CN112164324B - Organic light emitting display device with changing polarization state of emergent light - Google Patents
Organic light emitting display device with changing polarization state of emergent light Download PDFInfo
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- CN112164324B CN112164324B CN202010926819.6A CN202010926819A CN112164324B CN 112164324 B CN112164324 B CN 112164324B CN 202010926819 A CN202010926819 A CN 202010926819A CN 112164324 B CN112164324 B CN 112164324B
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/33—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being semiconductor devices, e.g. diodes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
Abstract
An organic light emitting display device with a changed polarization state of emergent light, the organic light emitting display device comprises a backlight source for providing a light source; the polarizing plate is arranged on one side of the backlight source, comprises a first polarizer protective film, a polarizer and a second polarizer protective film which are sequentially arranged along one side far away from the backlight source and is used for blocking reflected light of external incident light; wherein the second polarizer protective film has an in-plane retardation value of Re ═ λ/4+ n ═ λ0Wherein λ is (500-600) nm, λ0550nm, n is a natural number. The organic light-emitting display device provided by the invention can effectively change the polarization state of emergent light without additionally adding components, eliminates the phenomenon of intensity change when the polarized light element is observed at different angles, and increases the effective observation angle.
Description
Technical Field
The invention relates to the field of luminous display, in particular to an organic luminous display device capable of changing the polarization state of emergent light.
Background
For a novel Organic Light Emitting Display (OLED) device in the current display market, a combination of 1/4 wave plates and polarizing plates (circular wave plates) is used above an organic light emitting layer, i.e., on a surface close to an observation side, to eliminate the influence of light entering a display screen after natural light is reflected by an electrode plate of the light emitting layer in the environment. But this also presents a problem: the light emitted from the OLED display device passes through the polarizing plate and is linearly polarized in parallel with the polarization direction of the polarizing plate in the polarizing plate. However, with the increase of social informatization degree, the OLED device is widely applied to various large, small, indoor and outdoor instruments such as mobile phones, computers, televisions, digital cameras and other interactive windows, for example, car navigation systems, advertisement display panels, and the like. The opportunities for people to see display devices such as mobile phones, advertising panels, navigation panels, etc. through polarizing elements such as polarized sunglasses, automobile windshields, etc. are greatly increased. If the light transmission direction of the polarized glasses is perpendicular to the polarization direction of the light emitted from the OLED display device, the image on the display device cannot be seen in a dark state of the visual field.
In the prior art, an 1/4 wave plate is additionally arranged on the outer side of a polarizing plate of a display device, namely the polarizing plate close to the observation side, so that polarized light emitted by the display device can be effectively converted into circularly polarized light, and the phenomenon of darkening of the visual field cannot occur when the display device is observed through a polarizing element. However, this method obviously increases the number of steps for manufacturing the display device, increases the cost, and also greatly increases the thickness of the entire display device, which cannot meet the market demand for thinning the display device.
In addition, conventionally, a polyester film having a high in-plane retardation value is used on the outside of a polarizing plate on the observation side, and the orientation axis of the oriented polyester film is attached to the polarizer of the polarizing plate at 45 °. However, this method can only simply convert linearly polarized light emitted from the display device into elliptically polarized light to eliminate a dark state when viewed through the polarizing element. However, this method can only make the polarization state reach the elliptical polarization state, and cannot fundamentally solve the phenomenon of darkening the visual field. In addition, the polyester film can cause the proportion of the thermal shrinkage in the longitudinal direction and the thermal shrinkage in the transverse direction to be mismatched through simple asynchronous stretching, and when the polyester film is heated in the subsequent coating processing or the service process, the shrinkage proportion in the two directions and the generated internal stress are unbalanced, so that the larger fluctuation of the retardation value is caused, and the functional failure or the display effect is deteriorated. The light emitted from the OLED device is linearly polarized light, and when the OLED device is observed through the polarizing element, the observation field of view becomes dark or even extinction appears in a full dark state along with the change of the observation angle.
Disclosure of Invention
In view of the above, one of the main objectives of the present invention is to provide an organic light emitting display device with a function of changing the polarization state of the emergent light, so as to at least partially solve at least one of the above technical problems.
In order to achieve the above object, the present invention provides an organic light emitting display device with a changed polarization state of outgoing light, comprising:
a backlight source for providing a light source; and
the polarizing plate is arranged on one side of the backlight source, comprises a first polarizing film protective film, a polarizing film and a second polarizing film protective film which are sequentially arranged along one side far away from the backlight source and is used for blocking reflected light of external incident light;
wherein, theThe second polarizer protective film has an in-plane retardation value Re ═ λ/4+ n ═ λ0Wherein λ is (500-600) nm, λ0550nm, n is a natural number.
Based on the above technical solution, the organic light emitting display device with the function of changing the polarization state of the emergent light according to the present invention has at least one of the following advantages over the prior art:
1. the organic light-emitting display device provided by the invention can effectively change the polarization state of emergent light without additionally adding components, eliminates the phenomenon of intensity change when the polarized light element is observed at different angles, and increases the effective observation angle;
2. compared with the prior art, the polarizing plate of the display device near the observation side uses the protective film with 1/4 wave plate effect on the observation side; emergent light of the display device can be converted into circularly polarized light or approximately circularly polarized light after passing through the film, so that the problem of the dependence of the display brightness along with the observation angle can be fundamentally solved;
3. in the preparation process of the protective film, the thickness and the heat shrinkage performance of the film are accurately adjusted and controlled through the special heat treatment step, the fluctuation of the optical performance of the film in the post-processing and using processes caused by process reasons or external environments is solved, the uniformity and the stability of the optical performance are ensured, and the processing and using reliability of the display device is improved.
Drawings
Fig. 1 is a schematic structural diagram of an organic light emitting display device according to an embodiment of the present invention.
Description of the reference numerals:
100-organic display device; 20-a backlight source; 21-an organic light-emitting layer; 22-a cathode; 23-an anode; 30-a polarizing plate; 31-a polarizing plate; 32 — a first polarizer protective film; 33-second polarizer protective film.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the accompanying drawings in combination with the embodiments.
In order to solve the above problems, the present invention provides an organic light emitting display device, a polarizer protective film and a method of manufacturing the same. Specifically, the polarizer protective film on the viewing side of the polarizer in the organic light-emitting display device has the function of 1/4 wave plate. When the linearly polarized light emitted from the polarizer passes through the polarizer protective film with 1/4 wave plate function on the surface layer, the emergent light is converted from polarization state to approximate circular polarization state or even circular polarization state, thus effectively improving the phenomenon of visual field intensity change when the polarizer is observed at different angles. In the invention, the function of 1/4 wave plates is given to the polarizer protective film, so the thickness of the display device is not additionally increased, and in addition, in order to ensure that the precision of the retardation value of the protective film is not influenced by subsequent processing conditions and service working conditions, the invention better solves the problem of the fluctuation of the retardation value of the polarizer protective film in the processing and service processes by researching and controlling the stretching process and the heat shrinkage of the protective film base film.
The invention discloses an organic light emitting display device, comprising:
a backlight for providing a light source; and
the polarizing plate is arranged on one side of the backlight source, comprises a first polarizer protective film, a polarizer and a second polarizer protective film which are sequentially arranged along one side far away from the backlight source and is used for blocking reflected light of external incident light;
wherein the second polarizer protective film has an in-plane retardation value of Re ═ λ/4+ n ×. λ0Wherein λ is (500-600) nm, λ0550nm, n is a natural number.
In some embodiments of the present invention, an included angle between the slow axis direction of the second polarizer protective film and the absorption axis of the polarizer is 30 to 50 degrees.
In some embodiments of the present invention, the second polarizer protective film has a thermal shrinkage rate of less than 5% in both slow axis and fast axis directions after being left at 130 to 160 ℃ for 10 to 40 minutes.
In some embodiments of the present invention, the second polarizer protective film has a light transmittance of less than 10% at a wavelength of less than 385 nm.
In some embodiments of the present invention, a ratio of a thermal shrinkage rate of the second polarizer protective film in a fast axis direction to a thermal shrinkage rate in a slow axis direction is 0.8 to 1.2.
In some embodiments of the present invention, the second polarizer protective film has a thickness of 10 to 300 um;
in some embodiments of the present invention, the second polarizer protective film has a thickness uniformity D of less than 5%;
in some embodiments of the present invention, D ═ D (D)max-dmin)/d*100％，dmaxIs the maximum value of the thickness of the protective film of the second polarizing plate, dminIs the minimum value of the thickness of the second polarizer protective film, and d is the average value of the thickness of the second polarizer protective film.
In some embodiments of the present invention, the calculation formula of the in-plane retardation value of the second polarizer protective film is:
re ═ Δ n × d, where Δ n is a difference in refractive index between the slow axis direction and the fast axis direction in the plane of the second polarizer protective film, and d is a thickness of the second polarizer protective film.
In some embodiments of the present invention, a method for preparing the second polarizer protective film includes:
preparing a casting sheet from a polymer raw material;
longitudinally stretching the casting sheet to obtain a first oriented film;
transversely stretching the first oriented film to obtain a second oriented film;
and heat setting the second orientation film to obtain the first polarizer protective film.
In some embodiments of the invention, the longitudinal stretching temperature is Tg-Tg +30 ℃, and the longitudinal stretching magnification is 1-5 times, wherein Tg is the glass transition temperature of the raw material;
in some embodiments of the invention, the transverse stretching temperature is Tg +10 ℃ to Tg +50 ℃, and the transverse stretching magnification is 2-6 times, wherein Tg is the glass transition temperature of the raw material;
in some embodiments of the invention, the heat-setting temperature is 200 ℃ to 250 ℃.
In some embodiments of the invention, the feedstock comprises polyester;
in some embodiments of the invention, the polyester comprises at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-1, 4-cyclohexanedimethanol, bisphenol a terephthalate, and copolymers of the foregoing derivatives.
The technical solution of the present invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings. It should be noted that the following specific examples are given by way of illustration only and the scope of the present invention is not limited thereto.
The chemicals and raw materials used in the following examples were either commercially available or self-prepared by a known preparation method.
As shown in fig. 1, the organic light emitting display device 100 of the present embodiment includes a backlight 20 and a polarizing plate 30; the polarizing plate 30 includes a first polarizer protective film 32, a polarizer 31, and a second polarizer protective film 33.
The second polarizer protective film 33 has an in-plane retardation value Re ═ λ/4+ n ×. λ0Wherein λ is (500-600) nm, λ0550nm, n is a natural number.
The in-plane retardation of the first polarizer protective film 32 may be Re ═ λ/4+ n ═ λ0Wherein λ is (500-600) nm, λ0The thickness is 550nm, n is a natural number, and the transparent protective film can be common without limitation.
The backlight 20 is composed of an organic light emitting layer 21, a cathode 22 and an anode 23, wherein the organic light emitting layer may be an organic light emitting small molecule compound or a conjugated polymer as a light emitting material.
The polarizing plate 30 is composed of 2 polarizer protective films and a polarizer interposed therebetween. The polarizing plate may be manufactured by a known method. For example, the polyvinyl alcohol film is prepared by processes of swelling, iodine dyeing, washing, stretching orientation in boric acid, color complementing through potassium iodide solution, drying through an oven and the like.
Among them, the second polarizer protective film 33 preferably has an in-plane retardation value Re ═ λ/4+ n ×. λ from the viewpoint of changing the polarization state of linearly polarized light0Wherein λ is (500-600) nm, λ0550nm, n is a natural number, and λ is preferred0N is a natural number, wherein the number is (510-590) nm; because the human eye is most sensitive to light at 550nm wavelength and visible light passing through the material is dispersive with wavelength (follows a cauchy distribution); when lambda is0< 500nm time or lambda0When the thickness is more than 600nm, the function of 1/4 wave plates of the light source side protective film is lost, and linearly polarized light cannot be effectively converted into circularly polarized light, so that the effect of suppressing reflected light is affected. The retardation value of the polarizer protective film may be measured directly by a commercially available instrument or may be measured by another instrument capable of measuring the retardation value of the film. The phase difference tester of RETS-100L series from Tsukamur is used in the invention.
The thickness of the second polarizer protective film 33 is not particularly limited without affecting the effect of the present invention, and is generally 10 to 300um, and more preferably 20 to 100um according to the demand of the current display market, because when the thickness of the film is less than 10um, the uniformity after the sample is extremely difficult to be ensured, and the mechanical properties of the film, including tensile strength, tear property and thermal stability, are significantly reduced. It is particularly preferred when the lower limit of the thickness is 30 um. On the other hand, if the thickness of the second polarizer protective film 33 exceeds 300um, the thickness of the entire polarizer will be greatly increased, making the entire display panel as thick, and therefore, it is not preferable. From the practical performance perspective, the preferred thickness interval is 30 ~ 100 um.
The in-plane retardation of the second polarizer protective film 33 is determined by both the thickness and the in-plane birefringence, i.e., Re ═ Δ n × d, where Δ n is the difference in refractive index between the slow axis direction and the fast axis direction in the plane of the stretched polyester film, and d is the thickness of the film. In order to reduce the variation in the in-plane retardation Re due to the thickness error, the thickness uniformity is preferably 5% or less, more preferably 4% or less, particularly preferably 3% or less, and even more preferably 1% or less. Thickness uniformity Using D TableI.e. D ═ Dmax-dmin) 100% of/dx, D is a measure of the thickness uniformity, DmaxAnd dminThe maximum and minimum thickness values, respectively, and d is the average thickness value. The specific test method is that a point is taken every 2cm along the processing direction of the protective film, the total point is 80-100 points, and a spiral micrometer or other thickness measuring tools with the precision reaching 0.001mm are adopted for thickness measurement.
In principle, the material of the second polarizer protective film 33 is not critical in the present invention, and the solution of the present invention is universal, and any thermoplastic material with adjustable retardation value can be used in the stretching process. The type of the polyester resin is not particularly limited, and any polyester resin obtained by condensing a dicarboxylic acid and a diol can be used. Examples of dicarboxylic acid components that can be used for producing the polyester resin include: terephthalic acid, azelaic acid, dimer acid, phthalic acid, isophthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, diphenylcarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylsulfone carboxylic acid, anthracene dicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, hexahydroisophthalic acid, malonic acid, dimethylmalonic acid, succinic acid, 3-diethylsuccinic acid, hexahydroterephthalic acid, glutaric acid, 2-dimethylglutaric acid, trimethyladipic acid, adipic acid, 2-methyladipic acid, pimelic acid, sebacic acid, suberic acid, dodecanedicarboxylic acid, and the like.
Examples of the diol component that can be used for producing the polyester resin include: ethylene glycol, propylene glycol, 1, 2-cyclohexanedimethanol, hexamethylene glycol, neopentyl glycol, 1, 4-cyclohexanedimethanol, decamethylene glycol, 1, 4-butanediol, 1, 3-propanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, and the like.
Any 1 or 2 or more kinds of dicarboxylic acid component and diol component constituting the polyester resin may be used. Examples of suitable polyester resins for forming the polyester film include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and more preferably: polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, and these may further contain other copolymerization components.
When the second polarizer protective film 33 is attached to the polarizer, the slow axis of the side polarizer protective film closer to the observation side (i.e., the second polarizer protective film 33) preferably forms an angle of 30 ° to 50 ° with the absorption axis of the polarizer. Since even if the protective film has the function of 1/4 wave plates, if linearly polarized light is to be converted into a circularly polarized state, the angle between the optical axis of the wave plate and the direction of the optical axis of the polarizing plate needs to be 45 °. Therefore, it is preferable that the angle between the slow axis of the protective film and the absorption axis of the polarizing plate when the second polarizer protective film 33 is attached to the polarizing plate on the side close to the light source is 40 ° to 50 °, and more preferably 43 ° to 47 °, because in this angle range, the polarized light is already almost close to circularly polarized light after passing through the protective film having the function of 1/4 wave plate; if the included angle between the slow axis of the protective film and the absorption axis of the polarizer is strictly limited to 45 °, this will cause a great challenge to the bonding process between the protective film and the polarizer, which is not favorable for mass production. The optical axis directions of the polarizer and the polarizer protective film may be measured by a RETS-100L phase difference meter from tsukamur corporation.
The second polarizer protective film 33 preferably has a heat shrinkage rate of less than 5% when left at 150 ℃ for 30 minutes, specifically, a heat shrinkage rate of less than 5% in both the slow axis direction and the fast axis direction, and more preferably less than 2%. Since the protective film shrinks by heat in the subsequent lamination with the polarizer or other functional coating processes if the heat shrinkage exceeds 5%, the base film warps, which affects the uniformity of retardation value and thus the display effect.
From the viewpoint of use, the second polarizer protective film 33 preferably controls the ratio of the heat shrinkage in the fast axis direction to the heat shrinkage in the slow axis direction to be 0.8 to 1.2, and more preferably 0.85 to 1.1, because when the ratio is less than 0.8, even if the base film is not warped when the heat shrinkage ratio is less than 2% in the post-coating process and the bonding process with the polarizer, the birefringence change due to the internal stress caused by the difference in the heat shrinkage ratio in the fast axis and slow axis directions still occurs in the coating and heat curing stage, which may cause the 1/4 wave plate to fail in function and fail to change the linear polarization state of the emitted light.
The second polarizer protective film 32 is prepared as follows:
(1) method for producing cast sheet
The specific production method is described by taking polyethylene terephthalate as an example. The polyester cast sheet of the present invention has an ABA three-layer structure, and specifically, a small amount of a shedding agent (slipping agent) is added to at least the a layer to improve the releasability between the melt cast sheet and the extrusion die. The opening agent is not particularly limited, and may be organic or inorganic without affecting the effect of the present invention. Organic, such as oleamide, may be cited, and inorganic, such as talc, diatom, silica, may be cited as the opening agent. The silica opening agent is preferable from the viewpoint of suppressing yellowing of the end portions of the cast piece.
For the size of the opening agent, the preferable granularity is 1-10 um, and more preferably less than 1.5-5 um. Because, although an increase in the particle size of the opening agent contributes to an increase in the slip effect, the surface haze is also increased. However, when the particle size is less than 1.5um, the slipping effect cannot be ensured.
In the surface layer containing the opening agent, the concentration of the opening agent is preferably 500 to 9000ppm, and more preferably 800 to 6000 ppm. Because the content of the opening agent in the film is also calculated in ppm, if the content of the opening agent is too high, the optical property and the mechanical property of the film are influenced; however, if the content is too low, the blocking problem of the film cannot be solved.
The addition method of the opening agent may be one in which the opening agent is added during polyester synthesis to prepare a polyester master batch, or one in which a fixed concentration of the opening agent is physically mixed with polyester chips and then re-granulated in a twin-screw extrusion granulator.
For the B layer of an ABA three-layer cast sheet, it is preferable to add an amount of uv absorber to the B layer to obtain excellent uv blocking performance. Since the polarizer is generally formed by iodine-dyeing and stretching a polyvinyl alcohol (pva) film, the polarizer protective film has a transmittance of 10% or less at a wavelength of 390nm in view of protection of polarization performance of the polarizer. Since ultraviolet rays less than 390nm destroy the structure of polyiodide ions in the polarizer and eventually cause the polarizer to fail, it is preferable that the protective film 33 for the second polarizer have a light transmittance of 5% or less at a wavelength of 390 nm. The transmittance at a wavelength of 390nm can be measured by an ultraviolet spectrophotometer.
It is preferable to obtain the ultraviolet absorption function of the second polarizer protective film 33 that an ultraviolet absorber is added when preparing an unstretched cast sheet, and specifically, the ultraviolet absorber is completely mixed with resin particles, and then fed into an extruder to be melt-mixed, and then an unstretched cast sheet is prepared to impart the ultraviolet absorption function to the stretched film. Further, the ultraviolet absorbing function may be imparted to the polarizer protective film by coating a coating liquid containing an ultraviolet absorbing substance on the surface of the biaxially stretched film and then curing the coating liquid.
For the present invention, there is no particular limitation on the ultraviolet absorber that can impart the functional effect of ultraviolet absorption to the film. It may be inorganic or organic. The ultraviolet absorber is preferably an organic ultraviolet absorber from the viewpoint of light transmittance of the film. As the organic ultraviolet absorber, there may be mentioned salicylates, benzophenones, benzotriazoles, triazines, trimethoxybenzoates, p-aminobenzoic acids, benzoates, camphor derivatives, benzamidines, benzoxazines and the like.
For benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers and acrylonitrile-based ultraviolet absorbers, for example, are: dihydroxy-4, 4 '-dimethoxybenzophenone, 2- [ 2' -hydroxy-5 '- (methacryloyloxyethyl) phenyl ] -2H-benzotriazole, 2' -2, 2 ', 2- [ 2' -hydroxy-5 '- (methacryloyloxymethyl) phenyl ] -2H-benzotriazole, 2- [ 2' -hydroxy-5 '- (methacryloyloxypropyl) phenyl ] -2H-benzotriazole, 4' -tetrahydroxybenzophenone, 2, 4-di-tert-butyl 5-chlorobenzotriazol-2-yl) benzene, 2- (2 '-light-3' -tert-butylmethylbenzene) -5-chlorobenzotriazole, and mixtures thereof, 2- (5-chloro (2H) -benzotriazol-2-yl) -4-methyl-6- (tert-butyl) phenol, 2' -methylenebis (4- (1, 1, 3, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol, etc. As the benzoxazine-based ultraviolet absorber, for example, the following steps are: 2, 2' - (1, 4-phenylene) bis (3, 1-benzoxazin-4-one), 1-benzoxazin-4-one, 2-methyl-3, 2-butyl-3, 1-benzoxazin-4-one, 2-phenyl-3, 1-benzoxazin-4-one, and the like.
In addition, various additives such as phosphorus compounds, antistatic agents, light stabilizers, flame retardants, heat stabilizers, antioxidants, antigelling agents, surfactants, and the like are contained in addition to the ultraviolet absorbers in a range not to impair the effects of the present invention to increase the ultraviolet absorbing effect and light stability of the film.
Specifically, the production of the ABA three-layer structure cast sheet described above can be achieved in the following manner. Without limiting the dry form, the water content of the material for the layer B of polyethylene terephthalate pellets containing an ultraviolet absorber and the material for the layer a of polyethylene terephthalate pellets containing a opener is reduced to 500ppm or less, and in order to ensure that the subsequent melt extrusion process is stable and the polyester does not degrade, it is more preferable to reduce the water content of the polyester pellets to 200ppm or less, and it is more preferable to reduce the water content of the polyester pellets to 100ppm or less.
The dried polyester chips are melt-extruded through an extruder, and the use of the extruder is not limited, and the melt-extrusion can be performed by using a single screw extruder, a twin screw extruder, and melt-extrusion based on their various derivatives, and the melt of the a layer and the melt of the B layer are distributed into a die to be compounded in the form of ABA through a distributor, and are quenched through a chill roll to cast the chips.
Taking a conventional single-screw extruder as an example, specifically, the temperature of a feeding section is Tm +/-30 ℃, Tm is the melting temperature of the polyester raw material, the temperature of a compression section is Tm-Tm +35 ℃, and the temperature of a homogenization section is Tm-Tm +35 ℃; the temperature of the neck ring mold is Tm-Tm +30 ℃; more preferably, the temperature of the feeding section is Tm +/-20 ℃, the temperature of the compression section is Tm-Tm +15 ℃, and the temperature of the homogenization section is Tm + 15-Tm +30 ℃; the temperature of the neck ring mold is Tm + 15-Tm +30 ℃; because the temperature in the feeding section is lower than Tm, the single screw extruder will not provide enough forward driving force to feed the material into the compression section, and if the temperature in the feeding section is higher than Tm +30 ℃, the polyester chips will melt in the feeding section due to the over-high temperature and cannot enter the compression section. If the temperature of the compression section is lower than Tm, the material cannot be completely plasticized in the compression section, and if the temperature is higher than Tm +35 ℃, the material is easy to melt and break, so that the pressure of the front section is unstable. The principle for the homogenization section and die temperature settings is the same as described above.
In order to filter out foreign substances in the raw materials and some particles which are not fully plasticized, a high-precision screen is preferably added to the extruder during melt extrusion. The preferred filtration precision is less than 50um or less. However, in order to minimize the influence of impurities on the film display effect and mechanical properties, the filtration accuracy is more preferably 10um or less.
(2) Stretching process
The polyester-based protective film used for the second polarizer protective film 33 in the present invention may be prepared by an asynchronous biaxial stretching process, or may be prepared by a uniaxial stretching process, or may be prepared by oblique stretching. It is more preferable to use asynchronous biaxial stretching because the mechanical properties of the uniaxially stretched film in the machine direction are very poor and the requirements for equipment are too high for the oblique stretching process. Therefore, asynchronous biaxial stretching is preferable from the viewpoint of the demand for mechanical properties and the realization of industrialization at a reduced cost.
Specifically, the asynchronous stretching includes longitudinal stretching after preheating and subsequent transverse stretching. The longitudinal stretching and the transverse stretching are not required for the stretching form, and any form of known single point stretching, two point stretching, clamp stretching, and the like can be adopted.
Longitudinal stretching
Specifically, the preheating temperature before longitudinal drawing is in the vicinity of Tg (glass transition temperature of the polyester raw material). Preferably Tg-10 ℃ to Tg +10 ℃. The longitudinal stretching temperature is preferably Tg to Tg +30 ℃, more preferably Tg +10 to Tg +20 ℃. The longitudinal stretching has no requirement on the stretching speed, and can be set according to the actual production level of a production line. The longitudinal stretching ratio is preferably 1-5, and more preferably 1.2-4. Because if the stretching ratio is too small, the structure in the cast sheet cannot be uniformly stretched in the subsequent transverse stretching, if the longitudinal stretching ratio is too large, crystallization occurs in the longitudinal stretching, so that the stress in the transverse stretching of the sample is too difficult, the structure is hardly uniformly stretched, and the film breaking phenomenon is easily caused. Therefore, the longitudinal stretch ratio is preferably 1.2 to 3.5.
Post-longitudinal drawing heat treatment
In order to ensure that the ratio of the heat shrinkage in the longitudinal direction to the heat shrinkage in the transverse direction is in the range of 0.8 to 1.2, it is preferable in the present invention to perform heat treatment after longitudinal stretching. The preferred heat treatment temperature is from Tg-20 ℃ to Tg +20 ℃, more preferably from Tg-10 ℃ to Tg +10 ℃. When the heat treatment temperature is less than Tg-20 deg.C, the molecular chains in the stretched film will be rapidly frozen, failing to obtain sufficient relaxation of the molecular chains in the stretching direction. When the temperature is higher than Tg +20 ℃, the temperature is too high, the mobility of the molecular chain is too strong, and excessive relaxation in the stretching direction is caused, resulting in a decrease in the tensile strength in that direction.
The heat treatment time is preferably 15 to 60 seconds. The time heat treatment time is selected in a manner similar to the above-described temperature selection. The molecular chain cannot be sufficiently relaxed by the heat treatment time period. The molecular chain is excessively relaxed with a long heat treatment time. Therefore, the heat treatment time is more preferably 20 to 40 seconds.
Stretching in transverse direction
From the viewpoint of structural uniformity and processability, it is preferable to perform a preheating treatment before transverse stretching after longitudinal stretching and before transverse stretching. Specifically, the preheating temperature is preferably from Tg to Tg +50 ℃ and more preferably from Tg +10 ℃ to Tg +40 ℃ because the Tg of the film slightly increases after longitudinal stretching, and therefore the preferred lower preheating temperature is Tg +10 ℃. However, the preheating temperature is not so high, and if the preheating temperature is too high, cold crystallization (heat crystallization) of the film after longitudinal drawing is easily caused, the cold crystallization not only easily causes whitening of the film and influences the light transmittance, but also causes embrittlement and transverse drawing is not performed, so that the upper limit of the preheating temperature is preferably Tg +30 ℃.
From the viewpoint of controlling the structural uniformity and retardation value, the transverse stretching temperature is preferably Tg +10 to Tg +50 ℃, more preferably Tg +15 to Tg +35 ℃, and in this temperature region, it is possible to ensure that the sample is in a rubbery state above its glass transition temperature at the start of transverse stretching, and stretching is performed in such a state that the molecular orientation in the film has a linear-like relationship with the stretching ratio, which facilitates precise control of the orientation and retardation value of the film.
The transverse stretching ratio is preferably 2 to 6 times, more preferably 3 to 5.5 times, from the viewpoint of improving transverse mechanical properties of the film. Since the tensile strength in the stretching direction is monotonically and positively correlated with the stretching ratio, the lower limit of the stretch ratio in the transverse direction is not less than 3 times in order to increase the strength in the transverse direction. Further, since the mechanical properties in the longitudinal direction are relatively reduced as the stretch ratio in the transverse direction is larger, the upper limit of the stretch ratio in the transverse direction is not more than 5.5 times in order to obtain good mechanical properties in both the longitudinal direction and the transverse direction.
Heat setting after horizontal drawing
In order to improve the dimensional stability of the film and reduce the heat shrinkability of the film, it is preferable to perform a heat-setting treatment after stretching in the transverse direction at the above-mentioned stretching temperature and stretching magnification. The heat-setting treatment temperature is preferably 200 to 250 ℃. When the heat-setting temperature is less than 200 ℃, crystallization in the heat-setting stage is not complete, which is disadvantageous from the viewpoint of improving dimensional stability of the film. When the heat setting temperature is higher than 250 ℃, crystallization is fast, and the internal stress of the film is easy to be larger during heat setting, thereby influencing the uniformity of the retardation value in the film surface.
From the viewpoint of the internal stress of the film at the time of small heat setting, it is preferable to perform a shrinking treatment of 0.1% to 10% in the width direction at the time of heat setting.
(3) Functional modification
Priming treatment
In order to increase the adhesiveness between the polarizer protective film and the polarizer protective film, at least one surface of the film in the stretching process is subjected to hydrophilic treatment. Since the adhesion of the polarizer to the polarizer protective film is generally performed by pva (polyvinyl alcohol) water-dispersible solution, if the surface of the polarizer protective film is too smooth or hydrophilic, the adhesion between the polarizer and the polarizer protective film may be insufficient, i.e., weak. Specifically, the surface of the film may be treated by corona treatment using known surface treatment methods, for example, corona treatment, oxidation treatment, flame treatment, solvent treatment, and primer treatment, and the like may be used to modify the surface of the film to improve the adhesiveness of the surface.
From the viewpoint that the aging property of the modification effect has been industrially continuously produced, it is preferable to subject the primer treatment to increase the easy adhesion thereof. Specifically, it is preferable to apply a primer treatment to at least one surface of the film after the film is longitudinally stretched. The primary coating means that at least one surface of the film is coated with an organic solvent after the film is longitudinally stretched so as to increase the easy adhesion of the film. Specifically, it is preferable to have a coating liquid containing at least one of a polyester resin, a polyurethane resin, and a polyacrylic (ester) resin as a main component. The "main component" herein means a component that occupies 50% by mass or more of the solid component constituting the coating liquid. The coating liquid is preferably an aqueous coating liquid containing at least one of a water-soluble or water-dispersible copolymerized polyester resin, an acrylic resin, and a urethane resin. Examples of these coating liquids include: water-soluble or water-dispersible copolyester resin solutions, acrylic resin solutions, urethane resin solutions, and the like disclosed in japanese patent No. 3567927, japanese patent No. 3589232, japanese patent No. 3589233, japanese patent No. 3900191, and japanese patent No. 4150982. The refractive index of the resin solution is preferably 1.5 to 1.7 in order to adjust the light transmittance of the film. If the refractive index of the coating liquid is greatly different from that of the polyester base film, the surface of the base film may be fogged, the haze is increased, and the light transmittance is reduced, so that the refractive index of the coating liquid is preferably close to that of the base film. The refractive index can be controlled by adding appropriate organic or inorganic particles to the coating liquid.
As a method of coating liquid, a known method can be used. Examples of the method include a reverse roll coating method, a gravure coating method, a kiss coating method, a roll brush method, a spray coating method, a knife coating method, a wire bar coating method, and a doctor blade (pipe) method, and these methods may be used alone or in combination for coating.
Functional surface treatment
In addition, in order to impart the function of the protective film for a polarizing plate as described above to protect a hard coat layer, the above stretched film may be subjected to a coating layer having one or more functions of antistatic, anti-staining, anti-reflection, anti-scratch, anti-glare according to a known method.
Example 1
Evaluation of display Effect
An organic light-emitting source was used as a light-emitting source of a display device (12864-. Wherein the slow axis direction of the polyester film and the absorption axis direction of the polarizing plate were attached at the following angles. On the observation side of the display device, the liquid crystal display device was observed with one polarizing plate interposed therebetween in a state where the absorption direction of the polarizing plate was different from the absorption axis of the polarizing plate in the polarizing plate on the observation side in the liquid crystal display device, and evaluated according to the following criteria.
Evaluation of superior light luminance:
o: the brightness of emergent light of the display device is unchanged along with the change of an observation angle;
a tangle-solidup: the brightness of the emergent light of the liquid crystal display device is slightly changed along with the change of the observation angle;
x: the brightness emitted by the liquid crystal display device is obviously changed along with the change of the observation angle;
measurement of Heat shrinkage
Cutting the stretched film into a square with the side length of 100mm by taking the mechanical advancing direction and the direction vertical to the mechanical advancing direction as sides, then flatly paving the square on an aluminum plate with the thickness of 12mm, putting the aluminum plate and the film into an oven with the temperature of 150 ℃ for 30 minutes, and taking out. The length of the film on the aluminum plate in both directions was measured and recorded as L, and the heat shrinkage was calculated by the following formula:
heat shrinkage factor (100-L)/100 × 100%.
Layer B masterbatch preparation
Taking PET polyester chips with the viscosity of 0.67dl/g, adding a uv3638 type ultraviolet absorbent ((2, 2' - (1, 4-phenylene) bis (4H-3, 1-benzoxazine-4-one)) with the mass fraction of 0.8%, drying, feeding into a double-screw mixing extruder, extruding at 280 ℃ for 5 minutes, and granulating to prepare a master batch with the ultraviolet absorbent in the core layer.
Preparation of layer A masterbatch
Taking PET polyester chips with the viscosity of 0.67dl/g, adding 2000ppm concentration fraction silica particles with the granularity of 2um, and fully and physically mixing uniformly to obtain the master batch containing the opening agent for the surface layer.
Preparation of cast sheet
And drying the B layer master batch at 160 ℃ to ensure that the water content is less than 100ppm, putting the B layer master batch into a single-screw extruder, setting the temperature of a feeding section to be 265 ℃, the temperature of a compression section to be 275 ℃, the temperature of a homogenizing section to be 275 ℃, the temperature of a neck mold to be 275 ℃, and adjusting the rotating speed of a screw and the rotating speed of a metering pump to ensure that the pressure after the pump is stabilized at 1.2 MPa. And (3) putting the layer A master batch into a double-screw extrusion auxiliary machine, setting the temperature of a melt extrusion section to be 260 ℃ and gradually increased to 270 ℃, and setting the temperature of a melt conveying section and a die head to be 272 ℃. And (3) tightly pressing the three layers of solution flowing out of the neck ring mold on a cooling roller by adopting an electrostatic adhesion mode for quenching, keeping the temperature of the cooling roller constant at 30 ℃, and adjusting the extrusion amount to ensure that the thickness ratio of the three layers of the film is 15: 70: 15 to manufacture amorphous casting sheets with different thicknesses.
Adopting the cast sheet, longitudinally stretching 2.3 times at 90 ℃, then thermally relaxing at 90 ℃ for 30 seconds, then coating a layer of polyester solution with the refractive index of 1.62 on the upper surface and the lower surface of the film at 30 ℃ by a spraying method, drying and curing at 95 ℃ for 50 seconds by using a thermal convection mode to ensure that the coating weight after drying is 0.2g/m2, then transversely stretching 4.2 times at 105 ℃, and thermally treating at 230 ℃ for 15 seconds to obtain a biaxially oriented film with the thickness of 82 um; the polyester film was attached to the polarizer at 45 ° in the slow axis direction.
Example 2
The same procedure as in preparation example 1 was repeated except that the stretching in the machine direction was 1.8 times and then heat-treated at 80 ℃.
Example 3
The same procedure as in preparation example 1 was repeated except that the heat treatment was carried out at 65 ℃ after stretching 2.5 in the machine direction.
Example 4
After the longitudinal stretching, heat treatment was carried out for 10 seconds, and the process was the same as that of preparation example 3.
Example 5
Stretching in machine direction 2 times and stretching in transverse direction 4.5 times, the rest being the same as the procedure for preparation of example 3.
Example 6
Stretching in the machine direction was 1.8 times and stretching in the transverse direction was 4.7 times, the rest being the same as in the production example 5.
Example 7
Stretching in the machine direction was 2.8 times and stretching in the transverse direction was 5.1 times, and the rest was the same as in the method for preparing example 1.
Example 8
Stretching in the machine direction was 2.1 times and stretching in the transverse direction was 4.5 times, and the rest was the same as in the method for preparing example 5.
Example 9
The stretching in the machine direction was 2.7 times and the stretching in the transverse direction was 4.8 times, and the rest was the same as that in the production example 5.
Comparative example 1
The stretching was 1 times in the machine direction and 4.8 times in the transverse direction, and the rest was the same as that of preparation example 3.
Comparative example 2
The same procedure as in preparation example 3 was repeated except that the heat treatment was not carried out after the longitudinal stretching.
Comparative example 3
The polyester film was attached so that the slow axis direction thereof was 0 ° to the light absorption axis of the polarizer in the same manner as in preparation example 3.
The quotient (a) and remainder (b) of integers obtained by dividing the in-plane retardation values Re and Re of the polarizer protective films by 500 were counted at a center wavelength l0 of 550nm, and the display effects and the heat shrinkage and heat shrinkage ratio were filled in table 1.
TABLE 1
From the results shown in the attached table 1, it was found that the observation effect was very good for all of example 3, example 5 and example 9, and the observation effect was very poor for example 1, example 7, comparative example 2 and comparative example 3.
Industrial applicability
According to the polarizer protective film and the display device provided by the invention, the phenomenon that the visual field brightness is darkened or a dark state appears when the display device is observed through the polarizer element can be effectively improved, and the display effect is improved. In addition, the solution of the present invention has a low manufacturing cost, and thus has very high industrial feasibility.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. An organic light emitting display device comprising:
a backlight for providing a light source; and
the polarizing plate is arranged on one side of the backlight source and comprises a first polarizer protective film, a polarizer and a second polarizer protective film which are sequentially arranged along one side far away from the backlight source;
wherein the second polarizer protective film has an in-plane retardation value of Re ═ λ/4+ n ═ λ0Wherein λ is (500-600) nm, λ0550nm, n is a natural number; the second polarizer protective film is placed at 130-160 ℃ for 10-40 minutes, and then the slow axis direction and the fast axis direction are performedThe thermal shrinkage rates of the components are all less than 5 percent; the ratio of the heat shrinkage rate of the second polarizer protective film in the fast axis direction to the heat shrinkage rate of the second polarizer protective film in the slow axis direction is 0.8-1.2, and the included angle between the slow axis direction of the second polarizer protective film and the polarizer absorption axis is 45 degrees;
the method for preparing the second polarizer protective film comprises the following steps:
preparing a cast sheet from a polymer raw material;
longitudinally stretching the casting sheet to obtain a first oriented film;
transversely stretching the first oriented film to obtain a second oriented film;
the longitudinal stretching temperature is Tg-Tg +30 ℃, the longitudinal stretching magnification is 1-5 times, the Tg is the glass transition temperature of the raw materials, the transverse stretching temperature is Tg + 10-Tg +50 ℃, the transverse stretching magnification is 2-6 times, and the Tg is the glass transition temperature of the raw materials;
heat-setting a second alignment film to obtain the first polarizer protective film;
the polarizing plate is used for changing the polarization state of the backlight source emergent light so as to increase the observable visual angle of the organic light-emitting display device.
2. The organic light-emitting display device according to claim 1,
the second polarizer protective film has a light transmittance of less than 10% at a wavelength of less than 385 nm.
3. The organic light-emitting display device according to claim 1,
the thickness of the second polarizer protective film is 10-300 um;
the thickness uniformity D of the second polarizer protective film is less than 5%;
wherein D ═ D max-D min)/D × 100%, D max is the maximum value of the thickness of the second polarizer protective film, D min is the minimum value of the thickness of the second polarizer protective film, and D is the average value of the thickness of the second polarizer protective film.
4. The organic light-emitting display device according to claim 1,
the formula for calculating the in-plane retardation value of the second polarizer protective film is:
re ═ Δ n × d, where Δ n is a difference in refractive index between the slow axis direction and the fast axis direction in the plane of the second polarizer protective film, and d is a thickness of the second polarizer protective film.
5. The organic light-emitting display device according to claim 1,
the heat setting temperature is 200-250 ℃.
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