CN1928593A - Highly durable polarization plate and liquid crystal display - Google Patents
Highly durable polarization plate and liquid crystal display Download PDFInfo
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- CN1928593A CN1928593A CN 200610128139 CN200610128139A CN1928593A CN 1928593 A CN1928593 A CN 1928593A CN 200610128139 CN200610128139 CN 200610128139 CN 200610128139 A CN200610128139 A CN 200610128139A CN 1928593 A CN1928593 A CN 1928593A
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Abstract
The present invention provides a polarizer comprising a polarizing film, a first transparent protective film and a second transparent protective film, the polarizing film being between the first transparent protective film and the second transparent protective film, wherein the first transparent protective film has a water-vapor permeability of 50 g/m<2>.24 hours or less at 40 DEG C under a relative humidity of 90% and a water content of the polarizer is 2.0% by weight or less.
Description
Technical field
The present invention relates to be used for the polarizer with excellent durability of LCD.The invention still further relates to the LCD of using this polarizer.
Background technology
Recently, usually LCD is used for automobile and mobile phone, and requires LCD under the environment of high temperature or high temperature and humidity, to have reliability.Particularly, when they are used for automobile, need be in the permanance under the very harsh environment, even make their performance under the high temperature exposure in summer, also not cause deterioration.
LCD is following formation normally: two electrode base boards that will have a transparency electrode are settled with the arrangement that their transparency electrode faces with each other, between them, insert liquid crystal, to form liquid crystal cell, polarizer is added on the one or both sides of liquid crystal cell then.As for such polarizer, common following manufacturing polarizer: iodine or dichroic dye are absorbed in the polyvinyl alcohol (PVA), polyvinyl alcohol film is stretched and be orientated, to form polarizing coating, with the fit two sides of the polarizing coating that obtains of the film of celluosic resin, described celluosic resin is typically as triacetyl cellulose (TAC) then.
Because they are permeated by water easily because of their common high water vapour permeabilities, the color of the polarizing coating of being made by celluosic resin is delayed, and under the exposure of damp and hot (anti wet-heat) environment, their tone reversal, or their polarity reduces.
Therefore; the water vapour permeability that reduces polarizer protecting film is attempted: for example; the resin that use is lower than the water vapour permeability of celluosic resin, or provide surface treatment to reduce the water vapour permeability of diaphragm by exposed surface to celluosic resin.
Be the technology that constitutes diaphragm with the resin of low water vapour permeability below: Jap.P. S59-159109A (patent documentation 1) discloses the improvement of polarizer permanance; wherein liquid water content be 5% or two faces of lower polyvinyl alcohol (PVA) polarizing coating on, settling the water vapour permeability as diaphragm is 10g/m
2Density polyethylene film with high or polypropylene screen that it or lower single orientated polymer film, particularly list are orientated; And Jap.P. S60-159704A (patent documentation 2) also discloses the improvement of polarizer permanance, and wherein at least one side of polyvinyl alcohol (PVA) polarizing coating, settling water vapour permeability is 55g/m under 80 ℃, 95% relative humidity
2Hr or size change rate lower and after 100 ℃ are heated 30 minutes are-0.3 to 0% transparent protective film, particularly resin molding, described resin such as polymethylmethacrylate, polyethersulfone or polycarbonate.Jap.P. H7-77608A (patent documentation 3) also discloses the improvement of polarizer permanance, and wherein at least one side of polyvinyl alcohol (PVA) polarizing coating, the applying water vapour permeability is 200g/m under 80 ℃, 90% relative humidity
224 hours 100 μ m or lower and photoelastic coefficient are 1 * 10
-11Cm
2/ dyne or lower diaphragm, particularly thermoplasticity saturated norbornene resin molding.
Jap.P. 2003-183417A (patent documentation 4) discloses a kind of cellulose ester membrane, wherein by blending plastifier such as abietic resin, epoxy resin, ketone resin or tosyl polyimide resin, making the mass change cellulose esters is handled 48 hours under 80 ± 5 ℃, 90 ± 10% relative humidity after is 0 to 2%, and its water vapour permeability is 50 to 250g/m
224 hours.
Be the technology that the exposed surface of celluosic resin is provided the water vapour permeability of surface treatment to reduce diaphragm below: Jap.P. 2004-53797A (patent documentation 5) discloses; with the anti-reflecting layer of hard organic resin layer and multiple mineral compound with different refractivity with this sequential cascade on the plastic resin substrate; to form anti-reflective film; thereby the value that makes the anti-reflective film that the obtains vapor permeation speed under 60 ℃, 95% relative humidity be the plastic resin substrate vapor permeation speed half or lower, and this is worth and is 500g/m
2/ sky or lower; Disclose a kind of optically functional film with Jap.P. 2004-341541A (patent documentation 6), wherein used CVD (chemical vapor deposition) method on transparent substrate film, to form silicon oxide film with the moist grade of excellent anti.
In this class diaphragm that water vapour permeability is low any one is arranged at least one side of polyvinyl alcohol (PVA) polarizing coating, perhaps outermost particularly, and this demonstrates permanance excellent under hygrothermal environment; But if it is exposed under the hot environment of low humidity, this causes the deterioration of its outward appearance, as producing the surface imperfection of tool wrinkle, causes such as the problem to the adverse effect of liquid crystal display displays performance.
For example; Jap.P. 2000-321428A (patent documentation 7) notices; when being mounted with anti-reflecting layer on the surface of polarizer at its diaphragm, it is not enough that its thermotolerance becomes usually, and notice; this causes owing to settling anti-reflecting layer that water vapour permeability is reduced; therefore, in the document, provide a kind of polarizer; even this polarizer has anti-reflecting layer, its water vapour permeability is 10g/m
224 hours or higher.
On the contrary, have such situation, that is, on the surface of the transparent carrier of celluosic resin, the coating of liquid crystalline compound to be to form optical compensating layer, then this optical compensating layer is placed on the side of polarizing coating as diaphragm.In the case, on transparent carrier, form alignment films usually in advance, so that liquid-crystal compounds is positioned on the predetermined direction.For example, Jap.P. H9-179125A (patent documentation 8) discloses, and alignment films is provided on transparent carrier, thereby obtains having the carrier of alignment films, on alignment films, provide the optical anisotropic layer that constitutes by dish-shaped compound (optical compensating layer) then, to form optical compensating gage.
The material that is used for alignment films must be considered their positioning performance, coating performance, optical property and permanance and selection aptly; But, select the material of water tolerance deficiency usually, reason need to be positioning performance and coating performance.For example, above mentioned patent documentation 8 is recommended the material of polyvinyl alcohol (PVA) as alignment films.When alignment films or coating are the materials of water tolerance deficiency when constituting, the polarizer that obtains is in the permanance deficiency that contains under the environment of big water gaging, thereby LCD is broken down under high temperature and high humidity.Particularly, when any one deck in the layer that constitutes polarizer makes the adhesive strength deteriorates of their expectations owing to water, remainder the layer when expanding along with the absorption-desorption effect of heat or moisture or shrinking, produce external carbuncle, therefore, described stress makes usually and produces layering between the layer or they are destroyed itself.
Summary of the invention
One of purpose of the present invention is to develop a kind of polarizer that is used for LCD; described polarizer has low water vapour permeability; even can protect polarizing coating under hygrothermal environment, also not to be subjected to influence of moisture; and the deterioration that does not cause its outward appearance, and under the environment of high temperature and low humidity, keep favourable display quality.
Another object of the present invention is to develop a kind of polarizer, even this polarizer contains the low layer of water tolerance, also lessly influenced by water.
A first aspect of the present invention provides a kind of polarizer; it comprises: polarizing coating, first transparent protective film and second transparent protective film; described polarizing coating is between first transparent protective film and second transparent protective film, and wherein the water vapour permeability of first transparent protective film under 40 ℃, 90% relative humidity is 50g/m
224 hours or lower, and the liquid water content of polarizer is 2.0 weight % or lower.
First transparent protective film preferably has and polarizing coating opposite surfaces surface treated.When first transparent protective film originally had the high water vapor perviousness, first transparent protective film can carry out surface treatment, to have the water vapour permeability of aforesaid value.In the case, first transparent protective film can be celluosic resin such as triacetyl cellulose.This transparent protective film contains the triphenyl phosphate of 3 to 10 weight % as plastifier usually, to improve moldability.In addition, when first transparent protective film carries out surface treatment, can provide the anti-reflecting layer of metallic compound from the teeth outwards, to reduce water vapour permeability by sputter.
Second transparent protective film that clips polarizing coating with first transparent protective film together can have the optical compensating layer opposite with polarizing coating, with the compensation visual angle.
A second aspect of the present invention also provides a kind of polarizer; it comprises: polarizing coating, first hyaline membrane and second transparent protective film; described polarizing coating is between first transparent protective film and second transparent protective film, and wherein the water vapour permeability of first transparent protective film under 40 ℃, 90% relative humidity is 50g/m
224 hours or lower, and second transparent protective film has transparent carrier layer, water wettability alignment films and the liquid-crystal compounds coating that comprises celluosic resin successively, and fit on the described polarizing coating in its transparent carrier side.
In this polarizer, first transparent protective film also preferably has and polarizing coating opposite surfaces surface treated.
First transparent protective film preferably has and polarizing coating opposite surfaces surface treated.When first transparent protective film originally had the high water vapor perviousness, first transparent protective film can carry out surface treatment, to have the water vapour permeability of aforesaid value.In the case, first transparent protective film can be celluosic resin such as triacetyl cellulose.This transparent protective film contains the triphenyl phosphate of 3 to 10 weight % as plastifier usually, to improve moldability.In addition, when first transparent protective film carries out surface treatment, can provide the anti-reflecting layer of metallic compound from the teeth outwards, to reduce water vapour permeability by sputter.
In addition, the water wettability alignment films of second transparent protective film can be made of polyvinyl alcohol resin.The liquid-crystal compounds coating that constitutes second transparent protective film can be the optical compensating layer that comprises dish-shaped liquid crystal.Optical compensating layer can be the negative birefringence layer, it comprises the liquid-crystal compounds with disc structure unit, the dish face of wherein said disc structure unit can tilt with respect to the plane of transparent carrier, and the angle that is formed by the plane of the dish face of described disc structure unit and transparent carrier can be along the thickness direction of described optical compensating layer and change.Preferably the angle that is formed by the plane of the dish face of described disc structure unit and transparent carrier increases and increases along the thickness direction of the optical compensation distance along with optical compensation leafing transparent carrier.
In addition, can provide pressure sensitive adhesive layer on the outside of the liquid-crystal compounds coating that constitutes second transparent protective film, purpose is to conform to liquid crystal cell.
A third aspect of the present invention also provides a kind of LCD, and it comprises liquid crystal cell, and comprises any in the above-mentioned polarizer, and wherein polarizer fits in liquid crystal cell with its second transparent protective film side by pressure sensitive adhesive layer.
Polarizer of the present invention has the performance of excellent sealing moisture, this can make polarizer keep its optical quality under hygrothermal environment, and by the liquid water content in the control polarizer, even under dry and hot environment, also avoid the deterioration of its outward appearance, as producing the defective of tool wrinkle.Therefore, this polarizer can be used for LCD aptly, thereby improves the image displaying quality and the reliable permanance of display effectively.
In addition, according to the polarizer of second aspect present invention,, can be suppressed at the hydrophilic effect on the alignment films sharp although its possess hydrophilic property alignment films in second transparent protective film relies on and reduces by the first transparent protective film water vapour permeability.
Description of drawings
Fig. 1 is a schematic cross-section of describing an example of a kind of layer of structure of polarizer of the present invention.
Fig. 2 is a schematic cross-section of describing an example of the another kind of layer of polarizer of the present invention structure.
Fig. 3 is a schematic cross-section of describing to prepare the method for the polarizer among the embodiment 1.
Fig. 4 is a schematic cross-section of describing to prepare the method for the polarizer in the comparative example 1.
Fig. 5 is a synoptic diagram of describing to measure in embodiment 2 and the comparative example 2 method of testing of water permeability.
Fig. 6 is a curve map of describing the vapor permeation state among the embodiment 2.
Fig. 7 is a curve map of describing the vapor permeation state in the comparative example 2.
Fig. 8 is a reference picture of describing comparative example 3 observed tunnellings.
1 polarizing coating
2 first transparent protective films
3 second transparent protective films
The 3a transparent carrier
4 surface-treated layers
5 hard coats
The anti-reflecting layer that 6 sputters form
7 optical compensating layers
8 alignment films
9 liquid-crystal compounds coatings
10 pressure sensitive adhesive layers
20 polarizers
21 glass containers
22 temperature humidity instrument
Observed tunnelling on the 25 polarizer surfaces
Embodiment
An example of the layer structure of polarizer of the present invention is shown in the schematic cross-section of Fig. 1.Fig. 1 (A) is depicted as basic layer structure, and wherein polarizing coating 1 is inserted between transparent protective film 2 and 3 and constitutes polarizer.Among the present invention, as clipping one of two transparent protective films of polarizing coating 1, the water vapour permeability of first transparent protective film 2 under 40 ℃, 90% relative humidity is 50g/m
224 hours or lower, and under the situation of the polarizer that is limited by first aspect, the liquid water content of whole polarizer is 2.0 weight % or lower.Fig. 1 (B) is depicted as such example, and promptly the basic layer structure shown in Fig. 1 (A) provides preferred extra play.As shown in top figure, can be in the outside of first transparent protective film 2, in other words, the side opposite with polarizing coating 1 provides surface-treated layer 4.Second transparent protective film 3 can provide optical compensating layer 7, provides optical compensating layer 7 especially on its outside.Optical compensating layer 7 can provide by alignment films.When the polarizer applications that will have the layer structure shown in Fig. 1 when the display, second transparent protective film 3 or optical compensating layer 7 are placed in the liquid crystal cell side, and first transparent protective film 2 or surface-treated layer 4 be placed in watch side.Therefore, in the outside of second transparent protective film 3 or optical compensating layer 7, that is, the side opposite with polarizing coating 1 can provide pressure sensitive adhesive layer 10, is used to the liquid crystal cell of fitting.Each layer shown in Fig. 1 is explained as follows.
Polarizing coating 1 is transmission at the linearly polarized photon of the plane of specific direction internal vibration and is absorbed in the optical device of another linearly polarized photon of the plane internal vibration vertical with last plane.As instantiation, what comprise is the polyvinyl alcohol resin film of absorption and orientation dichroic dye.Polarizing coating comprises absorption and the orientation iodine polarizing coating as the I of dichroic dye, or absorption and orientation be as the dye polarizing film of the dichromatism organic dyestuff of dichroic dye, and can use any in them.
Transparent protective film 2 and 3 can use the conventional any resin molding that uses.Among the present invention, make they one of the water vapour permeability of transparent protective film 2 under 40 ℃, 90% relative humidity be 50g/m
224 hours or lower.Can measure the value of water vapour permeability according to standard JIS Z 0208.According to this standard, should under arbitrary temperature of 25 ℃ or 40 ℃, measure water vapour permeability; Therefore, adopt 40 ℃ temperature in this manual.And, measure and also be based on 28.3cm
3The area of (diameter is 6cm) and the thickness of film itself carry out with the film of sampling, and the water vapour permeability that the obtains value representation of measuring under these conditions.
As for the low transparent protective film of water vapour permeability; can use the film of the originally low thermoplastic resin of its water vapour permeability; for example, such as the resin of polyolefin, polymethylmethacrylate, polycarbonate, polyethylene terephthalate, ring-type-ethylenic resin (norbornene resin).As alternative, can use such resin molding, its water vapour permeability was originally high, but can rely on surface treatment etc. and be included in the framework of the present definition.The original high resin molding of water vapour permeability can comprise the film of celluosic resin, described celluosic resin such as triacetyl cellulose and diacetyl cellulose.The initial condition vapor permeability of tri acetyl cellulose membrane itself depends on its kind, is about 300 to about 550g/m under the film thickness of about 80 μ m
224 hours.
Transparent protective film 2 and 3, particularly cellulose-based resin film such as tri acetyl cellulose membrane, blending has the triphenyl phosphate of 3 to 10 weight % as plastifier usually, to improve moldability.Contained triphenyl phosphate wash-out from sample is being come out and precipitate and separate again, then concentrate and drying after, measure the content of triphenyl phosphate quantitatively by the absolute calibration curve method of gas chromatography.When in the transparent protective film that clips polarizing coating at least one contained as the triphenyl phosphate of plastifier and reduce the water vapour permeability of diaphragm, polarizer may cause the deterioration of its outward appearance under hot environment, as the defective of tool wrinkle.Therefore, when using such diaphragm, mode of the present invention, that is, the liquid water content that reduces whole polarizer is effective to be suppressed at the appearance degradation under the hot environment.
Transparent protective film can comprise the plastifier that is different from triphenyl phosphate, as other phosphate plasticizer and phthalate plasticizers, and comprises adjuvant, as benzophenone or benzotriazole UV absorbers.
The surface treatment method that offers transparency protected film strength and low water vapour permeability comprises: be used to provide the hard coating of smoothness or unevenness to handle.Hard coat is not particularly limited, by resin material itself as organic silicones, acrylic resin and carbamate-acrylate resin, or the potpourri example of the Packed above-mentioned resin of blending.Can be coated with known method such as spin coating and miniature gravure formula, solidify then, form these hard coats.The thickness of hard coat is about 1 to about 30 μ m, is preferably greater than to equal 3 μ m and smaller or equal to 20 μ m.Its refractive index is generally 1.65 or lower, and preferred in 1.45 to 1.65 scope.
For anti-reflection function being provided and accurately reducing water vapour permeability, the hard coat surface can provide the layer of following material with known method such as the coating of miniature gravure formula, vapour deposition or sputter: organic material, metal or metallic compound.In order to reduce water vapour permeability, particularly preferably be the method that forms metallic compound film on the hard coat surface by sputtering at.
Be used to form or the organic material of coated film comprises the polymkeric substance that contains one or more fluorine atoms.As for metal, preferably use aluminium, silver etc.Metallic compound is generally inorganic states, and can use inorganic oxide, inorganic sulphide and inorganic fluoride.The example of inorganic oxide can comprise monox, zinc paste, titanium dioxide, niobium oxide, cerium oxide, indium oxide-Xi, tungsten oxide, molybdena, antimony oxide, aluminium oxide, zirconia etc.The example of inorganic sulphide can comprise zinc sulphide, antimony trisulfide etc.The example of inorganic fluoride can comprise aluminum fluoride, barium fluoride, calcium fluoride, cerium fluoride, aluminum fluoride, lanthanum fluoride, lead fluoride, lithium fluoride, magnesium fluoride, fluoridize niobium, samaric fluoride, sodium fluoride, strontium fluoride, yttrium fluoride etc.When anti-reflecting layer is provided, needs one deck at least, but as required, can be multilayer.
Example with suitable surface-treated diaphragm comprises having double-deck film, and wherein lower floor is transparent acrylic compounds hard coat so that intensity and anti-reflection function to be provided, and the upper strata is the anti-reflecting layer of being made up of metallic compound that forms with sputter.
Second transparent protective film 3 can have high or low water vapour permeability, and usually, preferably has high relatively water vapour permeability; Particularly, preferably have under 40 ℃, 90% relative humidity greater than 50g/m
2The diaphragm of 24 hours value.The composition that is applied to this transparent protective film 3 can be identical or different with the composition that is applied to first transparent protective film 2.
Second transparent protective film 3 can provide optical compensating layer 7, to compensate by polarizer being installed in differing of causing on the LCD.
Optical compensating layer comprises for example following: the stretching resin film have the film that directivity differs in the face, described resin such as polycarbonate resin, polysulfone resin, polyarylate resin, triacetyl cellulose, diacetyl cellulose, a cyclic polyolefin resin; Have the film that thickness direction differs, it is to represent by the coating that forms the inorganic layer compound; With the optical compensation films that forms by the liquid-crystal compounds coating.Commercially available optical compensation films with liquid-crystal compounds coating comprises the Co. by Fuji Photo Film, " Wide View " film (so-called " WV film ") that Ltd. makes and " the Nippon Oil NH Film " that made by Nippon Oil Corporation.As alternative, optical compensating layer 7 can play transparent protective film by optical compensating layer 7 is directly fitted on the polarizing coating 1.Because the application type optical compensating layer directly or by alignment films is formed on the transparent carrier that is made of celluosic resin usually as required, this layer can fit in polarizing coating 1 with the transparent carrier side.
The angle that absorption axes by the slow axis of optical compensating layer 7 and polarizing coating 1 is formed is not particularly limited, and regulates aptly according to the standard of the LCD of using.Preferably, compare with the method for conventional laminated polarizing device and phase shift films, applying optical compensating layer 7 can more effectively suppress the formation of color dropout (dropout).
Transparency protected 2 and 3 can be the film that satisfies the water vapour permeability standard that limits among the present invention, and preferably also has the high grade of transparency and stable on heating film, and transparency is 80% or higher by luminous transmittance measuring, is preferably 85% or higher; And thermotolerance is counted 100 ℃ or higher by glass transition temperature, is preferably 120 ℃ or higher.Therefore, preferred diaphragm comprises for example plastic foil, described plastics such as triacetyl cellulose (TAC) and polyethylene terephthalate.
In the polarizer that limits by first aspect present invention, the liquid water content of whole polarizer is adjusted to 2.0 weight % or lower, this polarizer constitutes by polarizing coating 1 being inserted between first transparent protective film 2 and second transparent protective film 3.Although the liquid water content in the polarizer demonstrates high value usually, 2.5 weight % according to appointment, in the present invention, by eliminating the water that in polarizer, contains, even this polarizer at high temperature exposes the deterioration that also can not cause its outward appearance.
For the liquid water content with polarizer be suppressed to aforesaid low-level, employing be with polarizing coating dry fully method in its manufacturing step, after becoming polarizer, eliminate the method for water etc.The method of eliminating water after becoming polarizer can adopt conventional mode, for example vacuum drying and high temperature drying.
The liquid water content of the polarizer that this paper limits is based on the weight of the polarizer of measuring before or after the dry polarizer by exposing 0.5 hour under 100 ℃ atmosphere, the value of calculating according to following equation (I):
Pressure sensitive adhesive layer 10 can be made of adhesive resin such as acrylic resin, and described adhesive resin is known as contact adhesive, is also referred to as bonding agent.
The polarizer that description below is limited by above-mentioned second aspect.The basic structure of the polarizer that is limited by second aspect is shown in Fig. 2 (A), wherein constitutes polarizer by insert polarizing coating 1 between first transparent protective film 2 and second transparent protective film 3.The explanation of first transparent protective film 2 with on to regard to the described explanation of the polarizer that is limited by first aspect identical, and shown in Fig. 2 (B), preferably in its outside, promptly opposite side seating surface processing layer 4 with polarizing coating 1.Because except surface-treated layer 4 being placed in the outside of first transparent protective film 2, Fig. 2 (B) is identical with Fig. 2 (A), thus Fig. 2 (B) represent with identical numeric character corresponding to those parts of Fig. 2 (A), to avoid repetition of explanation.In the outside of second transparent protective film, promptly the outside of liquid-crystal compounds coating 9 can provide pressure sensitive adhesive layer 10, this pressure sensitive adhesive layer 10 with top with reference to figure 1 explained identical, thereby can fit liquid crystal cell.
First transparent protective film 2 can be the low film of original water vapour permeability, and this film is typically represented by the film of ring-olefinic or ethylenic resin; Or such film, itself originally had high water vapour permeability, typically as triacetyl cellulose, reduced its water vapour permeability as whole film by the surface-treated layer 4 that is provided at example shown in Fig. 2 (B).The common blending of film that is made of celluosic resin such as triacetyl cellulose has the triphenyl phosphate of 3 to 10 weight % as plastifier.
Second transparent protective film 3 is to form with this sequential cascade by the transparent carrier 3a that will comprise celluosic resin, water wettability alignment films 8 and liquid-crystal compounds coating 9, and fits on the polarizing coating 1 in the 3a of transparent carrier side.
Alignment films 8 is made of hydrophilic resin such as polyvinyl alcohol resin.Polyvinyl alcohol resin can be a modified polyvinylalcohol, for example, is introduced into alkyl and modified polyethylene alcohol.Alignment films 8 normally by form the coating that is made of this hydrophilic resin on transparent carrier 3a, is carried out friction treatment to the surface of this layer then and is prepared.
Liquid-crystal compounds coating 9 can be an optical compensating layer, and wherein coating contains the coating solution and the orientation of dish-shaped liquid crystal.Optical compensating layer is the negative birefringence layer preferably, it comprises the liquid-crystal compounds with disc structure unit, the dish face of wherein said disc structure unit is with respect to the plane inclination of transparent carrier, and the angle that is formed by the plane of the dish face of described disc structure unit and transparent carrier is along the thickness direction of described optical compensating layer and change.In this dihedral becomes, so-called mixed positioning also can be effective, wherein on aspect the thickness of optical compensation, the angle that is formed by the plane of the dish face of described disc structure unit and transparent carrier increases along with the increase of the distance of optical compensation leafing transparent carrier.In this formation, the angle that is formed by the plane of the dish face of described disc structure unit and transparent carrier can begin sequentially to increase to the scopes of about 50 degree about 5 from the transparent carrier side.The instantiation that forms the optical compensation films of alignment films and dish-shaped liquid crystal coatings on transparent carrier comprises: by Fuji Photo Film Co., and " Wide View " film (so-called " WVfilm ") that Ltd. makes etc.
Polarizer is to form by a side that optical compensation films is fitted in polarizing coating and the opposite side that will be fitted in polarizing coating by the transparent protective film that common triacetyl cellulose constitutes, wherein said optical compensation films is by forming the water wettability alignment films on the transparent carrier that is made of celluosic resin such as triacetyl cellulose, forming the liquid-crystal compounds coating again on the film that forms in front and constitute; In this polarizer, can observe with such phenomenon, promptly when being exposed to high-temperature and damp condition following time, moisture exerts an influence to the water wettability alignment films, and partially oriented film is bubbled from the liquid-crystal compounds coating at the edge of polarizer, thereby the bubble of tunnel-shaped (hole) begins at the edge, and spreads into polarizer inside.Below, this phenomenon can be called tunnelling.
The present invention has realized preventing that by using polarizer polarizer from producing tunnelling recited above; wherein polarizer is to form by following method: preparation is layered in film on the transparent carrier that is made of celluosic resin in this order with water wettability alignment films and liquid-crystal compounds coating; this film is fitted on the side of polarizing coating as second transparent protective film; and another first transparent protective film fitted on the opposite side of polarizing coating, wherein the water vapour permeability of first transparent protective film under 40 ℃, 90% relative humidity is equal to or less than predetermined value.Therefore, no matter the amount of the liquid water content of above-mentioned whole polarizer, this tunnelling also stops.Therefore, among the present invention, the polarizer that is limited by second aspect does not need to regulate the liquid water content of whole polarizer.
But, as what explain at the polarizer that limits by first aspect, because the deterioration of the inhibition outward appearance that lower liquid water content can normally cause under hot environment, as the defective of tool wrinkle, even therefore for the polarizer that is limited by second aspect, also the liquid water content of preferred whole polarizer is lower.
Embodiment
The present invention explains reference example in more detail, but should be understood that and the invention is not restricted to this.Because any value of the water vapour permeability among the embodiment all is to measure, omit the description of temperature and humidity therein under 40 ℃, 90% relative humidity.
As shown in Fig. 3 (A), be inserted between two transparent protective films 2 and 3 that constitute by triacetyl cellulose by the polarizing coating 1 that will constitute and prepare polarizer by the alignment films of iodine stain-polyvinyl alcohol (PVA).First transparent protective film that is placed on polarizing coating 1 one sides is that the CO. by TOPPAN PRINTING is provided on a side of tri acetyl cellulose membrane 2, the film of the hard coat 5 that LTD. makes; Second transparent protective film that is placed on polarizing coating 1 opposite side is the film that the optical compensating layer 7 that is made of dish-shaped liquid crystal aligning coating is provided by polyvinyl alcohol (PVA) alignment films (not shown) on a side of tri acetyl cellulose membrane 3, optical compensating layer 7 is by Fuji Photo Film Co., Ltd. make, its commodity are called " WV-SA "; And each diaphragm is fitted in polarizing coating 1 by bonding agent respectively with its tri acetyl cellulose membrane 2 or 3 sides.The thickness of polarizing coating 1 is about 25 μ m, and the thickness with tri acetyl cellulose membrane 2 of hard coat 5 is 85 μ m, and the thickness with tri acetyl cellulose membrane 3 of optical compensating layer 7 is about 83 μ m.
After polarizer is carried out vacuum drying treatment, as shown in Fig. 3 (B), will be formed on the surface of hard coat 5 by the anti-reflecting layer 6 usefulness sputtering methods that metal oxide film constitutes, so that anti-reflection function and low water vapour permeability to be provided.Herein in the reason, although the original value of the water vapour permeability of tri acetyl cellulose membrane 2 itself is 420g/m
224 hours, its water vapour permeability value became 2.40g/m after hard coat 5 and anti-reflecting layer 6 are provided on tri acetyl cellulose membrane 2
224 hours.Tri acetyl cellulose membrane 2 contained the triphenyl phosphate of 6.7 weight % before hard coat 5 is provided, and the tri acetyl cellulose membrane 3 with optical compensating layer 7 (" WV-SA ") also contains the triphenyl phosphate of 6.5 weight %.The liquid water content of the polarizer that obtains is 1.74 weight %.Therefore, what obtain is such polarizer, and wherein one of diaphragm has 2.40g/m
224 hours low water vapour permeability, two transparent protective films contain respectively and are lower than the triphenyl phosphate of 7 weight % as plastifier, and liquid water content as a whole is about 1.7 weight %.
Comparative example 1
As shown in Fig. 4 (A); prepare a transparent protective film by following method: will be by TOPPANPRINTING CO.; LTD. the hard coat 5 of Zhi Zaoing is provided on the side of tri acetyl cellulose membrane 2; on the surface of hard coat 5, form the anti-reflecting layer 6 that constitutes by metal oxide film with sputtering method then, so that anti-reflection function and low water vapour permeability to be provided.Another transparent protective film adopt with embodiment 1 in the identical film of second transparent protective film of use, it is by providing the optical compensating layer 7 (trade name " WV-SA ") that is made of dish-shaped liquid crystal aligning coating to prepare by alignment films on a side of tri acetyl cellulose membrane 3.Then; these two transparent protective films are fitted in the either side of the polarizing coating 1 that the alignment films by iodine stain-polyvinyl alcohol (PVA) constitutes respectively with its tri acetyl cellulose membrane 2 or 3 sides by bonding agent; as shown in Fig. 4 (B); prepare polarizer thus; it has the layer structure identical with embodiment 1, and polarizing coating 1 is inserted between two diaphragms.Identical among every layer thickness and the embodiment 1.
The water vapour permeability of layer after providing hard coat 5 and anti-reflecting layer 6 of tri acetyl cellulose membrane 2 is 2.40g/m
224 hours.Tri acetyl cellulose membrane 2 contained the triphenyl phosphate of 6.7 weight % before providing hard coat 5, and the tri acetyl cellulose membrane 3 with optical compensating layer 7 (" WV-SA ") contains the triphenyl phosphate of 6.5 weight %, and the liquid water content of the polarizer that obtains is 2.78 weight %.
The embodiment of evaluation test
(a) be used to the preparation of the sample assessed
The corresponding polarizer that obtains from embodiment 1 and comparative example 1 cuts out the sheet that is of a size of 30mm * 30mm or 100mm * 100mm, is then fitted on the glass plate by contact adhesive respectively, to form the assessment sample.
(b) assessment of polarizer permanance under hygrothermal environment
Will be in the above (a) make the sample be of a size of 30mm * 30mm and under 60 ℃, 90% relative humidity, place on 750 hours the basis and carry out the humidity resistance test, then measure the optical property of polarizer before and after test.Measure by following method: use the spectrophotometer of making by SHIMADZUCorporation that is used for ultraviolet and visible region " UV-2450 ", by adopting its optional annex " with the film fixator of polarizing coating ", in the transmission and absorption direction of polarizer, the transmitted spectrum of measurement in the wavelength coverage of 380nm to 700nm, and measure the chromaticity coordinates a of transmitted light according to JIS Z8729
*And b
*, and use to be equipped with and determine degree of polarization Py for above-mentioned spectrophotometric software " UV-Probe ".
Based on the degree of polarization Py of the degree of polarization Py after the humidity resistance test and initial (before the humidity resistance test), calculate the changes delta Py of degree of polarization according to following formula (II); And based on a after the humidity resistance test
*And b
*A with initial (before the humidity resistance test)
*And b
*, calculate tonal variation Δ a according to following formula (III)
*b
*:
Py-initial p y| (II) after the Δ Py=| test
Δ a
*b
*=[(a after the test
*-initial a
*)
2+ (the b after the test
*-initial b
*)
2]
1/2(III)
According to resulting result, the degree of polarization changes delta Py of the polarizer of embodiment 1 and comparative example 1 is respectively 0.05 or lower by poor (the representing with number percent) of degree of polarization, and tonal variation Δ a
*b
*Be 2 or lower.These results prove that any polarizer demonstrates favourable permanance under hygrothermal environment.
(c) durability evaluating of polarizer under dry and hot environment
Will be in the above (a) make the sample be of a size of 100mm * 100mm and under 85 ℃, drying-hot environment, place on 750 hours the basis and carry out heat-resistance test, the then sample appearance after the viewing test.According to the observation, the sample appearance that obtains among the embodiment 1 does not have deterioration, obtains favourable result; On the other hand, the defective of tool wrinkle appears in sample in its surface that obtain in the comparative example 1, thereby can not carry out the measurement about optical property such as degree of polarization.
Two kinds of films below the preparation are as first transparent protective film.
Embodiment 2: film is to prepare by following method: will be by TOPPAN PRINTING CO., LTD. the hard coat of Zhi Zaoing is provided on the side of tri acetyl cellulose membrane, on the surface of hard coat, form the anti-reflecting layer that constitutes by metal oxide film with sputtering method then, to have anti-reflection function and low water vapour permeability.The value of low water vapour permeability is 2.4g/m
224 hours.
Comparative example 2: film is to prepare by following method: will be by TOPPAN PRINTING CO., LTD. the hard coat of Zhi Zaoing is provided on the side of tri acetyl cellulose membrane (that is the film before, the film of preparation provides anti-reflecting layer in giving the above embodiments 2).The water vapour permeability value of this film is 296g/m
224 hours.Usually with the transparent protective film of this film as the demonstration side that will be placed in polarizer.
The film that is used for second transparent protective film is to prepare by following method: form the alignment films that is made of polyvinyl alcohol based resins on a side of tri acetyl cellulose membrane, on alignment films, form dish-shaped liquid crystal coatings (optical compensating layer) (trade name " WV-SA " then, by Fuji Photo Film Co., Ltd. makes; This film is identical with the film of use in embodiment 1 and the comparative example 1).
According to program depicted in figure 4, by using the first such transparent protective film and second transparent protective film, the preparation polarizer.That is, as shown in Fig. 4 (A), on a side of the polarizing coating 1 that the alignment films by iodine stain-polyvinyl alcohol (PVA) constitutes, by fit tri acetyl cellulose membrane 2 sides of above-mentioned first transparent protective film of bonding agent; And on the opposite side of polarizing coating 1, also by fit tri acetyl cellulose membrane 3 sides of above-mentioned second transparent protective film of bonding agent.Thus, as shown in Fig. 4 (B), produce by polarizing coating 1 being inserted in the polarizer that constitutes between two diaphragms.
The layer of acrylic psa (being made trade name " P236JP " by Lintec Corporation) is placed on optical compensating layer 7 sides of second transparent protective film of the polarizer that obtains thus, has the polarizer of pressure sensitive adhesive layer with preparation.With this polarizer with pressure sensitive adhesive layer by under 23 ℃, the atmosphere of 50% relative humidity, placing 3 days or longer time and moistening.
For this moistening polarizer, observe water permeability with pressure sensitive adhesive layer.Fig. 5 shows the sketch map of this water permeability observational technique.That is, temperature humidity instrument 22 is placed in the glass container 21, only edge of opening is thick thereon for the wall of described glass container 21, and glass container 21 seals by this upper shed edge of fitting with the pressure sensitive adhesive layer side of above-mentioned moistening polarizer 20.Glass container under this state is positioned over to be adjusted in 60 ℃, relative humidity be in 90% the baking oven.As time goes by and the humidity in the sight glass container 21 changes, and embodiment 2 the results are shown in Fig. 6, comparative example 2 the results are shown in Fig. 7.
According to these figure, prove as follows: have water vapour permeability and be 2.4g/m using
2Under the situation of the embodiment 2 (Fig. 6) of the polarizer of 24 hours first transparent protective film, too many even the in the past longer time of the humidity in the glass container does not increase yet after through 1 to 2 hour, thus suppressed the infiltration of water by the polarizer surface; On the other hand, have water vapour permeability and be 296g/m using
2Under the situation of the comparative example 2 (Fig. 7) of the polarizer of 24 hours first transparent protective film; commitment after just beginning to test; humidity in the glass container just reaches and the much the same level of the atmosphere of outside, and a large amount of thus water is by the surface seepage of polarizer.
The polarizer with pressure sensitive adhesive layer of preparation among the embodiment 2 is cut into the section of across corner about 8 inches (200mm), cutting mode be the absorption axes of section with respect to its long limit to be rotated counterclockwise 45 angles of spending, the section of being cut is fitted on the thick glass plate of 1.1mm with its pressure sensitive adhesive layer side, to form sample; Then, this sample with 50 ℃, 5 atmospheric condition compactings 20 minutes, was placed 24 hours then.Then, sample is placed on is adjusted in the baking oven that 65 ℃, relative humidity are 90% high-temperature and humidity, then, from baking oven, take out after 65 hours in the past, carry out outward appearance and observe, thereby on sample, do not find the generation of defective as peeling off or bubbling.
Comparative example 3
The polarizer with pressure sensitive adhesive layer that will in comparative example 2, prepare with embodiment 3 in identical mode test.Fig. 8 shows the closeup photograph of the polarizer of test back taking-up in its edge.Between the layer of second transparent protective film and polyvinyl alcohol (PVA) alignment films (" WV-SA "), produce and bubble; Particularly, observe a large amount of tunnelling 25 at the edge of polarizer.
Claims (19)
1. polarizer; it comprises: polarizing coating, first transparent protective film and second transparent protective film; described polarizing coating is between first transparent protective film and second transparent protective film, and wherein the water vapour permeability of first transparent protective film under 40 ℃, 90% relative humidity is 50g/m
224 hours or lower, and the liquid water content of described polarizer is 2.0 weight % or lower.
2. polarizer according to claim 1, wherein first transparent protective film has surface-treated surface, and this surface-treated surface is opposite with polarizing coating.
3. polarizer according to claim 2, wherein the water vapour permeability of the surface-treated surface of first transparent protective film under 40 ℃, 90% relative humidity is 50g/m
224 hours or lower.
4. polarizer according to claim 3, wherein first transparent protective film comprises celluosic resin.
5. polarizer according to claim 4, wherein first transparent protective film contains the triphenyl phosphate of 3 to 10 weight %.
6. polarizer according to claim 1, wherein first transparent protective film has anti-reflecting layer, and this anti-reflecting layer is opposite with polarizing coating.
7. according to any one described polarizer in the claim 1 to 6, wherein second transparent protective film has optical compensating layer, and this optical compensating layer is opposite with polarizing coating.
8. polarizer; it comprises: polarizing coating, first hyaline membrane and second transparent protective film; described polarizing coating is between first hyaline membrane and second transparent protective film, and wherein the water vapour permeability of first transparent protective film under 40 ℃, 90% relative humidity is 50g/m
224 hours or lower, and second transparent protective film has transparent carrier layer, water wettability alignment films and the liquid-crystal compounds coating that comprises celluosic resin successively, and fit on the described polarizing coating in its transparent carrier side.
9. polarizer according to claim 8, wherein first transparent protective film has surface-treated surface, and this surface-treated surface is opposite with polarizing coating.
10. polarizer according to claim 9, wherein the water vapour permeability of the surface-treated surface of first transparent protective film under 40 ℃, 90% relative humidity is 50g/m
224 hours or lower.
11. polarizer according to claim 10, wherein first transparent protective film comprises celluosic resin.
12. polarizer according to claim 11, wherein first transparent protective film contains the triphenyl phosphate of 3 to 10 weight %.
13. polarizer according to claim 8, wherein first transparent protective film has anti-reflecting layer, and this anti-reflecting layer is opposite with polarizing coating.
14. any one described polarizer in 13 according to Claim 8, wherein the water wettability alignment films comprises polyvinyl alcohol resin.
15. any one described polarizer in 13 according to Claim 8, wherein said coating is the optical compensating layer that comprises dish-shaped liquid crystal.
16. polarizer according to claim 15, wherein said optical compensating layer is the negative birefringence layer, it comprises the liquid-crystal compounds with disc structure unit, the dish face of wherein said disc structure unit is with respect to the plane inclination of transparent carrier, and the angle that is formed by the plane of the dish face of described disc structure unit and transparent carrier is along the thickness direction of described optical compensating layer and change.
17. optical compensating gage, it comprises the described polarizer of claim 16, and wherein the angle that is formed by the plane of the dish face of described disc structure unit and transparent carrier increases and increases along the thickness direction of the optical compensation distance along with optical compensation leafing transparent carrier.
18. polarizer according to claim 8, wherein pressure sensitive adhesive layer is on the outside of the liquid-crystal compounds coating of second transparent protective film.
19. a LCD, it comprises liquid crystal cell and according to any one described polarizer in claim 1 or 8, wherein polarizer fits in liquid crystal cell with its second transparent protective film side by pressure sensitive adhesive layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005258960 | 2005-09-07 | ||
| JP2005258960 | 2005-09-07 | ||
| JP2006174920 | 2006-06-26 |
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| Publication Number | Publication Date |
|---|---|
| CN1928593A true CN1928593A (en) | 2007-03-14 |
Family
ID=37858646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610128139 Pending CN1928593A (en) | 2005-09-07 | 2006-09-05 | Highly durable polarization plate and liquid crystal display |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101846849A (en) * | 2009-03-23 | 2010-09-29 | 索尼公司 | Color conversion sheet, lighting device and display device |
| CN101276014B (en) * | 2007-03-29 | 2011-05-25 | 富士胶片株式会社 | Protective film for polarizing plate, polarizing plate, and liquid crystal display device |
| CN102200603A (en) * | 2010-03-24 | 2011-09-28 | 住友化学株式会社 | Polarizing plate |
| CN104698671A (en) * | 2013-12-09 | 2015-06-10 | 日东电工株式会社 | Liquid crystal panel and image display apparatus |
| CN105793749A (en) * | 2013-12-03 | 2016-07-20 | 日东电工株式会社 | Polarizing film, polarizing film with adhesive layer, and image display device |
| CN105980892A (en) * | 2014-02-18 | 2016-09-28 | 日东电工株式会社 | Laminate and image display device |
| CN112055830A (en) * | 2018-05-01 | 2020-12-08 | 弗莱克英纳宝有限公司 | Liquid crystal display device having a plurality of pixel electrodes |
| CN114077003A (en) * | 2020-08-10 | 2022-02-22 | 三星Sdi株式会社 | Polarizing plate and optical display device comprising same |
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2006
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101276014B (en) * | 2007-03-29 | 2011-05-25 | 富士胶片株式会社 | Protective film for polarizing plate, polarizing plate, and liquid crystal display device |
| CN101846849A (en) * | 2009-03-23 | 2010-09-29 | 索尼公司 | Color conversion sheet, lighting device and display device |
| CN102200603A (en) * | 2010-03-24 | 2011-09-28 | 住友化学株式会社 | Polarizing plate |
| CN105793749A (en) * | 2013-12-03 | 2016-07-20 | 日东电工株式会社 | Polarizing film, polarizing film with adhesive layer, and image display device |
| CN105793749B (en) * | 2013-12-03 | 2020-04-24 | 日东电工株式会社 | Polarizing film, polarizing film with adhesive layer, and image display device |
| CN104698671A (en) * | 2013-12-09 | 2015-06-10 | 日东电工株式会社 | Liquid crystal panel and image display apparatus |
| CN104698671B (en) * | 2013-12-09 | 2019-11-19 | 日东电工株式会社 | Liquid crystal display panel and image display device |
| CN105980892A (en) * | 2014-02-18 | 2016-09-28 | 日东电工株式会社 | Laminate and image display device |
| CN112055830A (en) * | 2018-05-01 | 2020-12-08 | 弗莱克英纳宝有限公司 | Liquid crystal display device having a plurality of pixel electrodes |
| CN114077003A (en) * | 2020-08-10 | 2022-02-22 | 三星Sdi株式会社 | Polarizing plate and optical display device comprising same |
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Application publication date: 20070314 |