WO2019004767A1 - 기판 - Google Patents
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- WO2019004767A1 WO2019004767A1 PCT/KR2018/007390 KR2018007390W WO2019004767A1 WO 2019004767 A1 WO2019004767 A1 WO 2019004767A1 KR 2018007390 W KR2018007390 W KR 2018007390W WO 2019004767 A1 WO2019004767 A1 WO 2019004767A1
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- spacer
- substrate
- spacers
- hemispherical
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13392—Gaskets; Spacers; Sealing of cells spacers dispersed on the cell substrate, e.g. spherical particles, microfibres
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13398—Spacer materials; Spacer properties
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
Definitions
- the present application is directed to a substrate.
- Patent Document 1 discloses a so-called GH cell (Guest host cell) applying a mixture of a liquid crystal host (liqid crystal host) and a dichroic dye guest.
- spacers are located between the substrates to maintain the spacing between the two substrates.
- Patent Document 1 European Patent Publication No. 0022311
- the present application provides a substrate, for example, a substrate including a spacer or a substrate on which an alignment film is formed on a spacer of the substrate.
- the substrate of the present application comprises a base layer and a spacer present on the base layer.
- the substrate layer any substrate layer used in a substrate in a configuration of a known optical device such as, for example, an LCD (Liquid Crystal Display) can be applied without particular limitation.
- the substrate layer may be an inorganic substrate layer or an organic substrate layer.
- the inorganic base layer a glass base layer and the like can be exemplified.
- the organic base layer various plastic films and the like can be exemplified.
- Plastic films include TAC (triacetyl cellulose) film; Cycloolefin copolymer (COP) films such as norbornene derivatives; Polyacrylate films such as PMMA (poly (methyl methacrylate), polycarbonate films, polyolefin films such as PE (polyethylene) or PP (polypropylene), polyvinyl alcohol films, DAC (diacetyl cellulose)
- a polyether sulfone (PES) film, a polyetheretherketone (PES) film, a polyphenylsulfone (PPS) film, a polyetherimide (PEI) film, a polyethylenemaphthatate (PEN) film, a polyethyleneterephtalate (PET) Film or PAR (polyarylate) film, and the like can be exemplified, but are not limited thereto.
- the thickness of the substrate layer in the substrate of the present application is not particularly limited, and an appropriate range may be selected depending on the application.
- Spacers are present on the base layer.
- the spacer may be fixed to the substrate layer.
- the spacer may be fixed directly in contact with the substrate layer, or may be fixed on the other layer if there is another layer between the substrate layer and the spacer.
- the kind of the other layer includes a known layer necessary for driving the optical device, and for example, an electrode layer or a light-shielding layer described later can be exemplified.
- the spacer may be a hemispherical spacer having at least a hemispherical portion formed thereon.
- hemispherical portion in the present application may mean a portion of a spacer including a curved shape in which the trajectory of the cross section has a predetermined curvature.
- the trajectory of the cross section of the hemispherical portion may include a curved portion in which the center of curvature exists inside the cross section trajectory.
- the hemispherical portion may have a maximum curvature of a cross-sectional locus of 2,000 mm < -1 > or less.
- the curvature is a numerical value representing the degree of curvature of a line, and is defined as an inverse number of a radius of curvature which is a radius of a contact point at a predetermined point of the curve. In the case of a straight line, the curvature is zero, and as the curvature increases, the curve bends further.
- the degree of curvature of the hemispherical portion is controlled so that the maximum curvature of the cross-sectional locus of the hemispherical portion is 2,000 mm < -1 > or less so that uniform alignment treatment can be performed even when the alignment treatment of the alignment layer is performed on the hemispherical portion.
- the section for confirming the cross-sectional locus of the hemispherical portion may be any arbitrary plane for the base layer.
- the maximum curvature may mean the largest curvature among the curvatures for all the contact sources that can be obtained on the cross-sectional locus of the hemispherical portion.
- the end face of said hemispherical locus may not include a portion bent to a curvature greater than about 2,000 mm -1.
- the maximum curvature is In another example 1,800 mm -1 or less, 1,600 mm -1 or less, 1,400 mm -1 or less, 1,200 mm -1 or less, 1,000 mm -1 or less, 900 mm -1 or less, 950 mm -1 or less, 850 mm -1 or less, 800 mm -1 or less, 750 mm -1 or less, 700 mm -1 or less, 650 mm -1 or less, 600 mm -1 or less, 550 mm -1 or less, 500 mm -1 or less, 450 mm - 1 or less, 400 mm -1 or less, 350 mm -1 or less, 300 mm -1 or less, 250 mm -1 or less, 200 mm -1 or 150 mm -1 or less.
- the maximum curvature may be at least 5 mm -1, at least 10 mm -1, at least 15 mm -1, at least 20 mm -1, at least 25 mm -1, at least 30 mm -1, at least 35 mm -1 , At least 40 mm -1, at least 45 mm -1, or at least 50 mm -1 .
- the cross-sectional locus of the hemispherical portion may or may not include a portion having a curvature of zero, that is, a linear portion.
- FIG. 1 is an example of a cross section of a hemispherical portion that does not include a portion having a curvature of 0
- FIG. 2 is an example of a cross section of a hemispherical portion including a portion having a curvature of zero.
- the spacer includes at least the hemispherical portion as described above.
- the term top refers to the direction from the base layer toward the spacer formed on the base layer, and the bottom refers to the opposite direction of the top.
- the spacer may be formed in various shapes as long as it includes the hemispherical portion.
- the hemispherical spacer may have a shape in which the hemisphere is directly formed on the surface of the base layer 100 as shown in FIG. 1 or 2, or a columnar spacer including the hemisphere as shown in FIG. 3 or 4, Lt; / RTI >
- the hemispherical portion of the hemispherical spacer may not include a portion whose cross-sectional locus has a curvature of 0 as shown in Fig. 1 or Fig. 3, or the cross-sectional locus of the hemispherical spacer may have a curvature of 0 (A flat surface at the top).
- the hemispherical portion of the same shape as that of the hemispherical portion of the spacer of Fig. 1 or 3 is referred to as a hemispherical portion, and the hemispherical portion of the spacer of Fig. 1 or 3, The portion can be referred to as a flat hemispherical portion.
- H2 is the height of the hemispherical portion
- R is the radius of curvature of the hemispherical portion
- W1 is the length (width) of the flat surface of the flat hemispherical portion
- W2 is the width of the spacer
- H1 is the width Min < / RTI >
- the hemispherical portion may be a complete hemispherical shape or an approximately hemispherical shape.
- the complete hemispherical shape is a hemispherical shape that satisfies the following relational expression 1
- the approximate hemispherical shape can be a hemispherical shape that satisfies any of the following relational expressions 2 to 4.
- the hemispherical section may have a shape in which the cross-sectional shape satisfies any one of the following relational formulas (1) to (4).
- a is the horizontal length of the hemispherical section measured at the center of the imaginary contact circle of the hemispherical section
- b is the vertical length of the hemispherical section measured at the center of the virtual contact circle of the hemispherical section
- the radius of curvature in the relational expressions 1 to 4 corresponds to the length indicated by R in Figs.
- the virtual contact circle may mean a contact circle having the largest radius of curvature among a plurality of imaginary contact radii in contact with the curved line forming the hemispherical portion.
- a contact circle having the largest radius of curvature among a plurality of imaginary contact radii at arbitrary points of the curved line is expressed by the relational expressions 1 to 4
- the horizontal length is a length measured in a direction parallel to the base layer surface (100 in Figs. 1 to 4) at the center point of the virtual contact circle, (100 in Figs. 1 to 4).
- a is the distance from the center of the virtual contact circle of the hemispherical section in the horizontal direction to the point where the hemispherical portion measured ends.
- the horizontal length may be a length measured from the center of the virtual contact circle in the rightward direction and two lengths measured in the leftward direction.
- the a applied in the relational expressions 1 to 4 is a short length of the two lengths Length. 1 and 3, the horizontal length a is a value corresponding to 1/2 of the width W2 of the spacer. 2 and 4, the value (2a + W1) obtained by adding the length (width) W1 of the flat portion to twice the horizontal length (a) may correspond to the width W2 of the spacer.
- b is the distance from the center of the virtual contact circle of the hemispherical cross section to the point where the hemispherical portion first contacts with the hemisphere portion in the vertical direction.
- This vertical length (b) can be generally the same as the height of the hemispherical portion, for example, the length denoted by H2 in Figs.
- Fig. 5 shows a case in which the curved line of the hemispherical portion of the hemispherical portion satisfying the relational expression 1 has a complete circle curve, that is, a curve having the same virtual contact circle.
- a tapered portion may be formed at a lower portion of the spacer, for example, at a lower portion contacting the base layer side, the curved portion having a curvature center on the outer surface of the cross section.
- the dimensions of the spacer of the above-described type are not particularly limited, and can be suitably selected in consideration of, for example, the cell gap of the desired optical device, the aperture ratio, and the like.
- the height of the hemispherical portion may be in the range of 1 ⁇ to 20 ⁇ .
- the height may be 2 ⁇ or more, 3 ⁇ or more, 4 ⁇ or more, 5 ⁇ or more, 6 ⁇ or more, 7 ⁇ or more, 8 ⁇ or more, 9 ⁇ or more, 10 ⁇ or 11 ⁇ or more in another example.
- the height may also be 19 ⁇ m or less, 18 ⁇ m or less, 17 ⁇ m or less, 16 ⁇ m or less, 15 ⁇ m or less, 14 ⁇ m or less, 13 ⁇ m or less, 12 ⁇ m or less or 11 ⁇ m or less in other examples.
- the width of the hemispherical portion may be in the range of 2 ⁇ to 40 ⁇ .
- the width may be 4 ⁇ or more, 6 ⁇ or more, 8 ⁇ or more, 10 ⁇ or more, 12 ⁇ or more, 14 ⁇ or more, 16 ⁇ or more, 18 ⁇ or more, 20 ⁇ or 22 ⁇ or more in other examples.
- the width may be 38 ⁇ m or less, 36 ⁇ m or less, 34 ⁇ m or less, 32 ⁇ m or less, 30 ⁇ m or less, 28 ⁇ m or less, 26 ⁇ m or less, 24 ⁇ m or less or 22 ⁇ m or less in other examples.
- the height of the spacer is the same as the height of the hemispherical portion when the spacer has the shape as shown in Fig. 1 or 2.
- the height of the hemispherical portion plus the height H1 of the column It can be a number.
- the height may be in the range of 1 [mu] m to 50 [mu] m in one example.
- the height may be 3 ⁇ or more, 5 ⁇ or more, 7 ⁇ or more, 9 ⁇ or more, 11 ⁇ or more, 13 ⁇ or more, 15 ⁇ or more, 17 ⁇ or more, 19 ⁇ or more, 21 ⁇ or more, Mu m or more or 27 mu m or more.
- the height may be 48 ⁇ or less, 46 ⁇ or less, 44 ⁇ or less, 42 ⁇ or less, 40 ⁇ or less, 38 ⁇ or less, 36 ⁇ or less, 34 ⁇ or less, 32 ⁇ or less, 30 ⁇ or less, Mu m or less.
- the hemispherical spacer or the hemispherical column spacer as described above, it is possible to uniformly perform the alignment treatment even on the alignment film formed on the spacer, maintain a uniform cell gap, The performance of the device can be maintained excellent.
- the spacer can be formed using a known material.
- the spacer may be formed by including an ultraviolet curable resin.
- the ultraviolet curable resin can form the spacer.
- the specific kind of ultraviolet curable compound that can be used for forming the spacer is not particularly limited, and for example, an acrylate-based polymer material or an epoxy-based polymer may be used, but the present invention is not limited thereto.
- the method of manufacturing the spacer of the above-mentioned type by applying the above-mentioned materials in the present application is not particularly limited.
- the spacer may be manufactured by applying an imprinting method.
- the spacer may be manufactured by applying an imprinting mask as schematically shown in FIG.
- the mask shown in Fig. 11 has a concave hemispherical shape 9011 formed on one surface of a main body 901 having a light transmitting property, for example, ultraviolet ray transmitting property, and the surface of the main body 901 on which the hemispherical shape 9011 is formed Shielding film 902 is formed at a portion where the hemispherical shape is not formed. If necessary, the surface of the main body 901 on which the light-shielding film 902 is formed may be subjected to appropriate mold releasing treatment.
- FIG. 1 An exemplary process for fabricating the spacer using a mask of this type is shown in FIG.
- a layer 200 of an ultraviolet curable compound is formed on the surface of the base material layer 100 and the mask 900 is pressed on the layer 200 as shown in Fig.
- the layer 200 of the compound is cured by irradiating ultraviolet rays or the like from above the mask 900, the compound is cured according to the hemispherical shape formed in the mask 900 to form a spacer.
- the spacer may then be formed in a fixed form on the substrate layer 100 by removing the mask 900 and removing the uncured compound.
- the target hemispherical or hemispherical columnar spacer can be manufactured by adjusting the amount of ultraviolet light, the degree of squeezing of the mask, and / or the hemispherical shape of the mask 900 irradiated in the above process.
- the substrate of the present application may include, in addition to the substrate layer and the spacer, other elements required for driving the optical device. These elements are variously known, and typically include an electrode layer or a light-shielding layer. In one example, the substrate may further include an electrode layer and / or a light shielding layer between the base layer and the spacer. As the electrode layer, a known material can be applied. For example, the electrode layer may comprise a metal alloy, an electrically conductive compound, or a mixture of two or more thereof.
- metal such as gold, CuI, indium tin oxide (ITO), indium zinc oxide (IZO), zinc tin oxide (ZTO), zinc oxide doped with aluminum or indium, magnesium indium oxide, nickel tungsten oxide, Metal oxides such as ZnO, SnO 2 or In 2 O 3 , metal serrides such as gallium nitride and zinc selenide, and metal sulfides such as zinc sulfide.
- the transparent positive hole injecting electrode layer can also be formed using a metal thin film of Au, Ag or Cu and a laminate of a transparent material of high refractive index such as ZnS, TiO 2 or ITO.
- the electrode layer can be formed by any means such as vapor deposition, sputtering, chemical vapor deposition or electrochemical means. Patterning of the electrode layer is also possible in a known manner without any particular limitation, and may be patterned through a process using, for example, a known photolithography or a shadow mask.
- a known material may be used as the light-shielding layer.
- a commonly used metal layer a metal oxide layer, a metal nitride layer or a metal oxynitride layer, a layer containing an organic pigment and / or an inorganic pigment, .
- the substrate of the present application may further include an alignment layer present on the substrate layer and the spacer.
- another exemplary substrate of the present application comprises a substrate layer; A spacer present on the base layer; And an alignment layer formed on the base layer and the spacer.
- the kind of the alignment layer formed on the base layer and the spacer is not particularly limited, and a well-known alignment film, for example, a well-known rubbing alignment film or a photo alignment film can be applied.
- the method of forming the alignment film on the base layer and the spacer and performing the alignment treatment thereon is also in accordance with a known method.
- the alignment layer is formed on the spacer of the specific shape as described above, it can also have a unique shape.
- the shape of the orientation film may have a shape that follows the shape of the spacer existing in the lower portion.
- 13 is a diagram schematically showing the cross-sectional locus of the alignment film.
- Fig. 13 shows an example of the cross-sectional shape of the alignment film formed on the spacer, in which the upper portion has a hemispherical shape with a center of curvature formed inside the cross-section while having a predetermined width W3 and a height H3.
- the alignment film may also include the hemispherical portion described above.
- the hemispherical portion may have a maximum curvature of the cross-sectional locus of 2,000 mm < -1 > or less as in the case of the spacer.
- the maximum curvature is In another example 1,800 mm -1 or less, 1,600 mm -1 or less, 1,400 mm -1 or less, 1,200 mm -1 or less, 1,000 mm -1 or less, 900 mm -1 or less, 950 mm -1 or less, 850 mm -1 or less, 800 mm -1 or less, 750 mm -1 or less, 700 mm -1 or less, 650 mm -1 or less, 600 mm -1 or less, 550 mm -1 or less, 500 mm -1 or less, 450 mm - 1 or less, 400 mm -1 or less, 350 mm -1 or less, 300 mm -1 or less, 250 mm -1 or less, 200 mm -1 or 150 mm -1 or less.
- the maximum curvature may be at least 5 mm -1, at least 10 mm -1, at least 15 mm -1, at least 20 mm -1, at least 25 mm -1, at least 30 mm -1, at least 35 mm -1 , At least 40 mm -1, at least 45 mm -1, or at least 50 mm -1 .
- the cross-sectional locus of the hemispherical portion of the alignment film may or may not include a portion having a curvature of zero, that is, a linear portion.
- the height or width of the alignment layer formed on the spacer as described above is not particularly limited as long as it is determined according to the height and width of the spacer existing therebelow and the thickness of the formed alignment layer.
- the height of the hemispherical portion may be in the range of 1 ⁇ to 50 ⁇ .
- the height may be 2 ⁇ or more, 3 ⁇ or more, 4 ⁇ or more, 5 ⁇ or more, 6 ⁇ or more, 7 ⁇ or more, 8 ⁇ or more, 9 ⁇ or more, 10 ⁇ or 11 ⁇ or more in another example.
- the height is not more than 48 ⁇ m, not more than 46 ⁇ m, not more than 44 ⁇ m, not more than 42 ⁇ m, not more than 40 ⁇ m, not more than 38 ⁇ m, not more than 36 ⁇ m, not more than 34 ⁇ m, not more than 32 ⁇ m, Less than or equal to 26 ⁇ , less than or equal to 24 ⁇ , less than or equal to 22 ⁇ , less than or equal to 19 ⁇ , less than or equal to 18 ⁇ , less than or equal to 17 ⁇ , less than or equal to 16 ⁇ , less than or equal to 15 ⁇ , less than or equal to 14 ⁇ , less than or equal to 13 ⁇ , less than or equal to 12.
- the width of the hemispherical portion may be in the range of 1 ⁇ to 80 ⁇ .
- the width may be 2 ⁇ or more, 3 ⁇ or more, 4 ⁇ or more, 6 ⁇ or more, 8 ⁇ or more, 10 ⁇ or more, 12 ⁇ or more, 14 ⁇ or more, 16 ⁇ or more, 18 ⁇ or more, Or more.
- the width is not more than 78 ⁇ m, not more than 76 ⁇ m, not more than 74 ⁇ m, not more than 72 ⁇ m, not more than 70 ⁇ m, not more than 68 ⁇ m, not more than 66 ⁇ m, not more than 64 ⁇ m, 45 ⁇ m or less, 44 ⁇ m or less, 42 ⁇ m or less, 40 ⁇ m or less, 38 ⁇ m or less, 36 ⁇ m or less, 34 ⁇ m or less, 32 ⁇ m or less Or less, 30 mu m or less, 28 mu m or less, 26 mu m or less, 24 mu m or less, or 22 mu m or less.
- alignment treatment of the alignment film formed on the spacer by adjusting the shape of the spacer to a specific shape can be performed uniformly without being influenced by the step difference of the spacer.
- the shape of the alignment layer can be further controlled.
- the cross-section of the alignment film may be a curved line in which the center of curvature is formed on the outer side of the cross-section, as shown in Figs. 13 and 14, the region facing upward from a point of contact with the base layer in the cross-
- This shape can be formed, for example, in accordance with the shape of the spacer and the formation conditions of the orientation film.
- the base layer may include a plurality of spacers by including the same or different spacers, including hemispherical spacers as mentioned above. Such a plurality of spacers may be disposed on the base layer at the same time with predetermined regularity and irregularity. Specifically, at least a part of the plurality of spacers on the base layer is irregular in terms of being arranged so as to have mutually different pitches, but it may be regular in terms of being arranged with substantially the same density between regions determined according to a predetermined rule .
- At least some of the spacers disposed on the substrate layer may be arranged to have different pitches from one another.
- pitch can be defined as the length of the side of the closed figure when a part of the plurality of spacers is selected so as to form a closed figure in which no other spacer is present therein. Unless otherwise specified, the unit of the pitch is ⁇ .
- the formed figure to be formed may be triangular, square or hexagonal. That is, when three arbitrary spacers among a plurality of spacers are selected and connected to each other, the triangle is formed. When the four spacers are selected and connected to each other, the square is formed, and the six spacers are selected, When connected, the hexagon is formed.
- Fig. 15 is an example of a quadrilateral which is a closed figure formed by arbitrarily selecting four spacers among the spacers (black dots) existing on the base layer and connecting them with imaginary lines (dotted lines). However, in the case where spacers are formed so that other spacers are present in the inside as shown in FIG. 16, for example, as shown in FIG. 16, It is excluded at the time of decision.
- the ratio (%) of the number of sides having the same length among the sides of the triangle, quadrangle, or hexagon, which is the closed figure formed as described above (100 x (number of sides of the same length) 100 ⁇ (number of sides of the same length) / 4 in the case of hexagonal, and 100 ⁇ (number of sides of the same length) / 6 in the case of a hexagon can be 85% or less.
- the ratio may be 84% or less, 80% or less, 76% or less, 67% or less, 55% or 40% or less.
- the lower limit of the ratio is not particularly limited. That is, in some cases, since the lengths of all sides of the closed diagram may not be the same, the lower limit of the ratio may be 0%.
- the arrangement of the spacers of the present application is irregular in that at least some of them have different pitches, but this irregularity is controlled under a certain regularity.
- the regularity described above may mean that the arrangement density of the spacers is substantially close to each other in a certain region.
- the normal pitch of the plurality of irregularly arranged spacers is P
- a plurality of square regions having a length of one side of 10P on the surface of the substrate layer are arbitrarily selected.
- the standard deviation of the number of spacers is 2 or less.
- Fig. 17 is a diagram exemplarily showing a case where four square regions (dotted rectangle regions) having a length of one side of the above 10P are arbitrarily selected.
- normal pitch means that a plurality of spacers arranged on the base layer in an irregular manner are arranged so that virtually all of the spacers are arranged at the same pitch in consideration of the number of the spacers and the area of the base layer, Means the distance between the centers of the spacers.
- the standard deviation is a numerical value indicating the scattering degree of the number of the spacers, and is a numerical value determined by the square root of the amount of dispersion.
- a standard deviation of the number of spacers existing in the region after designating at least two or more of the square regions is arbitrarily set on the surface on which the spacer of the base layer is formed, its standard deviation is 2 or less.
- the standard deviation may be 1.5 or less, 1 or less, or 0.5 or less in other examples.
- the lower limit of the standard deviation means that the desired regularity is achieved as the numerical value is lower, so that the lower limit is not particularly limited and may be zero, for example.
- the number of the rectangular areas specified above is not particularly limited as long as the number of the rectangular areas is two or more, in an example, the rectangular areas are arbitrarily selected so as not to overlap each other on the surface of the base layer, At least about 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% of the total area of the substrate layer have.
- the range of the normal pitch P forming one side of the arbitrary rectangular area is not particularly limited as long as it can be determined by the number of spacers present on the base layer and the area of the base layer as described above, In the range of about 100 mu m to 1,000 mu m.
- the average number of spacers present in the randomly selected square regions as described above may be, for example, about 80 to about 150.
- the average number may be 82 or more, 84 or more, 86 or more, 88 or more, 90 or more, 92 or more, 94 or more, 96 or 98 or more.
- the average number is 148 or less, 146 or less, 144 or less, 142 or less, 140 or less, 138 or less, 136 or less, 134 or less, 132 or less, 130 or less, 128 Or less, 126 or less, 124 or less, 122 or less, 120 or less, 118 or less, 116 or less, 114 or less, or 112 or less.
- the ratio SD / A of the average number A of the spacers to the standard deviation SD mentioned above may be 0.1 or less. In other examples, the ratio may be 0.09 or less, 0.08 or less, 0.07 or less, 0.06 or less, 0.05 or less, 0.04 or less, or 0.03 or less.
- the average number (A) and the ratio (SD / A) may be changed depending on the case.
- the transmittance, the cell gap, and / or the uniformity of the cell gap required in the device to which the substrate is applied The above values may be changed.
- the standard deviation of the number of the spacers in each unit region may be 2 or less.
- the standard deviation thereof is 2 or less.
- the shape of each divided unit area is not particularly limited as long as the unit areas are divided so as to have the same area, but may be, for example, a triangular, square, or hexagonal area.
- the standard deviation in the above state may be 1.5 or less, 1 or less, or 0.5 or less in other examples, and the lower limit thereof is not particularly limited as described above, and may be 0, for example.
- the number of unit regions is not particularly limited, but in one example, the base layer may be divided into two or more, four or more, six or more, eight or more, or ten or more regions having the same area.
- the average number of the spacers existing in the area is 0 to 4 It can be in range.
- the average number may be 3.5 or less, 3 or less, 2.5 or less, 2 or less, or 1.5 or less in other examples.
- the average number may also be greater than or equal to 0.5 in other examples.
- the number of square regions having a normal pitch P of one side arbitrarily specified is not particularly limited as long as the number of square regions is two or more.
- the square regions are arbitrarily selected so as not to overlap each other on the surface of the base layer,
- the area occupied by the randomly selected area is at least about 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% Or more.
- the total density of the plurality of spacers can be adjusted so that the ratio of the area occupied by the spacers to the entire area of the base layer is about 50% or less. In another example, less than or equal to about 45%, less than or equal to about 40%, less than or equal to about 35%, less than or equal to about 30%, less than or equal to about 25%, less than or equal to about 20%, less than or equal to about 15%, less than or equal to about 10% , Not more than 9%, not more than 8.5%, not more than 8%, not more than 7.5%, not more than 7%, not more than 6.5%, not more than 6%, not more than 5.5%, not more than 5%, not more than 4.5% Or less, 2.5% or less, 2% or less, or 1.5% or less. In another example, the ratio may be about 0.1% or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more or 0.95% or more.
- the spacers are formed so as to maintain the uniform cell gap between the substrates, while ensuring uniform optical characteristics without causing so- can do.
- the above numerical values can be changed when necessary, for example, the numerical values can be changed in consideration of the transmittance, the cell gap, and / or the uniformity of the cell gap required in the device to which the substrate is applied .
- the plurality of spacers may be arranged such that the spacing normal distribution diagram represents a predetermined shape.
- the spacing normal distribution diagram is a distribution diagram showing the pitch between the spacers as the X-axis and the ratio of the spacers having the corresponding pitches as the Y-axis among all the spacers, wherein the ratio of the spacers was 1 It is the ratio that is obtained when.
- the pitch in the description related to the above-described spacing normal distribution is the length of the side in a triangle, square, or hexagon, which is the above-mentioned closed shape.
- the distribution diagram can be obtained by using a known random number coordinate program, for example, a CAD, MATLAB or STELLA random number coordinate program or the like.
- the plurality of spacers may be arranged such that the half height area in the distribution diagram is in the range of 0.4 to 0.95.
- the half height area may be 0.6 or more, 0.7 or more, or 0.85 or more in other examples.
- the half height area may be 0.9 or less, 0.85 or less, 0.8 or less, 0.75 or less, 0.7 or less, 0.65 or less, 0.6 or less, 0.55 or less or 0.5 or less in another example.
- the plurality of spacers may be arranged such that the ratio (FWHM / Pm) of the half height width (FWHM) to the average pitch (Pm) in the distribution diagram is 1 or less.
- the ratio (FWHM / Pm) may be 0.05 or more, 0.1 or more, 0.11 or more, 0.12 or more, or 0.13 or more in another example.
- the ratio FWHM / Pm is about 0.95 or less, about 0.9 or less, about 0.85 or less, about 0.8 or less, about 0.75 or less, about 0.7 or less, about 0.65 or less, about 0.6 or less, about 0.55 or less, About 0.5 or less, about 0.45 or less, or about 0.4 or less.
- the average pitch Pm is defined by the spacers selected when at least 80%, at least 85%, at least 90% or at least 95% of the spacers are selected to form the triangular, square or hexagonal shape as described above. Is the average of the length of each side of a triangle, square, or hexagon. Also, in the above, the spacers are selected such that the triangles, squares or hexagons formed do not share vertices with each other.
- the plurality of spacers may be arranged such that the half height width (FWHM) in the above distribution diagram is in the range of 0.5 mu m to 1,000 mu m.
- the half height width FWHM may be at least about 1 ⁇ , at least 2 ⁇ , at least 3 ⁇ , at least 4 ⁇ , at least 5 ⁇ , at least 6 ⁇ , at least 7 ⁇ , at least 8 ⁇ , 15 mu m or more, 16 mu m or more, 17 mu m or more, 18 mu m or more, 19 mu m or more, 20 mu m or more, 21 mu m or more, 22 mu m or more, 23 mu m or more, or 24 mu m or more.
- the half height width is about 900 ⁇ ⁇ , 800 ⁇ ⁇ , 700 ⁇ ⁇ , 600 ⁇ ⁇ , 500 ⁇ ⁇ , 400 ⁇ ⁇ , 300 ⁇ ⁇ , 200 ⁇ ⁇ , Or less, 90 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, 60 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, or 30 ⁇ m or less.
- the plurality of spacers may be arranged such that the maximum height (Fmax) of the spacing normal distribution is at least 0.006 and less than 1.
- the maximum height Fmax may be about 0.007 or more, about 0.008 or more, about 0.009 or more, or about 0.0095 or more in other examples.
- the maximum height Fmax is about 0.9 or less, about 0.8 or less, about 0.7 or less, about 0.6 or less, about 0.5 or less, about 0.4 or less, about 0.3 or less, about 0.2 or less, about 0.1 or less, About 0.08 or less, about 0.07 or less, about 0.06 or less, about 0.05 or less, about 0.04 or less, about 0.03 or less, or about 0.02 or less.
- the spacers When a plurality of spacers are arranged to have a spacing normal distribution of the above-described type, when the optical device is implemented through the substrate, the spacers maintain a uniform cell gap between the substrates while causing a so- So that uniform optical characteristics can be ensured.
- the normal arrangement state is a state in which a plurality of spacers are arranged on the base layer so as to form an equilateral triangle, a square, or a regular hexagon having the same length on all sides.
- 19 is a state in which spacers are arranged to form the square as an example.
- the length P of one side of the square in this state may be equal to the normal pitch mentioned above.
- a circle area having a radius having a length proportional to the length P of one side is designated on the basis of a point where one spacer exists, and the one spacer is randomly
- the program is set to move to For example, FIG.
- FIG. 19 schematically shows a form in which a circle area having a radius of 0.5% of a length of 50% of the length P is set and the spacer moves to an arbitrary point in the area.
- the above arrangement can be achieved by applying the above movement to spacers of at least 80%, 85%, 90%, 95% or 100% (all spacers).
- the ratio to the length P which is the radius of the original area
- the ratio to the length P can be defined to be irregular.
- the irregularity degree is about 50%.
- the irregularity in the design scheme is at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35% , About 45% or more, about 50% or more, about 55% or more, about 60% or more, or about 65% or more. In one example, the irregularity may be about 95% or less, about 90% or less, about 85% or less, or about 80% or less.
- the steady state starts from a square.
- the steady state may be another shape such as an equilateral triangle or a regular hexagon. In this case, the above arrangement can also be achieved.
- the means for designing the arrangement of the spacers in the above manner is not particularly limited, and a known random number coordinate program, for example, a CAD, MATLAB, STELLA or Excel random number coordinate program can be used.
- a mask having a pattern according to the design may be manufactured, and the spacer may be implemented by applying the mask to the lithography or imprinting method described above have.
- the present application is also directed to an optical device formed using such a substrate.
- An exemplary optical device of the present application may include a second substrate opposing the substrate and the substrate and spaced apart from the substrate by a spacer of the substrate.
- a light-modulating layer may be present in an interval between the two substrates.
- the term optical modulation layer in the present application may include all known types of layers capable of changing at least one of the characteristics such as the polarization state, transmittance, color tone, and reflectance of the incident light according to purposes.
- the light modulating layer may be a liquid crystal layer that is switched between a diffusion mode and a transmissive mode by on-off of a voltage, for example, a vertical electric field or a horizontal electric field, A liquid crystal layer switched between a transmissive mode and a cut-off mode, a liquid crystal layer switched between a transmissive mode and a color mode, or a liquid crystal layer switching between color modes of different colors.
- a light modulating layer for example, a liquid crystal layer, capable of performing the above-described actions is variously known.
- a liquid crystal layer used in a typical liquid crystal display.
- the light modulating layer may include various types of so-called guest host liquid crystal layers, polymer dispersed liquid crystals, pixel-isolated liquid crystals, A particle device (Suspended Particle Deivice) or an electrochromic device.
- the polymer dispersed liquid crystal layer is a superordinate concept including a pixel isolated liquid crystal (PILC), a polymer dispersed liquid crystal (PDLC), a polymer network liquid crystal (PNLC), a polymer stabilized liquid crystal .
- the polymer dispersed liquid crystal layer (PDLC) may include, for example, a polymer network and a liquid crystal region containing a liquid crystal compound that is dispersed in a state of being phase-separated from the polymer network.
- optical modulation layer is not particularly limited, and any known method may be employed without any limitations depending on the purpose.
- the optical device may further include additional known functional layers such as a polarizing layer, a hard coating layer, and / or an antireflection layer, if necessary.
- additional known functional layers such as a polarizing layer, a hard coating layer, and / or an antireflection layer, if necessary.
- the present application is directed to a substrate on which a specific type of spacer is formed, a substrate comprising an orientation film formed on the spacer, and an optical device using such a substrate.
- a substrate on which a specific type of spacer is formed a substrate comprising an orientation film formed on the spacer, and an optical device using such a substrate.
- by controlling the shape of the spacer formed on the substrate even when the alignment film is formed on the alignment film and the alignment treatment is performed on the alignment film, uniform alignment treatment can be performed without being affected by the step difference of the spacer, A substrate or the like capable of providing a device can be provided.
- 1 to 4 are schematic views of the shape of the spacer of the present application.
- 5 to 10 are views for explaining the shape of the spacer of the present application.
- FIG. 11 is a view showing the shape of a mask which can be used for manufacturing the spacer of the present application according to an example.
- FIG. 12 is a schematic diagram of a process of fabricating a spacer using the mask shown in FIG.
- FIG. 13 and 14 are schematic diagrams of the cross section of the alignment film formed on the spacer.
- 15 to 17 are views for explaining the pitch between the spacers.
- 18 is an illustration of a distribution diagram of spacers.
- 19 is a diagram for explaining a method of implementing the irregularity degree.
- Fig. 20 and 22 are photographs showing the shape of the spacer manufactured in the embodiment, and Fig. 21 is a photograph showing the case where an alignment film is formed on the spacer in Fig.
- 23 to 25 are diagrams comparing the performance of the device of Example 7 and Comparative Example 1.
- a concave portion 9011 is formed in a PET (poly (ethylene terephthalate)) body 901, and a light-shielding layer (AlO x N y) is formed on a surface on which the concave portion 9011 is not formed. (902) and then forming a release layer on the light-shielding layer (902) and the recess (9011).
- the concave portion was formed in a hemispherical shape having a width of approximately 24 ⁇ to 26 ⁇ and approximately 9 ⁇ to 10 ⁇ .
- the concave portion was formed such that the arrangement of the spacers was such that the degree of irregularity described in FIG. 19 was about 70%.
- a crystalline ITO (Indium Tin Oxide) electrode layer was formed on a PC (polycarbonate) base layer (100 in FIG. 10), and a light shielding layer was formed thereon with a known material. Subsequently, about 2 to 3 mL of a mixture (UV resin) of a conventional ultraviolet curing type acrylate-based binder and an initiator used for manufacturing a column space was dropped on the light-shielding layer of the substrate layer. The mixture is then pressed with the imprinting mask to form a laminate including a base layer, an electrode layer, a light-shielding layer, a UV resin layer, and an imprinting mask layer, and the UV resin layer is cured . Through such a process, the condensing effect of the lens by the concave pattern of the mask 900 can be obtained, and the degree of curing of the cured portion can be increased.
- UV resin ultraviolet curing type acrylate-based binder and an initiator used for manufacturing a column space
- the uncured UV resin layer 200 is removed (developed), and the light shielding layer at the site where the uncured UV resin layer is removed is removed (etched) to form a semi-spherical shape on the ITO electrode layer and the shielding layer of the PC substrate layer Thereby forming spacers.
- FIG. 20 shows a photograph of a hemispherical spacer manufactured in the above manner.
- the hemispherical spacer shown in FIG. 20 had a hemispherical cross-section with a height of about 10 ⁇ m, a width of about 25 ⁇ m, and a maximum curvature of about 80 mm -1 . Further, the total height of the spacer was about 12 ⁇ to 13 ⁇ , and the width was about 25 ⁇ .
- a conventional polyimide rubbing alignment film was coated on a substrate layer having a spacer as shown in Fig. 20, and rubbed to form an alignment film.
- 21 is a view of an orientation film formed on the spacer as described above, and has a width of about 29 ⁇ and a height of about 11.5 ⁇ .
- a hemispherical spacer was prepared in the same manner as in Example 1 except that the hemispherical spacer having five different heights of all the spacers was prepared by controlling the degree of squeezing of the imprinting mask.
- the performance was compared using the substrate on which the alignment film prepared in Example 1 was formed and the substrate to which the conventional ball spacer as the spacer was applied.
- the other conditions are the same except that the spacer and the ball spacer prepared in Example 1 are used as the spacer and the ball spacer, respectively.
- FIG. 23 shows the result of evaluating the light leakage in the light shielding state when the substrate of Example 1 was applied
- FIG. 24 shows the results of evaluating light leakage in the light shielding state of the device using the substrate to which the ball spacer was applied (Comparative Example 1) Results. 23 and 24, it can be confirmed that the generation of light leakage is suppressed by the uniform alignment treatment in the case of this embodiment.
- Example 25 shows the results of evaluating the initial transmittance, the driving haze, the contrast ratio, and the image visibility of the device (CS, Example 7) to which the substrate of Example 1 was applied and the device (Ball (Comparative Example 1) , And it can be seen that the case of Example 7 shows better performance.
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Abstract
Description
Claims (15)
- 기재층 및 상기 기재층상에 존재하는 스페이서로서, 상부에 반구부를 가지는 반구형 스페이서를 포함하는 기판.
- 제 1 항에 있어서, 반구부의 단면 궤적의 최대 곡률이 2,000 mm-1 이하인 기판.
- 제 2 항에 있어서, 반구부의 단면 궤적은 곡률이 0 mm-1인 궤적을 포함하지 않는 기판.
- 제 1 항에 있어서, 반구부의 높이는 1㎛ 내지 20㎛의 범위 내에 있는 기판.
- 제 1 항에 있어서, 반구부의 폭은 2㎛ 내지 40㎛의 범위 내에 있는 기판.
- 제 1 항에 있어서, 스페이서의 높이가 1㎛ 내지 50㎛의 범위 내에 있는 기판.
- 제 1 항에 있어서, 스페이서의 하부에는 그 단면 궤적이 곡률 중심이 상기 단면의 외부에 형성되는 곡선 형태인 테이퍼부가 형성되어 있는 기판.
- 기재층; 상기 기재층상에 존재하는 스페이서; 및 상기 기재층과 스페이서상에 형성된 배향막을 포함하는 기판으로서,상기 스페이서상에 형성된 배향막의 상부가 반구 형태를 가지는 기판.
- 제 8 항에 있어서, 반구 형태의 단면 궤적의 최대 곡률이 2,000 mm-1 이하인 기판.
- 제 9 항에 있어서, 반구 형태의 단면 궤적은 곡률이 0 mm-1인 궤적을 포함하지 않는 기판.
- 제 8 항에 있어서, 스페이서상에 형성된 배향막의 높이가 1㎛ 내지 50㎛의 범위 내인 기판.
- 제 8 항에 있어서, 스페이서상에 형성된 배향막의 폭이 1㎛ 내지 80㎛의 범위 내인 기판.
- 제 1 항 또는 제 8 항에 있어서, 기재층상에 존재하는 복수의 스페이서가 존재하고, 상기 복수의 스페이서들 중 임의로 3개, 4개 또는 6개의 스페이서들을 선택하되, 상기 선택된 스페이서들이 내부에 다른 스페이서가 존재하지 않는 폐도형인 삼각형, 사각형 또는 육각형을 형성하도록 선택하였을 때에 상기 삼각형, 사각형 또는 육각형의 변의 길이들 중 적어도 하나가 상이하게 되도록 상기 스페이서들이 배치되어 있으며, 상기 복수의 스페이서들의 정상 피치가 P인 경우, 10P를 한변의 길이로 하는 정사각형 영역 내의 상기 스페이서의 개수들의 표준 편차가 2 이하인 기판.
- 제 1 항 또는 제 8 항의 기판 및 상기 기판과 대향 배치되어 있고, 상기 기판의 스페이서에 의해 상기 기판과의 간격이 유지된 제 2 기판을 포함하는 광학 디바이스.
- 제 14 항에 있어서, 기판 사이의 간격에는 액정 물질이 존재하는 광학 디바이스.
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EP18824235.8A EP3647862B1 (en) | 2017-06-30 | 2018-06-29 | Process for preparing a substrate for an optical device |
JP2019571601A JP2020525834A (ja) | 2017-06-30 | 2018-06-29 | 基板 |
CN201880039546.4A CN110770646B (zh) | 2017-06-30 | 2018-06-29 | 基板 |
US16/722,916 US11493807B2 (en) | 2017-06-30 | 2019-12-20 | Substrate |
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CN115826301A (zh) * | 2022-12-21 | 2023-03-21 | 广州华星光电半导体显示技术有限公司 | 液晶显示面板及其制作方法、液晶显示装置 |
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US20200124894A1 (en) | 2020-04-23 |
JP2020525834A (ja) | 2020-08-27 |
CN110770646B (zh) | 2023-07-14 |
EP3647862B1 (en) | 2024-04-03 |
CN110770646A (zh) | 2020-02-07 |
KR102166474B1 (ko) | 2020-10-16 |
EP3647862A1 (en) | 2020-05-06 |
US11493807B2 (en) | 2022-11-08 |
KR20190003053A (ko) | 2019-01-09 |
EP3647862A4 (en) | 2020-06-03 |
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