial tension can be carried out by above-mentioned multiple stage.
In uniaxial tension, can stretch along single shaft between the roller that peripheral speed is different, hot-rolling also can be used to stretch along single shaft.In addition, uniaxial tension both can be the dry type stretching carrying out in an atmosphere stretching, and also can be to stretch in the wet type making with solvent to carry out under the swelling state of polyvinyl alcohol resin film stretching.Stretching ratio is generally about 3 ~ 8 times.
As the method dyeed to polyvinyl alcohol resin film with dichromatism pigment, such as, can adopt this method of being flooded in the aqueous solution containing dichromatism pigment by film.As dichromatism pigment, iodine, dichroic organic dye can be used.Wherein, polyvinyl alcohol resin film preferably implements the process of flooding in water before dyeing process.
As the dyeing process utilizing iodine to carry out, the method for polyvinyl alcohol resin film is flooded in the aqueous solution containing iodine and potassium iodide usually adopted.In this aqueous solution, the content of iodine can be about every 100 weight parts water 0.01 ~ 1 weight portions.The content of potassium iodide can be about every 100 weight parts water 0.5 ~ 20 weight portions.In addition, the temperature of this aqueous solution can be about 20 ~ 40 DEG C.On the other hand, as the dyeing process utilizing dichroic organic dye to carry out, what usually adopt is the method for being flooded in containing the aqueous solution of dichroic organic dye by polyvinyl alcohol resin film.Aqueous solution containing dichroic organic dye can containing inorganic salts such as sodium sulphate as dyeing assistant.In this aqueous solution, the content of dichroic organic dye can be every 100 weight parts waters 1 × 10
-4about ~ 10 weight portions.The temperature of this aqueous solution can be about 20 ~ 80 DEG C.
As the boric acid process after the dyeing utilizing dichromatism pigment to carry out, what usually adopt is the method for being flooded in containing boron aqueous acid by dyed polyvinyl alcohol resin film.When using iodine as dichromatism pigment, should containing boron aqueous acid preferably containing potassium iodide.Amount containing boron aqueous acid mesoboric acid can be about every 100 weight parts water 2 ~ 15 weight portions.In this aqueous solution, the amount of potassium iodide can be about every 100 weight parts water 0.1 ~ 15 weight portions.The temperature of this aqueous solution can be more than 50 DEG C, such as, be 50 ~ 85 DEG C.
Polyvinyl alcohol resin film after boric acid process carries out washing process usually.Washing processing example will be as can by carrying out at water retting through the acid-treated polyvinyl alcohol resin film of boron.In washing process, the temperature of water is generally about 5 ~ 40 DEG C.
After washing, implement dry process, obtain polaroid 10.Dry process can use air drier, far infra-red heater to carry out.The thickness of polaroid 10 is preferably less than 15 μm, is more preferably less than 10 μm.It is favourable for the thickness of polaroid 10 being set to less than 15 μm to the filming of polarization plates and even liquid crystal indicator.The thickness of polaroid 10 is generally more than 4 μm.
(3) the 1st adhesive phases
1st adhesive phase 20 is for being present in the layer between polaroid 10 and brightness enhancement film 30.Typical case, the mode that the 1st adhesive phase 20 connects with the 1st adhesive phase 20 with polaroid 10 is directly laminated in polaroid 10.Such as known, when fit on polaroid 10 diaphragm and on stacked 1st adhesive phase 20 time, even if be also difficult to the stripping between adhesive phase and brightness enhancement film occurs under hygrothermal environment.1st adhesive phase 20 can be that the adhesive composition of major component is formed by the resin such with (methyl) acrylic acid series, rubber series, carbamate system, ester system, silicon-type, polyvingl ether system.Wherein, based on (methyl) acrylic resin of the excellences such as the transparency, weatherability, thermotolerance, the adhesive composition of polymkeric substance is desirable.Adhesive composition can be active energy ray curable, thermohardening type.
As above-mentioned (methyl) acrylic base polymkeric substance, preferably use such (methyl) acrylic ester base polymer of such as (methyl) butyl acrylate, (methyl) ethyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, employ the copolymerization system base polymer of above-mentioned (methyl) of more than two kinds acrylate.Preferably make polar monomer and base polymer copolymerization.As polar monomer, can enumerate such as (methyl) acrylic acid, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) hydroxy-ethyl acrylate, (methyl) acrylamide, N, N-dimethyl aminoethyl (methyl) acrylate, glycidyl (methyl) acrylate such, the monomer with carboxyl, hydroxyl, amide group, amino, epoxy radicals etc.
Adhesive composition is usually further containing crosslinking chemical.As crosslinking chemical, can illustrate: for metallic ion more than divalent and and form the material of carboxylic metallic salt between carboxyl; For polyhydric amine compounds and and form the material of amido link between carboxyl; For polyepoxides, polyvalent alcohol and and form the material of ester bond between carboxyl; And the material of amido link between carboxyl, is formed for polyisocyanate compounds.Wherein, polyisocyanate compounds is preferably.
Active energy ray curable adhesive composition is the adhesive composition with following character: be subject to the irradiation of the such active energy beam of ultraviolet, electron ray and solidify, before irradiation active energy beam, also there is cohesive, can the adherends such as film be sealed at, can be solidified by the irradiation of active energy beam and carry out the adjustment of closing force.Active energy ray curable adhesive composition is preferably ultraviolet hardening.In active energy ray curable adhesive composition, except base polymer, crosslinking chemical, further containing active energy beam polymerizable compound.And then, sometimes as required containing Photoepolymerizationinitiater initiater, light sensitizer etc.
Adhesive composition can contain for giving light scattering particulate; Pearl; Resin beyond base polymer; Tackifier; Filling agent; Antioxidant; Ultraviolet light absorber; Pigment; The adjuvants such as colorant.
1st adhesive phase 20 can by be coated on the organic solvent diluting liquid of above-mentioned adhesive composition on base material and to carry out drying and formed.Base material can be polaroid 10, brightness enhancement film 30, barrier film etc.When using active energy ray curable adhesive composition, can by irradiating to formed adhesive phase the solidfied material that active energy beam makes expectation.
1st adhesive phase 20 preferably shows the storage elastic modulus of 0.15 ~ 1MPa in the temperature range of 23 ~ 80 DEG C.Thereby, it is possible to suppress the change in size easily produced with the contraction of polaroid 10 under hygrothermal environment, improve the permanance of polarization plates.In addition, even if when the liquid crystal indicator (such as middle-size and small-size liquid crystal indicator used for mobile terminal) being equipped with polarization plates is placed under hygrothermal environment, the variation of polarization plates is also suppressed, thus can improve the reliability of liquid crystal indicator.
What " in the temperature range of 23 ~ 80 DEG C, show the storage elastic modulus of 0.15 ~ 1MPa " is meant to, and under the arbitrary temp within the scope of this, storage elastic modulus is the value in above-mentioned scope.Storage elastic modulus usually along with temperature rise and reduce gradually, thus, if 23 DEG C and 80 DEG C time storage elastic modulus all in above-mentioned scope, then can be considered as the storage elastic modulus shown at the temperature of this scope in above-mentioned scope.The storage elastic modulus of the 1st adhesive phase 20 can use commercially available determination of viscoelasticity device, such as show that the determination of viscoelasticity device " DYNAMICANALYZERRDAII " of that REOMETRIC Inc. shown in embodiment measures afterwards.
As the method for storage elastic modulus being adjusted to above-mentioned scope, can be set forth in the adhesive composition containing base polymer and crosslinking chemical and add oligomer, specifically carbamate (methyl) acrylic ester oligomer further, make active energy ray curable adhesive composition (preferred ultraviolet-curing adhesive composition).More preferably irradiate active energy beam, make the solidification of adhesive phase appropriateness.
The thickness of the 1st adhesive phase 20 can be 1 ~ 40 μm, the processability that collateral security is good and suppress the viewpoint of the change in size of polarization plates to be set out, and is preferably set to 3 ~ 25 μm (such as 3 ~ 20 μm).
(4) brightness enhancement film
Brightness enhancement film 30, sometimes also referred to as reflective polarizing film, can use the polarization conversion device having and make the emergent light from light source (backlight) be separated into the function of transmission polarisation and reflective polarizer or scattering polarisation.As mentioned above, by being configured on polaroid 10 by brightness enhancement film 30, the retroreflection light (again Kaesa light) as reflective polarizer or scattering polarisation can be utilized to improve outgoing efficiency from the linear polarization of polaroid 10 outgoing.Brightness enhancement film 30 is folded with the 1st adhesive phase 20 phase ground plane usually.
Brightness enhancement film 30 can be such as anisotropic emission polaroid.An example of anisotropic emission polaroid is the multiple film of anisotropy making the linear polarization transmission of a direction of vibration and the linear polarization of other direction of vibration is reflected, and its object lesson is the DBEF (Japanese Unexamined Patent Publication 4-268505 publication etc.) of 3M.Another example of anisotropic emission polaroid is the complex of cholesteric liquid crystal layer and λ/4 plate, and its object lesson is the PCF (Japanese Unexamined Patent Publication 11-231130 publication etc.) of day east electrician.Another example further of anisotropic emission polaroid is reflecting grating polaroid, its object lesson is, even if implement microfabrication to metal thus also can make that metallic grid reflecting polarizer of reflective polarizer outgoing (United States Patent (USP) No. 6288840 instructions etc.) in visible region, to be made an addition to by metal particle in polymer matrix and the film (Japanese Unexamined Patent Publication 8-184701 publication) stretched.
In brightness enhancement film 30 with the face of the 1st adhesive phase 20 opposite side on can be provided with hard conating, antiglare layer, light diffusion layer, there is the such optical layers of the phase separation layer of the phase difference value of 1/4 wavelength.By the formation of optical layers, can improve and the adaptation of backlight adhesive tape, the homogeneity showing image.The thickness of brightness enhancement film 30 can be about 10 ~ 100 μm, from the view point of the filming of polarization plates, is preferably 10 ~ 50 μm, is more preferably 10 ~ 30 μm.
In polarization plates of the present invention, the surface of the 1st adhesive phase 20 side in brightness enhancement film 30 implements surface activation process.This surface activation process is carried out prior to the laminating of brightness enhancement film 30 and the 1st adhesive phase 20.Thereby, it is possible to be difficult to the polarization plates 1 of stripping between generation the 1st adhesive phase 20 and brightness enhancement film 30, wet heat durability excellence under being formed in hygrothermal environment.
Surface activation process can be the hydrophilicity-imparting treatment on surface, both can be dry process also can be wet processed.As dry process, the discharge process that such as corona treatment, Cement Composite Treated by Plasma, glow discharge process are such can be enumerated; Flame treatment; Ozone treatment; UV ozone treatment; The ionization activity Irradiation etc. that UV treatment, electron ray process are such.As wet processed, the ultrasound wave process of the solvent such as using water, acetone such, alkali treatment, anchor coat process etc. can be illustrated.These process both can have been carried out separately also can combining two or more and carrying out.
Wherein, the stripping inhibition of the brightness enhancement film 30 under hygrothermal environment and the throughput rate of polarization plates, surface activation process is preferably corona treatment and/or Cement Composite Treated by Plasma.By these surface activation process, though the thickness of brightness enhancement film 30 little to less than 30 μm time, also effectively can suppress the stripping between the 1st adhesive phase 20 and brightness enhancement film 30 under hygrothermal environment.Wherein, the surface of brightness enhancement film 30 side in the 1st adhesive phase 20 can implement surface activation process in the lump, but only the surface enforcement surface activation process of brightness enhancement film 30 also can obtain sufficient effect.Surprisingly, the surface of brightness enhancement film 30 side only in the 1st adhesive phase 20 has little effect when implementing surface activation process on the contrary.
(5) diaphragm
Diaphragm 40 be in polaroid 10 with stacked alternatively film on the face of the 1st adhesive phase 20 opposite side.But, from the view point of the protection of polaroid 10, polarization plates preferably comprises diaphragm 40.Diaphragm 40 can be the film that formed by (preferably optically transparent) thermoplastic resin with light transmission, the polyolefin-based resins that described thermoplastic resin such as chain polyolefin-based resins (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system resin (norbornene resin etc.) is such; The cellulose-based resin that tri acetyl cellulose, diacetyl cellulose are such; The polyester based resin that polyethylene terephthalate, polybutylene terephthalate are such; Polycarbonate-based resin; (methyl) acrylic resin; Polystyrene resin; Polyvinyl chloride resin; Acrylonitrile-butadiene-styrene (ABS) system resin; Acrylonitrile-styrene system resin; Polyvinyl acetate system resin; Polyvinylidene chloride resin; Polyamide series resin; Polyacetal system resin; Noryl system resin; Polysulfones system resin; Polyethersulfone system resin; Polyarylate system resin; Polyamidoimide system resin; Polyimide system resin etc.Wherein, polyolefin-based resins, cellulose-based resin is preferably used.
As chain polyolefin-based resins, except the homopolymer of the such chain olefin of polyvinyl resin, acrylic resin, the multipolymer comprising chain olefin of more than two kinds can also be enumerated.
Cyclic polyolefin hydrocarbon system resin take cyclic olefin as the general name of the resin that polymerized unit is polymerized.Enumerate the object lesson of cyclic polyolefin hydrocarbon system resin, the multipolymer (representational is random copolymers) of the chain olefin having the addition polymer of the open loop of cyclic olefin (being total to) polymkeric substance, cyclic olefin, cyclic olefin and ethene, propylene such and graft polymer above-mentioned substance modification obtained with unsaturated carboxylic acid, its derivant and their hydride etc.Wherein, preferably use norbornene resin, norbornene resin uses the norborneol alkene monomer such as norborene, many rings norborneol alkene monomer as cyclic olefin.
Cellulose-based resin refers to; from the cellulosic hydroxyl that the raw celluloses such as cotton linter, wood pulp (hard wood pulp, soft wood pulp) obtain, part or all cellulose organic ester obtained by the replacement of acetyl group, propiono and/or bytyry or cellulose mixed organic acid ester of hydrogen atom.The material such as comprising cellulosic acetic acid esters, propionic ester, butyric ester and their mixed ester etc. can be enumerated.Wherein, tri acetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate is preferably.
The phase difference value of diaphragm 40 is controlled as the value desirable to liquid crystal indicator is useful.Such as, in the liquid crystal indicator of plane conversion (IPS) type, phase difference value in fact is preferably used to be the film of zero.Phase difference value is zero to refer in fact, in the face during wavelength 590nm phase difference value be below 10nm, wavelength 590nm time the absolute value of thickness direction phase difference value be below 10nm, wavelength 480 ~ 750nm time the absolute value of thickness direction phase difference value be below 15nm.
Can stretch to diaphragm 40 according to the type of liquid crystal indicator and/or shrink processing, give desirable phase difference value.
The thickness of diaphragm 40 can be about 1 ~ 100 μm, from the viewpoint such as intensity, operability, is preferably 5 ~ 60 μm, is more preferably 5 ~ 50 μm.If the thickness within the scope of this, then can mechanically protect polaroid 10, even if under being exposed to hygrothermal environment, polaroid 10 also can not shrink, and can ensure stable optical characteristics.
Diaphragm 40 can fit in polaroid 10 via bond layer.As the bonding agent forming bond layer, water system bonding agent or active energy ray-curable bonding agent can be used.
As water system bonding agent, the bonding agent, water system two-liquid type carbamate system emulsion bonding agent etc. that are formed by polyvinyl alcohol resin aqueous solution can be enumerated.Wherein, the water system bonding agent formed by polyvinyl alcohol resin aqueous solution can preferably be used.As polyvinyl alcohol resin, except the alcotex obtained except carrying out saponification process to the polyvinyl acetate of the homopolymer as vinyl acetate, can also use vinyl acetate and the multipolymer of other monomers of copolymerization with it can carry out saponification process and the polyvinyl alcohol (PVA) based copolymer that obtains or the modified polyvinylalcohol based polymer etc. that their hydroxylic moiety modification is obtained.Water system bonding agent can contain the crosslinking chemicals such as aldehyde compound, epoxy compound, melamine based compound, methylol compound, isocyanate compound, amines, multivalent metal salt.
When using water system bonding agent, preferably after polaroid 10 and diaphragm 40 are fitted, implement in order to dry operation is carried out in water contained in water system bonding agent removing.After drying process, can setting example as carried out the maintenance operation of maintenance (Raising raw) with the temperature of about 20 ~ 45 DEG C.
Above-mentioned active energy ray-curable bonding agent refers to the bonding agent solidified by the such active energy beam of irradiation ultraviolet radiation, can enumerate bonding agent, the bonding agent containing light reactive resin, the bonding agent etc. containing resin glue and photoreactivity crosslinking chemical such as containing polymerizable compound and Photoepolymerizationinitiater initiater.As polymerizable compound, the such photopolymerization monomer of photo-curable epoxy monomer, photo-curable (methyl) acrylic monomer, photo-curable carbamate system monomer, oligomer from photopolymerization monomer can be enumerated.As Photoepolymerizationinitiater initiater, the initiating agent of the material producing the such spike of Neutral radical, radical anion, radical cation containing the irradiation by the such active energy beam of ultraviolet can be enumerated.As the active energy ray-curable bonding agent containing polymerizable compound and Photoepolymerizationinitiater initiater, the bonding agent containing photo-curable epoxy monomer and light cationic polymerization initiators preferably can be used.
When using active energy ray-curable bonding agent, after polaroid 10 and diaphragm 40 being fitted, carrying out drying process as required, then carrying out curing process active energy ray-curable bonding agent being solidified by irradiating active energy beam.The light source of active energy beam is not particularly limited, preferably have at below wavelength 400nm and send out ultraviolet photodistributed, specifically, low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black lamp, microwave-excited mercury lamp, metal halide lamp etc. can be used.
When polaroid 10 is fitted with diaphragm 40, can in them at least the binding face of either party implement saponification process, corona treatment, Cement Composite Treated by Plasma etc.
(6) the 2nd adhesive phase and barrier films
The 2nd adhesive phase 50 be laminated on the outside surface of diaphragm 40 is can in order to polarization plates being pasted on the optional layer that miscellaneous part (such as liquid crystal cells, other bloomings) is arranged.About the composition of the adhesive composition of formation the 2nd adhesive phase 50, quote the above-mentioned record about the 1st adhesive phase 20.The storage elastic modulus of the 2nd adhesive phase 50 both can be identical with the 1st adhesive phase 20, also can be different.
Barrier film 60 is the films temporarily pasted to protect its surface before the 2nd adhesive phase 50 is fitted in miscellaneous part, such as, use the film formed the transparent resin such by polyethylene terephthalate to implement to utilize the process that the release agent of silicon-type etc. carries out and the film obtained.The surface of the 1st adhesive phase 20 also can be pasted with and barrier film same above to carry out temporarily pasting protection to its surface before laminating brightness enhancement film 30.
The manufacture method > of < polarization plates
The manufacture method of polarization plates of the present invention is the manufacture method of the polarization plates comprising polaroid, the 1st adhesive phase and brightness enhancement film successively, comprises following operation:
The surface of the 1st adhesive phase side in brightness enhancement film is implemented to the 1st operation of surface activation process, and
The 2nd operation of stacked 1st adhesive phase on the above-mentioned surface implementing surface activation process.
Be described with reference to the embodiment of Fig. 2 to the manufacture method of the polarization plates 1 shown in Fig. 1, as described below.First, via one side laminating diaphragm 40, thereon stacked 2nd adhesive phase 50 of bond layer at polaroid 10, meanwhile, at another side laminating the 1st adhesive phase 20 of polaroid 10, the duplexer 100 that the layer shown in Fig. 2 (a) is formed is obtained.As shown in the figure, can temporarily be pasted with barrier film 60 on the outside surface of the 2nd adhesive phase 50, on the outside surface of the 1st adhesive phase 20, temporarily be pasted with barrier film 70.
Next, after barrier film 70 is peeled off removing from the 1st adhesive phase 20 of duplexer 100, the stacked brightness enhancement film 30 by above-mentioned 1st operation, binding face (lamination surface) being implemented in advance to surface activation process in its release surface, obtains polarization plates 1 (Fig. 2 (b), the 2nd operation).Also can in the 1st adhesive phase 20 and the binding face of brightness enhancement film 30 implement surface activation process.
In the making of duplexer 100, form as long as can obtain the layer comprising the 2nd adhesive phase 50/ diaphragm 40/ polaroid 10/ the 1st adhesive phase 20 successively, stacked order is not limited to above-mentioned example.Such as, both can be following order: at a stacked guard film 40 of polaroid 10, on the 2nd adhesive phase 50 is set, then, at stacked 1st adhesive phase 20 of the another side of polaroid 10; Can be again following order: at a stacked guard film 40 of polaroid 10, at stacked 1st adhesive phase 20 of the another side of polaroid 10, then, diaphragm 40 arrange the 2nd adhesive phase 50.
Brightness enhancement film 30 both can be that monolithic laminating method (Mei Leaf Stickers is legal to the applying method of the 1st adhesive phase 20 of duplexer 100), also can be that-roller compound laminating method recorded in Japanese Unexamined Patent Publication 2004-262071 publication.In addition, can to produce with rectangular form, and when requirement is large, utilize roll-to-roll applying method be also useful (for following embodiment too.)。
Next, be described with reference to Fig. 3 another embodiment to the manufacture method of the polarization plates 1 shown in Fig. 1, as described below.First, via the one side laminating diaphragm 40 of bond layer at polaroid 10, on stacked 2nd adhesive phase 50, obtain the duplexer 200 that the layer shown in Fig. 3 (a) is formed.As shown in the figure, can temporarily be pasted with barrier film 60 on the outside surface of the 2nd adhesive phase 50, on the outside surface of polaroid 10, temporarily be pasted with surface protection film 90.Can in diaphragm 40 and in the binding face of the 2nd adhesive phase 50 and the 2nd adhesive phase 50 and diaphragm 40 binding face at least either party and polaroid 10 in and in the binding face of surface protection film 90 and surface protection film 90 and polaroid 10 binding face at least one party carry out the surface activation process such as corona treatment, Cement Composite Treated by Plasma.
On the other hand, after implementing surface activation process by above-mentioned 1st operation to the surface of brightness enhancement film 30, stacked 1st adhesive phase 20 on a surface, obtains duplexer 300.Also can in the 1st adhesive phase 20 and the binding face of brightness enhancement film 30 implement the such surface activation process of corona treatment, Cement Composite Treated by Plasma.As shown in the figure, the outside surface of the 1st adhesive phase 20 can temporarily be pasted with barrier film 80.
Next; by barrier film 80 from the 1st adhesive phase 20 of duplexer 300, surface protection film 90 is peeled off removing from the polaroid 10 of duplexer 200 after; on polaroid 10, laminating the 1st adhesive phase 20, obtains polarization plates 1 (Fig. 3 (b), the 2nd operation).
Have in the making of duplexer 200 of surface protection film 90, form as long as can obtain the layer comprising the 2nd adhesive phase 50/ diaphragm 40/ polaroid 10/ surface protection film 90 successively, stacked order is not limited to above-mentioned example.Such as, both can be following order: at a stacked guard film 40 of polaroid 10, on the 2nd adhesive phase 50 is set, then, at the another side laminate surface diaphragm 90 of polaroid 10; Also can be following order: at a stacked guard film 40 of polaroid 10, at the another side laminate surface diaphragm 90 of polaroid 10, then, diaphragm 40 arrange the 2nd adhesive phase 50.
< liquid crystal indicator >
Polarization plates of the present invention preferably can be applicable to liquid crystal indicator.Liquid crystal indicator comprises liquid crystal cells and fits in its surface, polarization plates of the present invention.Polarization plates can be carried out via adhesive phase (the 2nd adhesive phase 50 in the polarization plates 1 shown in Fig. 1) to the laminating of liquid crystal cells.Polarization plates of the present invention uses usually used as the polarization plates of the backlight side being configured at liquid crystal cells.The type of drive of liquid crystal cells can be known any mode, is preferably IPS type.The wet heat durability employing the liquid crystal indicator of polarization plates of the present invention is excellent.
embodiment
Embodiment and comparative example are below shown, the present invention will be described particularly further, but the invention is not restricted to these examples.Wherein, the storage elastic modulus of the thickness of film, phase difference value and adhesive phase measures by the following method.
(1) thickness
The digital micrometer " MH-15M " of (strain) Nikon is used to measure.
(2) phase difference value and thickness direction phase difference value in face
Be used as with " KOBRA-ADH " of the OjiScientificInstruments of the parallel-nicol rotary process phasometer that is principle, measure with the light of wavelength 590nm, 483nm or 755nm at 23 DEG C.
(3) storage elastic modulus
The storage elastic modulus G ' of adhesive phase measures according to following (I) ~ (III).
(I) take out 2 parts of samples from adhesive phase, each 25 ± 1mg, is shaped to substantial circular respectively.
(II) sample of the substantial circular of acquisition is pasted on the top and bottom of I type fixture, reinstates L-type holder with top and bottom one.The formation measuring sample is: L-type tool/bonding agent/I type tool/bonding agent/L-type fixture.
(III) for the storage elastic modulus G ' of the sample made by this way, the Measurement of Dynamic Viscoelasticity device " DVA-220 " using IT Survey control Co., Ltd. (ア イ テ ィ ー Meter Measuring system drives (strain)) to make, measures under the condition of temperature 23 DEG C, frequency 1Hz, initial strain 1N.
(making of the polaroid A that thickness is 7 μm)
Pass through dry type stretching, by polyvinyl alcohol film (average degree of polymerization about 2400, saponification degree more than the 99.9 % by mole) uniaxial tension about 5 times of thickness 20 μm, and then, under the state keeping tense situation, flood in the pure water of 60 DEG C after 1 minute, at 28 DEG C, be flood 60 seconds in the aqueous solution of 0.05/5/100 in the weight ratio of iodine/potassium iodide/water.Then, at 72 DEG C, be flood 300 seconds in the aqueous solution of 8.5/8.5/100 in the weight ratio of potassium iodide/boric acid/water.Then use the pure water of 26 DEG C after 20 seconds, 65 DEG C of dryings, obtain iodine and be adsorbed in polyvinyl alcohol film and the polaroid A of the thickness 7 μm of orientation occurs.
(making of the polaroid B of thickness 12 μm)
Use the polyvinyl alcohol film (average degree of polymerization about 2400, saponification degree more than 99.9 % by mole) of thickness 30 μm, in addition, to operate equally with polaroid A, obtain iodine and be adsorbed in polyvinyl alcohol film and the polaroid B of the thickness 12 μm of orientation occurs.
(preparation of brightness enhancement film C and D)
Prepare 2 kinds of following brightness enhancement films:
The brightness enhancement film C of thickness 26 μm; " AdvancedPolarizedFilm, the Version3 " of 3M,
The brightness enhancement film D of thickness 17 μm; " AdvancedPolarizedFilm, the Version4 " of 3M.
(preparation of diaphragm E and F)
Prepare 2 kinds of following diaphragms:
Diaphragm E; Cyclic polyolefin resin film that Japan Zeon (strain) makes (thickness direction phase difference value=-4.2nm during thickness direction phase difference value=2.5nm, wavelength 755nm during thickness direction phase difference value=2.8nm, wavelength 483nm in face when thickness 23 μm, wavelength 590nm when phase difference value=2.1nm, wavelength 590nm),
Diaphragm F; Cyclic polyolefin resin film that Japan Zeon (strain) makes (thickness direction phase difference value=2.8nm during thickness direction phase difference value=3.5nm, wavelength 755nm during thickness direction phase difference value=3.4nm, wavelength 483nm in face when thickness 13 μm, wavelength 590nm when phase difference value=0.8nm, wavelength 590nm).
(modulation of adhesive phase or preparation)
Modulate or prepare 2 kinds of following adhesive phases:
1st adhesive phase; Mould is utilized to be coated with machine, the mode of 15 μm is become with dried thickness, be coated on by the organic solvent solution adding urethane acrylate oligomer and isocyanate-based crosslinking chemical in butyl acrylate and acrylic acid multipolymer on the demoulding treated side of the barrier film formed by polyethylene terephthalate of the thickness 38 μm implementing demoulding process, (storage elastic modulus of this adhesive phase is 0.40MPa, is 0.18MPa 80 DEG C time 23 DEG C time for the dry and adhesive phase of band barrier film that obtains.)、
2nd adhesive phase; The adhesive phase that the demoulding treated side implementing the barrier film formed by polyethylene terephthalate of the thickness 38 μm of demoulding process is provided with the commercially available band barrier film of the acrylic adhesive layer of thickness 25 μm (does not coordinate urethane acrylate oligomer.The storage elastic modulus of this adhesive phase is 0.05MPa, is 0.04MPa 80 DEG C time 23 DEG C time.)。
(modulation of water system bonding agent)
For 100 weight parts waters, dissolve the carboxy-modified polyvinyl alcohol (PVA) (" KL-318 " of (strain) Kuraray) of 3 weight portions, modulation polyvinyl alcohol water solution.In the aqueous solution obtained, in the ratio mixed water soluble polyamide epoxy resin (" SumirezResin650 (30) ", solid component concentration 30 % by weight that ridge, field chemical industry (strain) is made) relative to 100 weight parts waters being 1.5 weight portions, obtain water system bonding agent.
< embodiment 1 >
Polarization plates is made by the step same with the step shown in Fig. 2.First, use above-mentioned water system bonding agent at the one side laminating diaphragm E of polaroid A.Before laminating, in diaphragm E and the binding face of polaroid A implement 15.9kJ/m
2corona treatment.Then, 80 DEG C of dryings 5 minutes, 40 DEG C of maintenances 168 hours.Next, in polaroid A with the face of diaphragm E opposite side on to fit the 1st adhesive phase.Before laminating, 15.9kJ/m is implemented to the binding face of polaroid A and the binding face of the 1st adhesive phase
2corona treatment.
Next, laminating the 2nd adhesive phase on the outside surface of diaphragm E.Before laminating, 15.9kJ/m is implemented to the binding face of diaphragm E and the binding face of the 2nd adhesive phase
2corona treatment.Finally, the barrier film of the 1st adhesive phase is peeled off, 15.9kJ/m is implemented to the one side of brightness enhancement film C
2corona treatment, then, brightness enhancement film C is fitted in the outside surface of the 1st adhesive phase with its side, corona treatment face, obtain polarization plates.
< embodiment 2 >
Use diaphragm F to replace diaphragm E, in addition, operate similarly to Example 1, make polarization plates.
< embodiment 3 >
Use brightness enhancement film D to replace brightness enhancement film C, in addition, operate similarly to Example 1, make polarization plates.
< embodiment 4 >
Use polaroid B to replace polaroid A, in addition, operate similarly to Example 1, make polarization plates.
< embodiment 5 >
Use polaroid B to replace polaroid A, in addition, operate similarly to Example 3, make polarization plates.
< embodiment 6 >
Polarization plates is made by the step same with the step shown in Fig. 3.First, use above-mentioned water system bonding agent at the one side laminating diaphragm E of polaroid A.Before laminating, 15.9kJ/m is implemented to the binding face in polaroid A in diaphragm E
2corona treatment.Then, 80 DEG C of dryings 5 minutes, 40 DEG C of maintenances 168 hours.Next, in polaroid A with coating surface diaphragm on the face of diaphragm E opposite side (" Toretekku (ト レ テ ッ Network) 7332 " that eastern beautiful processing film (strain) is made).Before laminating, 15.9kJ/m is implemented to the binding face of polaroid A
2corona treatment.And then, the 2nd adhesive phase that the outside surface of diaphragm E is fitted.Before laminating, 15.9kJ/m is implemented to the binding face of diaphragm E and the binding face of the 2nd adhesive phase
2corona treatment.
Next, in one side laminating the 1st adhesive phase (band barrier film) of brightness enhancement film C.Before laminating, 15.9kJ/m is implemented to the binding face of brightness enhancement film C and the binding face of the 1st adhesive phase
2corona treatment.Finally, after being peeled off by the barrier film of the surface protection film of polaroid A and the 1st adhesive phase, the exposed surface (outside surface) of the polaroid A exposed the stripping because of surface protection film implements 15.9kJ/m
2corona treatment, then, on its corona treatment face fit the 1st adhesive phase, obtain polarization plates.
< embodiment 7 >
Use diaphragm F to replace diaphragm E, in addition, operate similarly to Example 6, make polarization plates.
< embodiment 8 >
Use brightness enhancement film D to replace brightness enhancement film C, in addition, operate similarly to Example 6, make polarization plates.
< embodiment 9 >
Use polaroid B to replace polaroid A, in addition, operate similarly to Example 6, make polarization plates.
< embodiment 10 >
Use polaroid B to replace polaroid A, in addition, operate similarly to Example 8, make polarization plates.
< embodiment 11 >
1st adhesive phase, in the laminating of the exposed surface (face of exposing because of the stripping of surface protection film) of polaroid A, is not implemented the corona treatment of the exposed surface for polaroid A, in addition, is operated similarly to Example 6, makes polarization plates.
< comparative example 1 ~ 11 >
Do not carry out corona treatment with the binding face of the 1st adhesive phase in brightness enhancement film C or D, in addition, to operate equally with embodiment 1 ~ 11 respectively, make polarization plates.Wherein, in comparative example 6 ~ 11, before the laminating of brightness enhancement film C or D and the 1st adhesive phase, corona treatment is not carried out to the binding face of brightness enhancement film C or D, but corona treatment has been carried out to the binding face of the 1st adhesive phase.
(evaluation of wet heat durability)
Cut out the sample of 111mm × 65mm size from the polarization plates obtained, fit in alkali-free glass (" EAGLEXG " of Corning Incorporated) via the 2nd adhesive phase.For this glass gluing sample, in the baking oven of practicing system 60 DEG C of 90%RH, the wet heat durability of 500 hours is tested, and according to following benchmark, carries out visual assessment to the outward appearance of the sample after test.Show the result in table 1.Wherein, hurdle represents " surface activation process " in table 1 one is the presence or absence of the surface activation process of binding face for brightness enhancement film.
A: the stripping of arriving the interface of brightness enhancement film and adhesive phase unconfirmed in the end of polarization plates, outward appearance is good,
B: only confirm above-mentioned stripping in the end of polarization plates.
C: not only confirm above-mentioned stripping in the end of polarization plates, and stripping proceeds to central portion.
[table 1]
Claims (11)
1. a polarization plates, it comprises polaroid, adhesive phase and brightness enhancement film successively,
The surface of the described adhesive phase side in described brightness enhancement film implements surface activation process.
2. polarization plates according to claim 1, wherein,
Described adhesive phase connects with described brightness enhancement film.
3. polarization plates according to claim 1, wherein,
Described polaroid connects with described adhesive phase.
4. polarization plates according to claim 1, wherein,
Described surface activation process is corona treatment.
5. polarization plates according to claim 1, wherein,
The thickness of described brightness enhancement film is 10 ~ 30 μm.
6. polarization plates according to claim 1, wherein,
The thickness of described polaroid is less than 15 μm.
7. polarization plates according to claim 1, wherein,
The storage elastic modulus of described adhesive phase in the temperature range of 23 ~ 80 DEG C is 0.15 ~ 1MPa, thickness is 3 ~ 20 μm.
8. polarization plates according to claim 1, its comprise further be laminated in described polaroid with the diaphragm on the face of described adhesive phase opposite side.
9. polarization plates according to claim 8, wherein,
Described diaphragm is made up of polyolefin-based resins or cellulose-based resin.
10. a liquid crystal indicator, it comprises the polarization plates according to any one of liquid crystal cells and claim 1 ~ 9.
11. 1 kinds of manufacture methods, it is the manufacture method of the polarization plates comprising polaroid, adhesive phase and brightness enhancement film successively, comprising:
The surface of the described adhesive phase side in described brightness enhancement film is implemented to the operation of surface activation process, and
The operation of stacked described adhesive phase on the described surface implementing described surface activation process.
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| JP2014201375 | 2014-09-30 | ||
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Cited By (2)
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| CN107526206A (en) * | 2016-06-21 | 2017-12-29 | 住友化学株式会社 | Polarize board component |
| CN108931865A (en) * | 2017-05-29 | 2018-12-04 | 住友化学株式会社 | Polarize board group and liquid crystal display panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016118761A (en) * | 2014-12-22 | 2016-06-30 | 住友化学株式会社 | Polarizing plate and manufacturing method of the same, and set of polarizing plates, liquid crystal panel, and liquid crystal display device |
| JP6887222B2 (en) * | 2016-06-21 | 2021-06-16 | 住友化学株式会社 | Polarizing plate set |
| WO2018034081A1 (en) * | 2016-08-17 | 2018-02-22 | 住友化学株式会社 | Polarizing plate set |
| JP6455545B2 (en) * | 2016-08-17 | 2019-01-23 | 住友化学株式会社 | Set of polarizing plates |
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| KR20160038742A (en) | 2016-04-07 |
| TWI686629B (en) | 2020-03-01 |
| TW201616157A (en) | 2016-05-01 |
| JP2016071378A (en) | 2016-05-09 |
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