WO2022138197A1 - 隔壁付き基板、波長変換基板、および、ディスプレイ、ならびに、波長変換基板の製造方法 - Google Patents
隔壁付き基板、波長変換基板、および、ディスプレイ、ならびに、波長変換基板の製造方法 Download PDFInfo
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Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- 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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/1201—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/351—Thickness
Definitions
- the present invention relates to a substrate with a partition wall, a wavelength conversion substrate, a display, and a method for manufacturing a wavelength conversion substrate.
- OLED displays use an organic light emitting diode (OLED) or light emitting diode (LED) driven by an active matrix as a light source, and display at least a part of the light in full color by changing it with a wavelength conversion material.
- OLED organic light emitting diode
- LED light emitting diode
- These displays are characterized by the fact that multiple panels made in units can be combined in any shape and joined together, and the image can be controlled by a controller or the like to form a display of any size and resolution. It is called technology.
- Patent Document 1 As a method of using an OLED as a light source, a method of using an OLED that emits blue light is known (Patent Document 1). In this case, in the blue subpixel, the light from the OLED is transmitted and scattered without wavelength conversion, and in the green and red subpixels, the blue light from the OLED is converted into green and red by the wavelength conversion material, respectively. It is transparent.
- a blue light emitting LED is used as in the OLED, and in addition to a method of converting a part of light into red and green with a wavelength conversion material, an ultraviolet light emitting LED is used as a wavelength conversion material.
- An ultraviolet light emitting LED is used as a wavelength conversion material.
- the wavelength conversion material In these wavelength conversion type displays, it is necessary to arrange the wavelength conversion material in a pattern with a size corresponding to the OLED which is the light source and the subpixel of the LED.
- a photolithography method and an inkjet method Patent Document 3
- the wavelength conversion material is applied to the entire surface, exposed at a predetermined position, and then most of the material is removed by development. Therefore, the loss of the wavelength conversion material is large, and the process also repeats exposure and development multiple times. There were challenges that were necessary and complicated.
- the inkjet method is excellent in material efficiency because the wavelength conversion layer can be formed only at a desired position.
- FIG. 1 shows a schematic diagram showing a method of applying the wavelength conversion paste by the nozzle application method.
- the nozzle coating method has a space (manifold) for storing the paste 2 inside the coating head 1, and while relatively moving the coating head 1 facing the substrate 3, the pressurized pipe 4 connected to the space.
- this pixel is filled with a coating liquid corresponding to red, green, and blue, and each pixel functions as a sub-pixel, and each sub-pixel is collectively one pixel. It becomes.
- the viscosity of the paste can be higher than that of the inkjet method. Therefore, by designing the viscosity higher, it is possible to suppress the clogging of the nozzle due to the sedimentation of the particle components, so it is especially used in the coating of paste containing particles. ing.
- the partition walls that partition the wavelength conversion materials of each color are becoming thinner.
- a fine line pattern having a partition wall width of 20 ⁇ m or less is formed by a photolithography method, the adhesion between the partition wall and the base substrate is insufficient due to the thinning, and the partition wall is peeled off from the base during development. Occurs. This problem is particularly likely to occur at the outer periphery of the pattern. Therefore, it is conceivable to make the width of the partition wall constituting the outer peripheral portion of the pattern relatively thicker than the width of the partition wall existing inside.
- the discharge amount may not be stable immediately after the start of discharge of the coating liquid, so coating is performed up to the space (opening 7) surrounded by the partition wall used as a pixel in actual use.
- the discharge of the liquid is started. That is, the coating is started from the time point up to the outer peripheral portion of the region where the partition wall is provided. At this time, if the thickness of the partition wall constituting the outer periphery of the area where the partition wall is provided is thicker than the width of the inner partition wall, the coating liquid rides on the partition wall having the thick width, and the state continues for a while.
- the thick partition wall constituting the outer circumference is present, and the thick partition wall constituting the outer periphery is present at the jointed portion. Since they are joined to each other, the area of the non-pixel portion becomes large, and there is a problem that the joined portion is visually recognized as uneven when displaying on a display.
- the substrate with a partition wall of the present invention has the following configuration. That is, it is a substrate with a partition wall having a substrate and a partition wall in which a pattern is formed on the substrate, and the cells partitioned by the partition wall have a region arranged in a grid pattern, and the outer edge of the region is formed.
- the outermost partition wall formed or formed to surround the region has a width wider than the width of the partition wall forming other than the outer edge of the region, and is on an extension of the row of the grid array.
- a substrate with a partition wall that has a portion lower in height than the other portion on at least one side intersecting with the other portion and the portion lower in height than the other portion satisfies the following (1) or (2). ,. (1) When connected to a cell, the width at the connection portion shall be narrower than the width of the cell. (2) When not connected to a cell, the area should be larger than the area of the nearest cell.
- one of the preferred embodiments of the substrate with a partition wall of the present invention is a substrate with a partition wall satisfying the above (2), and the maximum width of a portion having a lower height than other parts of the partition wall located on the outermost side is set. It is a substrate with a partition wall, which is 98% or less of the width of the partition wall located on the outermost side corresponding to the portion having a height lower than the other portion showing the maximum width.
- one of the preferred embodiments of the substrate with a partition wall of the present invention is that the partition wall located on the outermost side is higher in the partition wall in a direction orthogonal to the extension line of the row of the grid-like arrangement than the other parts.
- the width of the portion where the proportion of the low portion of the portion is 50% or more and the proportion of the portion having a lower height than the other portion is 50% or more is the partition wall in which the portion is present. It is a substrate with a partition wall, which is 20% or less of the width of the above.
- a material for a display device such as a light emitting material or a wavelength conversion material such as a phosphor is used by reducing the variation in the film thickness of the material filled in the cells partitioned by the partition wall. In that case, it is possible to provide a display device having little variation in brightness and high display quality.
- the substrate with a partition wall of the present invention has a substrate and a partition wall.
- the substrate has a function as a support in a substrate with a partition wall.
- the substrate include a glass plate, a resin plate, a resin film, and the like. Further, these may be provided with a functional layer such as a color filter.
- a functional layer such as a color filter.
- the material of the glass plate non-alkali glass is preferable.
- the material of the resin plate and the resin film polyester, (meth) acrylic polymer, transparent polyimide, polyether sulfone and the like are preferable.
- the thickness of the glass plate and the resin plate is preferably 1 mm or less, preferably 0.8 mm or less.
- the thickness of the resin film is preferably 100 ⁇ m or less.
- the substrate with a partition wall has a partition wall on the substrate.
- the surface of the substrate on the side having the partition wall has cells partitioned by the partition wall, and the cells are opened on the surface surrounded by the top of the partition wall so that the fluorescent substance paste or the like can be filled. is doing.
- the cells partitioned by the partition wall are arranged in a grid pattern. It is planned that the region in which the cells are arranged in a grid pattern will be a region corresponding to pixels when the wavelength conversion substrate is used.
- the grid-like arrangement refers to an arrangement having at least one set of parallel-arranged partition walls in a group of cells arranged on a substrate surface. With such a grid-like arrangement, the wavelength conversion layer can be easily formed by the nozzle coating method by sweeping the nozzle while discharging the coating material in parallel with the partition walls arranged in parallel.
- the parallelism in the group of partition walls arranged in parallel is completely parallel, but when the nozzle for discharging the object to be coated is swept along the partition wall, the cell to be coated has an object to be coated. It is permissible for the bulkhead to be serpentine, curved or skewed to the extent that it can be filled.
- the outermost partition wall formed so as to form the outer edge of the region in which the cells are arranged in a grid pattern or to surround the region is other than the outer edge of the region. It has a width wider than the width of the partition wall forming the above (hereinafter, the outermost partition wall is referred to as a "frame portion" for convenience).
- FIG. 2 shows an enlarged view of the vicinity of the frame portion of the substrate with a partition wall in which the width of the outer edge portion (corresponding to the frame portion) of the group of cells partitioned by the conventional partition wall is larger than the width of the partition wall existing between the cells.
- the partition wall 6 is a color element in which cells are partitioned corresponding to each pixel of a red pixel (10R), a green pixel (10G), and a blue pixel (10B), and each pixel is grouped together. That is, the partition wall pattern portion 8 is formed as a pixel pattern in which pixels (referred to as RGB pixels (10) for convenience) are arranged at an arbitrary pitch.
- a frame portion 9 is provided on the outermost circumference of the partition wall pattern so as to surround the inner cell. Further, the substrate with a partition wall has a region where no partition wall is formed on the outside of the frame portion 9. In the present invention, the region where the outer partition wall of the frame portion 9 is not formed is referred to as a non-pixel portion (non-pixel portion 12) for convenience.
- the cells are arranged in a grid pattern, and when the outer shape of the cells is rectangular when viewed from the upper surface, it is stable to apply the cells in the long side direction using a nozzle. It is preferable from the viewpoint of sex. Therefore, in each figure, the coating material is discharged from the side of the region where the partition wall is not provided, in parallel with the partition wall forming the long side of the cell (hereinafter, may be referred to as “vertical partition wall” for convenience). The following will be described with reference to an example on the premise that the nozzle is swept and the coating is performed.
- the inner dimension width in the direction orthogonal to the vertical partition wall is defined as the cell horizontal width WA
- the internal dimension in the direction parallel to the vertical partition wall is defined as the cell vertical width LA .
- the width of the partition wall between adjacent cells is defined as the cell spacing wall width LB.
- the areas of the red pixels (10R), the green pixels (10G), and the blue pixels ( 10B ) are set to SR, SG, and SB, respectively, and the minimum value among the areas of the RGB pixels is the cell minimum area S. Let it be RGB MIN .
- the width of the partition wall located on the outermost side (frame portion) that the nozzle first reaches is defined as the frame portion vertical width LF (see FIG. 2).
- the frame portion vertical width LF see FIG. 2
- the columnar flow coating liquid from the nozzle runs on the frame portion 9, the coating liquid is disturbed, and the pixel film thickness at the pattern start portion fluctuates. Becomes larger.
- the width of the frame portion that also serves as the short side of the cell is about the same as the width of the partition wall that partitions the cells, that is, the cell spacing wall width (LB).
- the partition wall width As described above, in such a substrate with a partition wall, if a fine pattern having a partition wall width of 20 ⁇ m or less is used, the partition wall is peeled off during processing, which makes stable processing difficult.
- connection type buffer portion 13 the portion having a height lower than that of other portions of the frame portion.
- the frame portion 9 is the same.
- the portion is also connected to the outside of the region where the partition wall is provided, that is, the non-pixel portion 12.
- WF the width of the connection type shock absorber 13 is constant, but in that case, in order to reduce the change in coatability due to the application of the coating liquid on the frame portion 9, WF > ( WA /).
- WF ⁇ ( WA / 2) is further preferable in order to reduce the change in the filling amount of the coating liquid into the RGB pixels 10. Further, from the viewpoint of pattern workability and prevention of pattern peeling, it is preferable that WA > WF .
- connection type shock absorber 13 has a width narrower than the width of the connected cell at the portion (connection portion) connected to the cell, but is in the region where the partition wall is provided. It also has a widened part until it is connected to the outside.
- the width of the widest portion is the maximum value WF MAX of the width of the connection type buffer portion
- the width of the narrowest portion is the minimum value WF of the width of the connection type buffer portion.
- the vertical width ( LF ) of the frame portion is preferably LF > LB in order to maintain the pattern processability of the partition wall and the stability of coating, and LF ⁇ LA / 2. preferable.
- the height of the partition wall forming the frame portion corresponding to the connection type buffer portion 13 is lower, because the cushioning effect can be easily obtained, and it is 1 / of the height of the other portion of the partition wall forming the frame portion. It is usually 2 or less. This height is preferably 1/4 or less of the height of the other portion of the partition wall forming the frame portion, and most preferably the height is zero (that is, the substrate is exposed). The same can be said for the height of the partition wall forming the frame portion corresponding to the stand-alone shock absorber described later.
- the connected buffer or the stand-alone buffer described later When the connected buffer or the stand-alone buffer described later is connected to the cell or the non-pixel portion, and the height of the partition wall forming the frame portion corresponding to the connected buffer or the stand-alone buffer is zero. Is that the line segment connecting the ends of the frame portion on the connected cell side or the non-pixel portion side is the boundary between the connected buffer portion or the stand-alone buffer portion (and the relationship between the connected buffer portion and the cell). Connection).
- the connected buffer is connected to an adjacent (that is, provided corresponding to the adjacent pixel) connected buffer to form one connected buffer.
- the action of the stand-alone shock absorber described later can be further obtained, higher coating stability can be realized, and further, the thickness of the object to be coated to be filled in the cell is not sufficient. It is possible to suppress the uniformity, and when such a substrate with a partition wall is used as a wavelength conversion substrate, it is possible to prevent display unevenness on the outer peripheral portion of the display.
- the portion of the frame portion that is lower in height than the rest of the frame portion is not connected to the cell (stand-alone shock absorber 14).
- the stand-alone shock absorber 14 has an effect of substantially reducing the vertical width of the frame portion when focused on the sweep direction of the nozzle, and reduces the instability of coating due to the coating liquid from the nozzle riding on the frame portion. be able to.
- the area of the stand-alone shock absorber is larger than the cell minimum area ( SRGB MIN ), that is, it is preferable that SF> SRGB MIN .
- the width ( LBF ) of the partition wall separating the stand-alone shock absorber and the cell existing in the vicinity thereof is LBF > LB from the viewpoint of partition wall workability, and the coating instability due to the stand-alone shock absorber 14 It is preferable that LBF ⁇ LA / 2 so as not to hinder the effect of reduction.
- the maximum value ( LFO ) of the width of the stand-alone shock absorber 14 is 98% or less of the vertical width ( LF ) of the frame portion in which the stand-alone shock absorber 14 exists. Is preferable. By doing so, it is possible to suppress the peeling of the pattern from the frame portion provided with the independent buffer portion 14, and to suppress the decrease in the yield.
- the ( LFO / LF ) is more preferably 95% or less, still more preferably 90% or less.
- the stand-alone shock absorber 14 may be surrounded on all sides by a partition wall, but as shown in FIGS. 10 and 11, the wall forms a wall on the side opposite to the side where the partition wall constituting the RGB pixel 10 is provided. The part does not have to exist.
- Such a configuration is effective in reducing the substantial width of the frame portion from the viewpoint of sweeping the nozzle while suppressing the peeling of the partition wall by the frame portion, and is extremely advantageous in stabilizing the coating.
- the height of the partition wall forming the frame portion corresponding to the stand-alone shock absorber 14 is 1/20 or more of the height of the other portion of the frame portion, which is a viewpoint of suppressing peeling of the partition wall. It is preferable from.
- the proportion of a portion having a lower height than other parts is 50% in the frame portion in the direction orthogonal to the extension line of the row of the grid-like arrangement intersecting the frame portion.
- the width of the portion having the above-mentioned portion and having a portion having a height lower than the other portion of 50% or more may be 20% or less of the width of the partition wall in which the portion exists. Preferred (hereinafter, such a portion may be referred to as a "split portion").
- the width of the cut portion is preferably 10% or less of the vertical width of the frame portion.
- FIG. 14 shows a groove having a cross-sectional shape of LD3 in which a square is added to the top of a trapezoidal cross section when viewed in a direction perpendicular to the extension line of a frame portion 9 intersecting on an extension line of a row of grid-like arrangements.
- a certain cutting groove portion 15 is provided (see the cross-sectional view taken along the line AA').
- the connection type buffer portion 13 or the strip-shaped portion which is the groove, that is, the split portion is present. Will be there.
- FIG. 15 is a modified example in which the frame portion 9 is provided with a groove having a semicircular cross-sectional shape.
- the partition wall thickness (HD) of the split groove portion 15 is the partition wall film thickness ( H ) of the frame portion from the viewpoint of further suppressing the partition wall of the frame portion from peeling from the base in the partition wall pattern developing step. It is preferable that 1/20 or more of F ), that is, HD > 1/20 HF . Further, in order to improve the cutting accuracy, HD ⁇ HF is preferable, and HD ⁇ 1 / 2HF is more preferable.
- FIG. 16 shows an example in which a split groove portion 15 having a rectangular opening in the shape of an opening is provided in a frame portion 9 intersecting on an extension line of a row of grid-like arrangements.
- the connection type buffer portion 13 or the portion of the opening having a rectangular hole occupies 50% or more.
- FIGS. 18 to 20 show an example in which the frame portion 9 intersecting on the extension line of the rows of the grid arrangement is in contact with the connection type shock absorber portion 13 and the frame portion 9 is provided with the split groove portion 15 which is a notch portion.
- the connection type buffer portion 13 when viewed in the direction perpendicular to the extension line of the row of the grid-like arrangement, it is a connection type buffer portion 13, or a strip-shaped portion in which the notched portion occupies 50% or more. (Refer to the AA'cross section in each figure), that is, there is a split portion. Since the strip-shaped portion has a width of 20% or less of the vertical width ( LF ) of the frame portion, it is easy to divide the strip-shaped portion.
- FIGS. 21 to 22 are examples in which the frame portion 9 has the independent cushioning portion 14, and in the example shown in FIG. 21, the description of the split portion is the same as that described in FIG. In the example shown in 22, the content described in FIG. 16 is incorporated.
- the portion of the frame that is in contact with the nearest cell is the upper end of the frame 20, and the boundary of the split groove 15 that is closer to the upper end of the frame is the upper end of the split groove 21.
- the width ( LD1 ) of the upper end portion 20 of the frame and the upper end portion 21 of the cutting groove is LB ⁇ from the viewpoint of improving the accuracy of cutting. It is preferably LD1 .
- the width ( LD2 ) of the upper end portion 20 of the frame and the lower end portion 22 of the cutting groove is preferably LD2 ⁇ LF from the viewpoint of improving the accuracy of cutting.
- L D2 ⁇ 1 / 2LF because it is possible to realize a display with less image deviation and unevenness across the substrate.
- the width from the upper end portion 21 of the splitting groove to the lower end portion 22 of the splitting groove is the splitting groove portion width ( LD3 )
- the ratio of the splitting groove portion width to the vertical width of the frame portion ( LD3 / LF ) as described above. ) Is preferably 20% or less, more preferably 10% or less.
- Examples of the method of cutting the substrate include scribing cutting and laser cutting.
- Examples of scribing cutting include wheel scribing and laser scribing.
- Examples of the laser cutting include cutting using a fiber laser, a YAG laser, a CO 2 laser, a UV laser, an excima laser, an LD laser, a nanosecond pulse laser, a picosecond pulse laser, and a femtosecond pulse laser. ..
- the substrate with a partition wall of the present invention can be preferably used as a member of a display device. It is preferable that each cell is provided as a pattern corresponding to a pixel. Examples of the number of pixels of the display include 2,000 pixels vertically and 4,000 pixels horizontally. The number of pixels affects the resolution (fineness) of the displayed image. Therefore, it is necessary to form a number of pixels according to the required image resolution and the screen size of the display, and it is preferable to determine the pattern formation dimension of the partition wall accordingly. Further, it is preferable that the partition wall has a liquid-repellent property so that the coating liquid applied by the nozzle coating method flows into the cell without remaining on the top of the partition wall.
- the partition wall When the partition wall is filled with a material (wavelength conversion material) that converts the wavelength of an electromagnetic wave into another wavelength to form a wavelength conversion layer, light is transmitted / scattered from one pixel to an adjacent pixel. It is preferable to have a function to prevent the above.
- a material wavelength conversion material
- the height of the partition wall is preferably larger than the thickness of the cured product of the wavelength conversion paste when the cured product of the wavelength conversion paste is contained in the cell of the substrate with the partition wall.
- the height of the partition wall 6 is preferably 0.5 ⁇ m or more, and more preferably 5 ⁇ m or more.
- the height of the partition wall is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less, still more preferably 50 ⁇ m or less, from the viewpoint of more efficiently extracting light emission at the bottom of the layer containing the wavelength conversion light emitting material.
- the cell spacing wall width may be sufficient to improve the brightness by utilizing the light reflection on the side surface of the partition wall and suppress the color mixing of the light emitted from the cured product of the adjacent wavelength conversion paste due to light leakage.
- the cell spacing wall width is preferably 0.5 ⁇ m or more, and more preferably 10 ⁇ m or more.
- the cells partitioned by the partition walls in the partition wall-equipped substrate may be filled with a wavelength conversion material.
- the wavelength conversion material refers to a material having a wavelength conversion property that absorbs an electromagnetic wave and emits an electromagnetic wave having a wavelength different from the wavelength of the absorbed electromagnetic wave.
- a wavelength conversion substrate containing a wavelength conversion material is patterned and applied to prepare a wavelength conversion substrate, which can be combined with an OLED light source or an LED light source to form a full-color display.
- an inorganic phosphor or an organic phosphor can be used as the wavelength conversion material.
- a red phosphor that is excited by blue excitation light and emits red fluorescence is placed in a region corresponding to the red subpixel. It is preferable to use it as a wavelength conversion material, and in the region corresponding to the green subpixel, it is preferable to use a green phosphor that is excited by blue excitation light and emits green fluorescence as a wavelength conversion material, and it is preferable to use a blue subpixel. It is preferable not to use a wavelength conversion material in the region corresponding to.
- the wavelength conversion substrate of the present invention can also be used for a display of a method using a blue LED or an ultraviolet light emitting LED corresponding to each subpixel as a backlight.
- the light emission of each subpixel can be turned ON / OFF by driving the OLED or the active matrix of the LED.
- the inorganic phosphor emits each color such as green and red.
- Inorganic phosphors include those excited by excitation light with a wavelength of 400 to 500 nm and having a peak in the emission spectrum in the region of 500 to 700 nm, and nanoscale particles having unique optical characteristics according to quantum mechanics called quantum dots. Examples include inorganic semiconductor fine particles. Examples of the shape of the former inorganic phosphor include a spherical shape and a columnar shape. Examples of such inorganic phosphors include YAG-based phosphors, TAG-based phosphors, sialon-based phosphors, Mn 4+ activated fluoride complex phosphors, and the like. Two or more of these may be used.
- the quantum dot material is preferable. Since quantum dots have sharper peaks in the emission spectrum than other phosphors, the color reproducibility of the display can be improved. By using quantum dots with a relatively small particle size of several nm, it is possible to suppress the residue of inorganic phosphor particles on the partition wall and improve the bonding accuracy when manufacturing panels. Become. Further, for the same reason, it is possible to improve the accuracy of splitting by using quantum dots.
- Examples of the material of the quantum dot include semiconductors of group II-IV, group III-V, group IV-VI, and group IV.
- Examples of these inorganic semiconductors include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, and the like.
- Quantum dots may contain a p-type dopant or an n-type dopant. Further, the quantum dots may have a core-shell structure. In the core-shell structure, any suitable functional layer (single layer or multiple layers) may be formed around the shell depending on the purpose, and the surface of the shell may be surface-treated and / or chemically modified. ..
- the shape of the quantum dot examples include a spherical shape, a columnar shape, a flaky shape, a plate shape, an amorphous shape, and the like.
- the average particle size of the quantum dots can be selected according to the desired emission wavelength, and is preferably 1 to 30 nm. When the average particle size of the quantum dots is 1 to 10 nm, the peak in the emission spectrum can be sharpened in each of blue, green and red. For example, when the average particle size of the quantum dots is about 2 nm, blue light is emitted, when it is about 3 nm, green light is emitted, and when it is about 6 nm, red light is emitted.
- the average particle size of the quantum dots is preferably 2 nm or more, and preferably 8 nm or less.
- the average particle size of the quantum dots can be measured by a dynamic light scattering method. Examples of the device for measuring the average particle size include a dynamic light scattering photometer DLS-8000 (manufactured by Otsuka Electronics Co., Ltd.).
- Examples of the organic phosphor include a phosphor that is excited by blue excitation light and emits red fluorescence, and a phosphor that is excited by blue excitation light and emits green fluorescence, such as a pyrromethene derivative.
- Other examples include a perylene-based derivative, a porphyrin-based derivative, an oxazine-based derivative, and a pyrazine-based derivative that emit red or green fluorescence depending on the selection of the substituent. Two or more of these may be contained.
- a pyrromethene derivative is preferable because of its high quantum yield.
- the pyrromethene derivative can be obtained, for example, by the method described in JP-A-2011-241160.
- the organic phosphor is soluble in a solvent, a layer containing a wavelength conversion material having a desired thickness can be easily formed.
- the wavelength conversion layer may contain light scattering particles.
- the light-scattering particles blue light and ultraviolet light are scattered in the wavelength conversion layer, so that the optical path length becomes long, and the light conversion efficiency of the wavelength conversion material can be improved.
- the light-scattering particles are preferably barium sulfate, aluminum oxide, zirconium oxide, zinc oxide, or titanium oxide. Two or more of these may be contained.
- the refractive index of the light-scattering particles at a wavelength of 587.5 nm is preferably 1.60 to 2.70.
- the refractive index of the light-scattering particles By setting the refractive index of the light-scattering particles to 1.60 or more, the scattering property of blue light in the wavelength conversion layer by the light-scattering particles is improved, and the light conversion efficiency by the wavelength conversion material is likely to be improved.
- the refractive index of the light-scattering particles to 2.70 or less, excessive scattering by the light-scattering particles is suppressed, and the emitted light after wavelength conversion can be easily taken out of the cell.
- the refractive index of at least one kind is in the above range.
- the content of the light-scattering particles is preferably 1% by weight or more, more preferably 5% by weight or more, and further preferably 10% by weight or more in the solid content from the viewpoint of further improving the light conversion efficiency.
- the content of the light-scattering particles is preferably 70% by weight or less, more preferably 60% by weight or less, and 50% by weight or less in the solid content from the viewpoint of suppressing the decrease in luminous efficiency due to the concentration quenching of the wavelength conversion material. Is even more preferable.
- the solid content here means all the components contained in the wavelength conversion paste, excluding the volatile components such as the solvent. The amount of solid content can be determined by heating the wavelength conversion paste at 150 ° C.
- the wavelength conversion layer is preferably formed by curing the wavelength conversion paste.
- the wavelength conversion paste is a paste material containing a wavelength conversion material, and can be easily applied to a substrate with a partition wall by a nozzle coating method by appropriately designing the composition.
- the method of curing the wavelength conversion paste is not particularly limited, but a method of curing a wavelength conversion paste containing a polymerizable compound with heat or light, or a method of volatilizing a solvent from a wavelength conversion paste containing a solvent to cure it. And so on.
- the wavelength conversion paste may contain a monomer as a polymerizable compound.
- the monomer in the present invention refers to a compound polymerized by an active species generated by the reaction of a polymerization initiator described later.
- the monomer used for the wavelength conversion paste is preferably a compound having an ethylenically unsaturated double bond in the molecule.
- the monomer preferably has two or more ethylenically unsaturated double bonds in the molecule.
- the monomer preferably has a (meth) acrylic group.
- the double bond equivalent of the monomer is preferably 400 g / mol or less from the viewpoint of further improving the sensitivity in pattern processing.
- Examples of the monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, diethylene glycol dimethacrylate, and triethylene.
- Glycol dimethacrylate tetraethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropanetriacrylate, trimethylolpropanedimethacrylate, trimethylolpropanetrimethacrylate, 1,3-butanediol diacrylate, 1, 3-Butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1 , 10-Decandiol Dimethacrylate, Dimethyrol-Tricyclodecanediacrylate, Pentaerythritol Triacrylate, Pentaerythritol Tetraacrylate, Pentaerythritol
- the content of the monomer in the wavelength conversion paste is preferably 1% by weight or more, more preferably 10% by weight or more, still more preferably 30% by weight or more in the solid content from the viewpoint of increasing the solid content ratio of the wavelength conversion paste.
- the content of the monomer is preferably 80% by weight or less, more preferably 70% by weight or less in the solid content.
- the wavelength conversion paste may contain a polymerization initiator.
- the polymerization initiator is reacted by light irradiation or heating, so that the polymerization of the monomer proceeds by the active species generated from the polymerization initiator, and the exposed portion of the wavelength conversion paste is exposed. Can be cured.
- the polymerization initiator may be any radical initiator or cation initiator, that is, any one that reacts with light (including ultraviolet rays and electron beams) or heat to generate active species such as radicals and cations. good. Among these, a radical initiator is preferable.
- the polymerization initiator include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-).
- ⁇ -Aminoalkylphenone compounds such as morpholin-4-yl-phenyl) -butane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2,4 , 6-trimethylbenzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) -phosphinoxide, etc.
- Phenylphenone compound 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, 4-azidobenzalacetopheno Acetphenone compounds such as 2-phenyl-2-oxyacetate compounds; ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (2-ethyl) hexyl, ethyl 4-diethylaminobenzoate, Examples thereof include benzoic acid ester compounds such as 2-benzoyl methyl benzoate. Two or more of these may be contained.
- the wavelength conversion paste contains 2,4,6-trimethylbenzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy) in order to suppress coloration caused by the polymerization initiator. It is preferable to contain an acylphosphine oxide-based polymerization initiator such as benzoyl)-(2,4,4-trimethylpentyl) -phosphine oxide.
- the content of the polymerization initiator in the wavelength conversion paste is preferably 0.01% by weight or more, preferably 0.1% by weight or more, based on the solid content, from the viewpoint of efficiently advancing the reaction by the polymerization initiator. More preferred.
- the content of the polymerization initiator is preferably 20% by weight or less, more preferably 10% by weight or less in the solid content.
- the wavelength conversion paste may appropriately contain a polymer, a solvent, a dispersant and the like.
- the polymer may be, for example, a silicon resin such as polyvinyl acetate, polyvinyl alcohol, ethyl cellulose, methyl cellulose, polyethylene, polymethyl siloxane or polymethyl phenyl siloxane, polystyrene, butadiene / styrene copolymer, polystyrene, etc.
- a silicon resin such as polyvinyl acetate, polyvinyl alcohol, ethyl cellulose, methyl cellulose, polyethylene, polymethyl siloxane or polymethyl phenyl siloxane, polystyrene, butadiene / styrene copolymer, polystyrene, etc.
- Preferred examples include polyvinylpyrrolidone, polyamide, high molecular weight polyether, copolymer of ethylene oxide and propylene oxide, polyacrylamide, acrylic resin and the like.
- the solvent may be, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2.
- -Alcohols such as butanol, 3-methyl-3-methoxy-1-butanol, diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether; methyl ethyl ketone, acetyl acetone, methyl Ketones such as propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; amide
- the viscosity of the wavelength conversion paste is 1 sec -1 when measured by attaching the Plate P35 Ti L manufactured by the same company to a rheometer (HAAKE MARS; Thermo Fisher Scientific Co., Ltd.) and setting the gap to 200 ⁇ m.
- the viscosity at the shear rate of is preferably 1,000 to 500,000 mPa ⁇ s. By setting the viscosity to 1000 mPa ⁇ s or more, even when the paste is stored for a long period of time after preparation, particle components such as (B) light-scattering particles are less likely to settle.
- the viscosity is more preferably 3,000 mPa ⁇ s or more, and further preferably 5,000 mPa ⁇ s or more.
- the viscosity is more preferably 400,000 mPa ⁇ s or less, and further preferably 300,000 mPa ⁇ s or less.
- the dispersant may be, for example, "Disperbyk” (registered trademark) 106, 108, 110, 180, 190, 2001, 2155, 140, 145 (hereinafter, trade name. Big Chemie). Co., Ltd.) and the like are preferable.
- the wavelength conversion substrate of the present invention is preferably produced by applying a wavelength conversion paste to the substrate with a partition wall of the present invention by a nozzle coating method and curing the substrate.
- the display device of the present invention has the wavelength conversion substrate and a light source.
- a light source selected from a blue OLED, a blue LED, and an ultraviolet light emitting LED capable of driving an active matrix is preferable.
- a photosensitive polyimide resin is applied onto a glass substrate having a TFT pattern capable of driving an active matrix, and an insulating film is formed by a photolithography method. After sputtering aluminum as the back electrode layer, patterning is performed by a photolithography method to form a back electrode layer in an opening without an insulating film.
- Alq 3 tris (8-quinolinolato) aluminum
- dicyanomethylenepyran, quinacridone, and 4,4'-bis were formed on Alq 3 as a light emitting layer.
- 2,2-Diphenylvinyl A white light emitting layer doped with biphenyl is formed.
- N, N'-diphenyl-N, N'-bis ( ⁇ -naphthyl) -1,1'-biphenyl-4,4'-diamine is formed as a hole transport layer by a vacuum vapor deposition method.
- ITO is formed into a film by sputtering as a transparent electrode to produce an OLED having a blue light emitting layer.
- a display can be manufactured by adhering the OLED thus obtained to face the above-mentioned wavelength conversion substrate with a sealing agent.
- the wavelength conversion board itself of the present invention may have an OLED or an LED.
- a display can be manufactured by sequentially forming a partition wall and a wavelength conversion layer on a substrate having an OLED or an LED.
- the solid content concentration of the polysiloxane solution was determined by the following method. 1.5 g of the polysiloxane solution was weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid. The weight of the solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration of the polysiloxane solution was determined from the ratio to the weight before heating.
- the weight average molecular weight of polysiloxane was determined by the following method. Using a gel permeation chromatography (GPC) device (HLC-8220; manufactured by Toso Co., Ltd.) and using tetrahydrofuran as a fluidized layer, "JIS K 7252-3 (established date: March 20, 2008). GPC analysis was performed based on "day)", and the polystyrene-equivalent weight average molecular weight was measured.
- GPC gel permeation chromatography
- the content ratio of each repeating unit in polysiloxane was determined by the following method. A polysiloxane solution is injected into a 10 mm diameter "Teflon”® sample tube and 29 Si-NMR (Nuclear Magnetic Resonance) measurements are performed to give a specific organosilane to the integrated value of the entire silicon derived from the organosilane. The content ratio of each repeating unit was calculated from the ratio of the integrated value of silicon derived from. 29 Si-NMR measurement conditions are shown below.
- the raw materials used to prepare the wavelength conversion paste are as follows.
- Light-scattering particles 1 AA-1.5 (alumina, average particle size 1.6 ⁇ m, manufactured by Sumitomo Chemical Co., Ltd.)
- Wavelength conversion material 1 Lumidot 530 CdSe (green quantum dot material, manufactured by Sigma-Aldrich)
- Wavelength conversion material 2 Lumidot 640 CdSe (red quantum dot material, manufactured by Sigma-Aldrich)
- Photopolymerization Initiator 1 "Irgacure” (registered trademark) OXE01 (manufactured by BASF Japan Ltd.)
- Monomer 1 NK-9PG (polypropylene glycol # 400 dimethacrylate, which is a bifunctional methacrylate) (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
- Polymer 1 "Etocell” (registered trademark) STD7 (I) (cellulose ethyl ether
- a wavelength conversion paste for green subpixels After partial weighing, kneading with a 3-roller kneader, filtering with an SHP-400 filter (manufactured by Loki Techno Co., Ltd.) while applying a pressure of 100 to 400 kPa with air to obtain a wavelength conversion paste for green subpixels. rice field. Further, a wavelength conversion paste for red subpixels was obtained in the same manner except that the wavelength conversion material 1 was replaced with the wavelength conversion material 2. Further, a light scattering paste for blue subpixels was obtained in the same manner except that the wavelength conversion material 1 was not added.
- a resin composition for partition walls was spin-coated on a 10 cm square non-alkali glass substrate (made by AGC Technoglass Co., Ltd., thickness 0.7 mm) and hot plate (SCW-636, manufactured by SCREEN Semiconductor Solutions Co., Ltd.). ) was dried at a temperature of 90 ° C. for 2 minutes to prepare a dry film.
- the prepared dry film was formed into the partition wall shapes of Examples 1 to 17 and Comparative Examples 1 to 4, which will be described later, using a parallel light mask aligner (PLA-501F, manufactured by Canon Inc.) and using an ultrahigh pressure mercury lamp as a light source.
- Exposure was performed with an exposure amount of 200 mJ / cm 2 (i-line) via a corresponding photomask. Then, using an automatic developing device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 100 seconds with a 0.045 wt% potassium hydroxide aqueous solution, and then rinsing was performed with water for 30 seconds. Further, using an oven (IHPS-222, manufactured by Espec Co., Ltd.), it is heated in air at a temperature of 230 ° C. for 30 minutes, and a pattern is formed on a glass substrate in the shape of FIGS. 2 to 22 having a height of 20 ⁇ m. A substrate with a partition wall was produced.
- the outline of the shape and arrangement of the partition walls (including the frame portion) in the partition wall-equipped substrate used in each Example and Comparative Example is as follows.
- Example 1 FIG. 5
- Example 2 FIG. Example 3: FIG. Example 4: FIG. 9
- Example 5 FIG. 10
- Example 6 FIG. 11
- Example 7 FIG. 12
- Example 8 FIG. 13
- Example 9 FIG. 14
- Example 10 FIG. Example 11: FIG. Example 12: FIG. 17
- Example 13 FIG. Example 14: FIG. 19
- Example 16 FIG. 21
- FIG. 22 Comparative Example 1: FIG. 2 Comparative Example 2: FIG. 3 Comparative Example 3: FIG. 4 Comparative Example 4: FIG.
- the minimum value SRGB MIN was obtained from the measured SR, SG , and SB .
- the height of the partition wall in which the connected buffer or the stand-alone buffer is connected to the cell or the non-pixel portion and forms the frame portion corresponding to the connected buffer or the stand-alone buffer is zero.
- the line segment connecting the ends of the frame portion on the connected cell side or the non-pixel portion side was regarded as the boundary of the connected buffer portion or the stand-alone buffer portion.
- the shape of the partition wall of the prepared substrate with a partition wall was observed with an optical microscope, and the number of defects such as chips was measured.
- the ratio of the number of partition wall lattices with defects to the total number of lattices was A, 1% or more and less than 10% was B, and 10% or more was C.
- a to B are pass levels, A is the best, and B is the next best.
- a wavelength conversion paste is applied to the substrates with partition walls of Examples 1 to 17 and Comparative Examples 1 to 4 by the following method, and then the applied paste is dried and cured, and then a laser microscope (color 3D laser microscope VK-9710) is applied. , (Manufactured by KEYENCE CORPORATION), an optical microscope image was taken from the top surface in camera mode, and the film thickness at the center of the cell was measured.
- the coating head one having 51 discharge ports having a discharge port diameter of 50 ⁇ m and a discharge port length of 130 ⁇ m arranged at a pitch of 300 ⁇ m in the longitudinal direction of the coating head was used.
- a multi-lab coater manufactured by Toray Engineering Co., Ltd.
- a pressure of 500 to 1,500 kPa is applied to the coating head by air, and the traveling speed with respect to the substrate is 20 to 200 mm.
- Wavelength conversion for green subpixels is performed by applying a nozzle to the substrate with a partition wall in a direction parallel to the long side direction of the partition wall while ejecting the wavelength conversion paste for green subpixels while changing the wavelength within the range of / s. Filled with paste. Next, by shifting the base position by 100 ⁇ m in the direction perpendicular to the stripe of the partition wall, applying in the same manner, and further shifting by 100 ⁇ m and applying in the same manner again, the entire range of 7 cm in length and 1.5 cm in width is applied. A wavelength conversion paste for green subpixels was applied to the cells.
- the wavelength conversion substrate produced by the above method was observed with a laser microscope, and the RGB pixel film thickness was evaluated.
- the maximum value in any color pixel is the minimum in the film thickness of each subpixel of continuous RGB pixels at the coating start position in the center of the partition pattern and the film thickness of each continuous subpixel in the center of coating in the center of the partition pattern.
- the film thickness of pixels of the same color is defined as D when it is 20% or more thicker than the value, C when it is 15% or more and less than 20% thick, B when it is 10% or more and less than 15% thick, and A when it is less than 10% thick.
- the wavelength conversion substrates obtained in each Example and Comparative Example were irradiated with blue light to evaluate the display characteristics.
- As the blue light source a blue backlight light source for LCD taken out by disassembling a commercially available liquid crystal monitor (SW2700PT, manufactured by BenQ) was used.
- the display characteristics were evaluated based on the following criteria.
- C The display quality is low due to visible display unevenness on the inner peripheral portion of the display surface.
- D There is clearly visible display unevenness in the inner peripheral portion of the display surface, there is a difference in brightness between the in-plane central portion and the outer peripheral portion, and the display quality is extremely low.
- the wavelength conversion substrate obtained in each Example and Comparative Example was cut into a frame portion by a scribing device (MTC series, manufactured by Samsung Diamond Industrial Co., Ltd.), and the cutting accuracy was evaluated.
- the substrate after cutting the scribing was photographed with an optical microscope image from the top surface with a laser microscope (color 3D laser microscope VK-9710, manufactured by KEYENCE CORPORATION) in camera mode, and evaluated based on the following criteria.
- A It is divided at the frame portion, there is no local division, cracks, cracks, etc. in the pixel portion, and there are no defects such as peeling or partial defects in the partition wall of the lattice portion and the frame portion.
- B It is divided at the frame portion, and there are no local divisions, cracks, cracks, etc. in the pixel portion, but there are defects such as peeling and partial defects in the partition wall of the lattice portion and the frame portion.
- C Although it is divided at the frame portion, there are local divisions, cracks, cracks, etc. at the pixel portion.
- D Locally or entirely, it is divided outside the frame.
- the first embodiment has good display characteristics because it has an area connecting the cell and the non-pixel portion
- the second embodiment has an area connecting the cell and the non-pixel portion
- the area of the cell in the frame portion is the embodiment. Since it is larger than 1, the variation in the film thickness of the monochromatic pixel is improved and the display characteristics are further improved.
- Comparative Example 1 with respect to Examples 1 and 2, since there is no region connecting the cell and the non-pixel portion in the frame portion and there is no buffer portion in the frame portion, the monochromatic pixel film thickness variation is large and the display characteristics are improved. It was bad. Further, in Comparative Example 2 and Comparative Example 3, although the variation in the film thickness of the monochromatic pixel was low, the partition wall was peeled off at the time of pattern processing because the frame portion was not present, and the display characteristics were remarkably inferior.
- Examples 7 and 8 have a connection type shock absorber and have a large area thereof with a partition wall, the display characteristics are better.
- Example 9 has a connection type buffer portion and a split groove portion as in Example 1, not only the display characteristics are good, but also the split accuracy is also good.
- Example 10 the display characteristics are good as in Example 1, the film thickness of the split groove portion is extremely thin, or the split groove portion is provided in contact with the connection type buffer portion. Therefore, the cutting accuracy was even better than that of Example 9.
- the 16th embodiment has the groove portion for cutting in addition to having the independent cushioning portion as in the 4th embodiment, not only the display characteristics are good but also the cutting accuracy is good.
- the breaking accuracy of Example 17 was even better than that of Example 16.
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Abstract
Description
(1)セルに接続している場合は、接続部における幅は、当該セルの幅よりも狭い幅であること。
(2)セルに接続していない場合は、最も近傍のセルの面積よりも大きな面積であること。
ポリシロキサン溶液の固形分濃度は、以下の方法により求めた。アルミカップにポリシロキサン溶液を1.5g秤取し、ホットプレートを用いて250℃で30分間加熱して液分を蒸発させた。加熱後のアルミカップに残った固形分の重量を秤量して、加熱前の重量に対する割合からポリシロキサン溶液の固形分濃度を求めた。
装置:核磁気共鳴装置(JNM-GX270、日本電子(株)製)
測定法:ゲーテッドデカップリング法
測定核周波数:53.6693MHz(29Si核)
スペクトル幅:20000Hz
パルス幅:12μs(45°パルス)
パルス繰り返し時間:30.0秒
溶媒:アセトン-d6
基準物質:テトラメチルシラン
測定温度:23℃
試料回転数:0.0Hz。
1000mLの三口フラスコに、トリフルオロプロピルトリメトキシシランを147.32g(0.675mol)、3-メタクリロキシプロピルメチルジメトキシシランを40.66g(0.175mol)、3-トリメトキシシリルプロピルコハク酸無水物を26.23g(0.10mol)、3-(3,4-エポキシシクロヘキシル)プロピルトリメトキシシランを12.32g(0.05mol)、ジブチルヒドロキシトルエン(BHT)を0.808g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を171.62g仕込み、室温で撹拌しながら水52.65gにリン酸2.265g(仕込みモノマーに対して1.0重量%)を溶かしたリン酸水溶液を30分間かけて添加した。その後、フラスコを70℃のオイルバスに浸けて90分間撹拌した後、オイルバスを30分間かけて115℃まで昇温した。昇温開始1時間後に溶液温度(内温)が100℃に到達し、そこから2時間加熱撹拌し(内温は100~110℃)、ポリシロキサン溶液を得た。なお、昇温および加熱撹拌中、窒素95体積%、酸素5体積%の混合気体を0.05L/分流した。反応中に副生成物であるメタノール、水が合計131.35g留出した。得られたポリシロキサン溶液に、固形分濃度が40重量%となるようにPGMEAを追加し、ポリシロキサン溶液(ポリシロキサン溶液A)を得た。なお、得られたポリシロキサンの重量平均分子量は4,000であった。また、ポリシロキサンにおける、トリフルオロプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-トリメトキシシリルプロピルコハク酸無水物、3-(3,4-エポキシシクロヘキシル)プロピルトリメトキシシランに由来する繰り返し単位のモル比は、それぞれ67.5mol%、17.5mol%、10mol%、5mol%であった。
白色顔料として、二酸化チタン顔料(R-960、BASFジャパン(株)製)5.00gに、樹脂としてポリシロキサン溶液Aを5.00g混合し、ジルコニアビーズが充填されたミル型分散機を用いて分散し、顔料分散液を得た。次に、顔料分散液9.98g、DAA0.71g、ポリシロキサン溶液Aを1.57g、光重合開始剤として、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(О-アセチルオキシム)(BASFジャパン(株)製)0.050g、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(BASFジャパン(株)製)0.400g、光塩基発生剤として、2-(3-ベンゾイルフェニル)プロピオン酸1,2-ジイソプロピル-3-[ビス(ジメチルアミノ)メチレン]グアニジニウム(富士フイルム和光純薬(株)製)0.100g、光重合性化合物として、ジペンタエリスリトールヘキサアクリレート(新日本薬業(株)製)1.20g、撥液化合物として、光重合性フッ素含有化合物(“メガファック”(登録商標)RS-76-E、DIC(株)製)の40重量%PGMEA希釈溶液1.00g、3’,4’-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート((株)ダイセル製)0.100g、エチレンビス(オキシエチレン)ビス[3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート](BASFジャパン(株)製)0.030g、アクリル系界面活性剤(“BYK”(登録商標)352、ビックケミージャパン(株)製)のPGMEA10重量%希釈溶液0.100g(濃度500ppmに相当)を、PGMEA4.76gに溶解させ、撹拌した。次いで、5.0μmのフィルターでろ過を行い、隔壁用樹脂組成物を得た。
粒度分布測定装置(MT3300;日機装(株)製)の水を満たした試料室に光散乱性粒子を投入し、300秒間超音波処理を行った後に粒度分布を測定し、累積分布に対して50%となる粒子径(d50)を平均粒子径とした。
波長変換ペーストの作製に用いた原料は次のとおりである。
光散乱性粒子1:AA-1.5(アルミナ、平均粒子径1.6μm、住友化学(株)製)
波長変換材料1:Lumidot 530 CdSe(緑色量子ドット材料、シグマアルドリッチ社製)
波長変換材料2:Lumidot 640 CdSe(赤色量子ドット材料、シグマアルドリッチ社製)
光重合開始剤1:“Irgacure”(登録商標) OXE01(BASFジャパン(株)製)
モノマー1:NK-9PG(2官能メタクリレートであるポリプロピレングリコール#400ジメタクリレート)(新中村化学工業(株)製)
ポリマー1:“エトセル”(登録商標)STD7(I)(セルロースエチルエーテル)(DDPスペシャルティ・プロダクツ・ジャパン(株)製)
溶媒1:プロピレングリコールメチルエーテルアセテート(富士フイルム和光純薬(株)製)
(波長変換ペーストの調製)
光散乱性粒子1を25重量部、波長変換材料1を5重量部、光重合開始剤を0.1重量部、モノマー1を34.9重量部、ポリマー1を15重量部、溶媒を20重量部秤量した後、3本ローラー混練機にて混練した後、空気によって100~400kPaの圧力をかけながらSHP-400フィルター((株)ロキテクノ製)でろ過し、緑色サブピクセル用波長変換ペーストを得た。また、波長変換材料1を波長変換材料2に置き換えた以外は同様にして、赤色サブピクセル用波長変換ペーストを得た。また、波長変換材料1を加えないこと以外は同様にして、青色サブピクセル用光散乱ペーストを得た。
10cm角の無アルカリガラス基板(AGCテクノグラス(株)製、厚み0.7mm)上に隔壁用樹脂組成物をスピンコートし、ホットプレート(SCW-636、(株)SCREENセミコンダクータソリュージョンズ製)を用いて、温度90℃で2分間乾燥し乾燥膜を作製した。作製した乾燥膜を、パラレルライトマスクアライナー(PLA-501F、キヤノン(株)製)を用いて、超高圧水銀灯を光源とし、後述する実施例1~17、および比較例1~4の隔壁形状に対応するフォトマスクを介して、露光量200mJ/cm2(i線)で露光した。その後、自動現像装置(AD-2000、滝沢産業(株)製)を用いて、0.045重量%水酸化カリウム水溶液を用いて100秒間シャワー現像し、次いで水を用いて30秒間リンスした。さらに、オーブン(IHPS-222、エスペック(株)製)を用いて、空気中、温度230℃で30分間加熱し、ガラス基板上に、高さ20μmの、図2~22の形状でパターン形成された隔壁付き基板を作製した。なお、各実施例および比較例で用いた隔壁付き基板における隔壁(額縁部を含む)の形状および配置の概要は、次に示すとおりである。
実施例2:図6
実施例3:図8
実施例4:図9
実施例5:図10
実施例6:図11
実施例7:図12
実施例8:図13
実施例9:図14
実施例10:図15
実施例11:図16
実施例12:図17
実施例13:図18
実施例14:図19
実施例15:図20
実施例16:図21
実施例17:図22
比較例1:図2
比較例2:図3
比較例3:図4
比較例4:図7
(隔壁パターン部寸法、額縁部寸法の評価方法)
作製した隔壁付き基板を、レーザー顕微鏡(カラー3Dレーザー顕微鏡 VK-9710、(株)キーエンス製)で上面方向からカメラモードで光学顕微鏡像を撮影し、実施例1~17および比較例1~4におけるWA、LA、LB、SR、SG、SB、WF、WF MAX、WF MIN、LF、LFO、LBF、SF、HF、HD、LD1、LD2、LD3を付属のソフトウェアで測定した。また、WF MAXはWFの最大値、WF MINはWFの最小値とした。また、測定したSR、SG、SBより最小値SRGB MINを求めた。なお、面積を求める際、接続型緩衝部または独立型緩衝部がセルまたは非画素部に接続し、かつ、接続型緩衝部または独立型緩衝部に対応する額縁部をなす隔壁の高さがゼロである場合は、接続しているセル側または非画素部側における額縁部の端を結ぶ線分を接続型緩衝部または独立型緩衝部の境界とみなした。
作製した隔壁付き基板について、光学顕微鏡により隔壁の形状を観察し、欠け等の欠損の数を計測した。欠損がある隔壁格子数の全格子数に占める割合が1%未満のものをA、1%以上10%未満のものをB、10%以上ものをCとした。A~Bが合格レベルであり、Aが最も優れており、Bがそれに次いで優れている。
実施例1~17、および比較例1~4の各隔壁付き基板に、以下の方法で波長変換ペーストを塗布し、次いで塗布したペーストを乾燥・硬化し、レーザー顕微鏡(カラー3Dレーザー顕微鏡 VK-9710、(株)キーエンス製)で上面方向からカメラモードで光学顕微鏡像を撮影し、セルの中心部の膜厚を測定した。塗布ヘッドとして、吐出口直径50μm、吐出口長130μmの吐出口を塗布ヘッドの長手方向に300μmピッチで51個配列して有するものを用いた。塗布装置としては、マルチラボコータ(東レエンジニアリング(株)製)を用いて、ノズルの左端の吐出口が、充填対象となるセルを構成する隔壁の左端から0.5cmの直線上にくるように位置をアライメントし、さらにストライプに沿ってノズルが掃引されるようにノズルの進行方向をアライメントした後、前記塗布ヘッドに空気によって500~1,500kPaの圧力をかけ、基板に対する進行速度を20~200mm/sの範囲内で変化させて前記の緑色サブピクセル用波長変換ペーストを吐出させながら、前記隔壁付き基板に、隔壁の長辺方向と平行方向にノズル塗布することにより、緑色サブピクセル用波長変換ペーストを充填した。次に、隔壁のストライプに平行な方向に垂直な方向に100μm口金位置をずらし、同様に塗布し、さらに100μmずらして再度同様に塗布することで、長さ7cm、幅1.5cmの範囲の全セルに緑色サブピクセル用波長変換ペーストを塗布した。次に、口金位置を隔壁のストライプに平行な方向に垂直な方向に1.5cm右に動かして同様の作業を行うことを3回繰り返し、緑色サブピクセル用波長変換ペーストを7cm×6cmの範囲の前開口に塗布した。その後、ホットプレート上で100℃10分乾燥し、さらに窒素雰囲気下で超高圧水銀灯により露光量200mJ/cm2(i線)で露光して硬化させ、波長変換層を形成した。このとき波長変換層の厚みが、単位格子の中央部において20μmとなるように塗布時の圧力、進行速度を調整した。
各実施例および比較例により得られた波長変換基板に青色光を照射して、表示特性を評価した。青色光源としては、市販の液晶モニター(SW2700PT、BenQ社製)を分解して取り出したLCD用青色バックライト光源を用いた。
表示特性を、以下の基準に基づき評価した。
A:表示輝度が面内一様であり、欠陥が無く表示品位が高い。
B:表示面内外周部に注視しなければ判別できない程度に僅かに表示ムラがあるが、輝度は面内一様であり、表示品位が高い。
C:表示面内外周部に視認できる程度の表示ムラがあり表示品位が低い。
D:表示面内外周部に明確に視認できる表示ムラがあり、輝度は面内中心部と外周部で差があり、表示品位が極めて低い。
各実施例および比較例により得た波長変換基板を、スクライビング装置(MTCシリーズ、三星ダイヤモンド工業社製)にて額縁部を割断し、割断精度を評価した。スクラインビング割断後の基板をレーザー顕微鏡(カラー3Dレーザー顕微鏡 VK-9710、(株)キーエンス製)で上面方向からカメラモードで光学顕微鏡像を撮影し、以下の基準に基づき評価した。
A:額縁部にて割断されており、画素部における局所的な割断、ヒビ、クラック等がなく、かつ格子部および額縁部の隔壁に剥がれや部分的欠損等の欠陥が無い。
B:額縁部にて割断されており、画素部における局所的な割断、ヒビ、クラック等は無いが、格子部および額縁部の隔壁に剥がれや部分的欠損等の欠陥が有る。
C:額縁部にて割断されているが、画素部における局所的な割断、ヒビ、クラック等がある。
D:局所的あるいは、全体的に額縁部外にて割断されている。
2 ペースト
3 基板
4 加圧配管
5 吐出孔
6 隔壁
7 開口部、セル
8 隔壁パターン部
9 額縁部
10 RGBピクセル
10R 赤色画素
10G 緑色画素
10B 青色画素
12 非画素部
13 接続型緩衝部
14 独立型緩衝部
15 割断用溝部
20 額縁上端部
21 割断用溝上端部
22 割断用溝下端部
Claims (8)
- 基板と該基板上に形成された隔壁とを有した隔壁付き基板であって、前記隔壁によって区画されたセルが格子状に配列された領域を有し、かつ、前記領域の外縁を形成し、または、前記領域を囲むよう形成された、最も外側に位置する隔壁は、前記領域の外縁以外を形成する隔壁の幅よりも広い幅を有するとともに、前記格子状配列の列の延長線上で交差する少なくとも一方の側では他所よりも高さの低い部分を有しており、かつ、当該他所よりも高さの低い部分は、次の(1)または(2)を充足することを特徴とする隔壁付き基板。
(1)セルに接続している場合は、接続部における幅は、当該セルの幅よりも狭い幅であること
(2)セルに接続していない場合は、最も近傍のセルの面積よりも大きな面積であること - 前記(2)を充足する隔壁付き基板において、前記最も外側に位置する隔壁の他所よりも高さの低い部分の最大幅は、当該最大幅を示す他所よりも高さの低い部分に対応する最も外側に位置する隔壁の幅の98%以下であることを特徴とする請求項1記載の隔壁付き基板。
- 前記最も外側に位置する隔壁において、当該隔壁内に、前記格子状配列の列の延長線に直交する方向にみて、他所よりも高さの低い部分の存在する割合が50%以上となる部分を有し、かつ、当該他所よりも高さの低い部分の存在する割合が50%以上となる部分の幅は、その部分が存する前記隔壁の幅の20%以下であることを特徴とする請求項1または2記載の隔壁付き基板。
- 請求項1~3のいずれかに記載の隔壁付き基板の前記格子状に配列されたセル内に、電磁波の波長を他の波長に変換する材料が充填された波長変換基板。
- 請求項4に記載の波長変換基板と、有機発光ダイオードおよび発光ダイオードの何れかまたは両方とが具備されたディスプレイ装置。
- 前記電磁波の波長を他の波長に変換する材料として量子ドット蛍光体が用いられた請求項5に記載のディスプレイ装置。
- 前記電磁波の波長を他の波長に変換する材料として無機蛍光体が用いられた請求項5または6に記載のディスプレイ装置。
- 請求項1~3のいずれかに記載の隔壁付き基板に、電磁波の波長を他の波長に変換する材料をノズルから吐出して塗布を行う工程を有する波長変換基板の製造方法であって、前記の塗布は隔壁付き基板の前記他所よりも高さの低い部分が存在する最も外側に位置する隔壁の側から当該部分を通るように塗布を行うことを特徴とする、波長変換基板の製造方法。
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- 2021-12-09 KR KR1020237004923A patent/KR20230121028A/ko unknown
- 2021-12-09 JP JP2021574794A patent/JPWO2022138197A1/ja active Pending
- 2021-12-09 WO PCT/JP2021/045294 patent/WO2022138197A1/ja active Application Filing
- 2021-12-17 TW TW110147562A patent/TW202230836A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006261106A (ja) * | 2005-02-16 | 2006-09-28 | Toray Ind Inc | プラズマディスプレイ用部材およびその製造方法、プラズマディスプレイ用背面板の製造方法、プラズマディスプレイ |
JP2007095696A (ja) * | 2005-09-29 | 2007-04-12 | Samsung Sdi Co Ltd | プラズマディスプレイパネル |
JP2009104953A (ja) * | 2007-10-24 | 2009-05-14 | Fuji Electric Holdings Co Ltd | 有機elディスプレイパネル |
WO2014129067A1 (ja) * | 2013-02-19 | 2014-08-28 | Jsr株式会社 | 波長変換フィルム、波長変換基板、波長変換素子および表示素子 |
CN103647013A (zh) * | 2013-10-28 | 2014-03-19 | 吴震 | 波长转换装置的制造方法和发光装置 |
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JPWO2022138197A1 (ja) | 2022-06-30 |
CN116802713A (zh) | 2023-09-22 |
KR20230121028A (ko) | 2023-08-17 |
TW202230836A (zh) | 2022-08-01 |
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