WO2015152085A1 - 隔壁付基板 - Google Patents
隔壁付基板 Download PDFInfo
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- WO2015152085A1 WO2015152085A1 PCT/JP2015/059751 JP2015059751W WO2015152085A1 WO 2015152085 A1 WO2015152085 A1 WO 2015152085A1 JP 2015059751 W JP2015059751 W JP 2015059751W WO 2015152085 A1 WO2015152085 A1 WO 2015152085A1
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- substrate
- thin film
- partition
- partition wall
- layer
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- 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
- H10K59/122—Pixel-defining structures or layers, e.g. banks
-
- 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
- H10K59/17—Passive-matrix OLED displays
- H10K59/173—Passive-matrix OLED displays comprising banks or shadow masks
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
Definitions
- the present invention relates to a substrate with a partition, a light-emitting device, and a method for manufacturing the same.
- a light-emitting device using an organic electroluminescent element (hereinafter referred to as an organic EL element) as a light source is known.
- an organic EL element an organic electroluminescent element
- a display device using an organic EL element as a light source of a pixel is known.
- the display device includes a substrate, partition walls that define predetermined sections on the substrate, and organic EL elements that are respectively provided in a plurality of sections defined by the partition walls.
- the organic EL element is formed by laminating a first electrode, one or a plurality of organic thin film layers, and a second electrode in this order in each section.
- the organic thin film layer can be formed by a coating method. That is, the organic thin film layer supplies a coating liquid containing a material to be the organic thin film layer to a predetermined partition (a concave portion that is an area surrounded by the partition walls) by a predetermined coating method, and dries and solidifies the coating liquid. Can be formed.
- the partition walls are usually made of a material exhibiting a predetermined liquid repellency. In this case, if the liquid repellency of the partition walls is too high, the coating liquid dries while being repelled by the partition walls. Therefore, when viewed from one side in the thickness direction of the partition walls (hereinafter referred to as “in plan view”), The thickness of the end of the organic thin film layer on the partition wall side becomes thinner than the thickness of the central part, in other words, the thickness of the organic thin film layer in each recess becomes non-uniform. There is.
- an object of the present invention is to provide a substrate with a partition including a partition having a structure that can be manufactured with a smaller number of steps, and a light-emitting device including the partition.
- the present invention is a substrate with a partition including a substrate and a single-layer partition defining a preset recess on the substrate,
- the one-layer partition has a liquid-repellent portion that exhibits liquid repellency,
- the liquid repellent portion is a side surface that extends to the upper surface portion of the partition wall that is outside the recess portion, and that defines the recess portion of the partition wall, from the end portion of the upper surface portion to the end on the substrate side. It is related with the board
- the present invention also relates to the substrate with a partition wall, wherein a liquid repellent material imparting liquid repellency is distributed in the liquid repellent portion.
- the present invention also relates to the substrate with a partition, wherein the one-layer partition has an acute angle between the side surface and the substrate.
- the present invention also relates to the substrate with a partition, wherein the partition is a structure obtained by curing a photosensitive resin composition containing an acrylic resin.
- the present invention also relates to a light emitting device including the substrate with a partition and a plurality of organic EL elements respectively provided in the recess defined by the partition.
- the organic EL element has a pair of electrodes and one or more organic thin film layers provided between the pair of electrodes.
- the organic thin film layer formed by a coating method includes the thickness of the organic thin film layer at the position P1 of the central portion of the concave portion in plan view, the organic thin film layer,
- the present invention relates to the light emitting device, wherein the height from the substrate at the position P2 of the upper end portion of the interface with the side surface of the partition wall satisfies the relationship of the following formula (1). P1 + 500 ⁇ P2 (1)
- the present invention is also a method for manufacturing the substrate with a partition, Forming a thin film comprising a photosensitive resin composition containing a liquid repellent material on the substrate; An exposure step of exposing the thin film; A development step of developing the exposed thin film to form a structure to be the one-layer partition; A curing baking step of forming the one-layer partition by heating the structure, The angle formed between the side surface of the structure and the substrate is an obtuse angle, The one-layer partition formed in the curing and baking step relates to a method for manufacturing a substrate with a partition, wherein an angle formed between a side surface and the substrate is an acute angle.
- the present invention provides a step of preparing the substrate with a partition, Forming a plurality of organic EL elements each having a pair of electrodes and one or more organic thin film layers provided between the pair of electrodes in the recess,
- the present invention relates to a method for manufacturing a light-emitting device, in which a coating liquid containing a material to be the organic thin film layer is supplied to the recess and solidified to form the organic thin film layer.
- the present invention relates to the method for manufacturing the light emitting device, wherein the step of providing the organic EL element further includes a step of surface-treating the substrate with a partition wall using ozone water before supplying the coating solution.
- FIG. 1 is a cross-sectional view schematically showing an enlarged part of the display device of the present embodiment.
- FIG. 2 is a plan view schematically showing an enlarged part of the display device of the present embodiment.
- FIG. 3 is a cross-sectional view schematically showing an enlarged end of the partition wall facing the recess.
- FIG. 4 is a diagram for explaining a manufacturing process of the display device.
- FIG. 5 is a diagram for explaining a manufacturing process of the display device.
- FIG. 6 is a diagram for explaining a manufacturing process of the display device.
- FIG. 7 is a diagram for explaining a manufacturing process of the display device.
- FIG. 8 is a diagram for explaining a manufacturing process of the display device.
- FIG. 9 is a diagram for explaining a manufacturing process of the display device.
- the light-emitting device of this embodiment includes a substrate and a substrate with a partition wall including a single-layer partition wall that defines a recess on the substrate, and a plurality of organic EL elements respectively provided in the recesses defined by the partition wall.
- the present invention relates to a light emitting device including an element.
- the one-layer partition has a liquid-repellent portion exhibiting liquid repellency, and the liquid-repellent portion extends to the upper surface of the partition outside the recess and defines the recess of the partition.
- a side surface extending from an end of the upper surface portion to an intermediate position between the end portion on the substrate side.
- the organic EL element of this embodiment is configured by laminating a first electrode, an organic thin film layer, and a second electrode in this order from the substrate side.
- the light emitting device of the present embodiment can be used as, for example, a display device or a lighting device.
- examples of the display device include an active matrix drive display device and a passive matrix drive display device.
- the light emitting device of this embodiment can be applied to both types of display devices.
- an active matrix driving display device and a light emitting device applied to the display device will be described as an example.
- FIG. 1 is a cross-sectional view schematically showing an enlarged part of the display device of this embodiment.
- FIG. 2 is a plan view schematically showing an enlarged part of the display device of the present embodiment.
- the display device 1 includes a substrate 2, a partition wall 3 that defines a recess that is a partition set in advance on the substrate 2, and a plurality of recesses defined by the partition wall 3. And a plurality of organic EL elements 4 provided in the.
- a plurality of recesses in a matrix shape 5 is provided in a lattice shape that defines 5 or a stripe shape that defines a plurality of linear recesses extending substantially in parallel.
- lattice-like partition 3 was provided is shown.
- a plurality of recesses 5 are defined in the substrate 2 by the partition walls 3 and the substrate 2.
- the partition 3 is provided in a region where the plurality of recesses 5 are not defined.
- the recesses 5 are arranged at a predetermined interval in the X direction (first axial direction) and at a predetermined interval in the Y direction (second axial direction).
- the X direction and the Y direction are respectively set in directions orthogonal to the Z direction, which is the thickness direction of the substrate 2, and orthogonal to each other.
- the shape of the recess 5 in plan view is not particularly limited.
- the recessed part 5 can be made into substantially rectangular shape, substantially elliptical shape by planar view, for example. In the present embodiment, a plurality of concave portions 5 that are substantially rectangular in plan view are provided.
- the forward taper shape means, for example, as shown in FIG. 1, the side surface of the partition wall 3 that defines the recess 5 when cut by a plane extending in the direction orthogonal to the Y direction, and the main surface of the substrate 2.
- the angle formed between the side surface of the single-layer partition wall 3 and the substrate 2 is an acute angle. That is, the thickness of the end 3a of the partition wall 3 that faces the recess 5 (projects toward the center of the recess 5 in a plan view) is formed in a tapered shape that decreases toward the opposite side wall of the recess 5.
- a so-called reverse tapered partition wall 3 in which an angle formed between the side surface of the partition wall 3 and the main surface of the substrate 2 is set to an obtuse angle may be used.
- the angle formed between the side surface of the partition wall 3 or the side surface of the structure to be described later and the main surface of the substrate 2 may be referred to as the inclination angle of the partition wall 3 or the inclination angle of the structure body.
- the partition 3 is provided in a region excluding a region where the organic EL element 4 is provided.
- the partition 3 is provided in a region excluding a region where the first electrode 6 is mainly provided. That is, the end 3 a of the partition wall 3 is provided so as to overlap at least a part of the peripheral edge of the first electrode 6. Note that the end 3 a of the partition wall 3 does not need to be formed so as to cover the entire peripheral edge of the first electrode 6.
- the partition wall 3 is provided so that the end 3 a of the partition wall 3 covers at least two opposite sides of the four sides of the first electrode 6 having a square shape, for example. May be.
- the end 3 a of the partition wall 3 is provided so as to cover the entire peripheral edge of the first electrode 6.
- FIG. 3 is a cross-sectional view schematically showing an enlarged end of the partition wall 3 facing the recess 5.
- FIG. 3 only the substrate 2 and the partition wall 3 are shown, and other components are omitted.
- the partition wall 3 composed of only one layer is provided on the substrate 2. That is, the partition wall 3 of the present embodiment is different from the partition wall in which a plurality of layers are stacked.
- the partition wall 3 has a liquid repellent portion 11 exhibiting liquid repellency on the surface layer portion 23 which is the surface thereof. That is, a liquid repellent material imparting liquid repellency is distributed in the liquid repellent portion 11.
- “showing liquid repellency” means that the contact angle with respect to anisole is 20 ° or more.
- the liquid repellent portion 11 is not provided on the entire surface layer portion 23 of the partition wall 3.
- the liquid repellent portion 11 extends to a part of the surface layer portion 23 of the partition wall 3. Further, the liquid repellent portion 11 extends from the end 15 of the upper surface portion 21 to the end portion 16 on the substrate 2 side on the side surface defining the recess 5 except for the upper surface portion 21 of the surface layer portion 23 of the partition wall 3. It extends to midway position 22 between. In other words, the liquid repellent portion 11 does not extend from the midway position 22 to the end portion 16 on the substrate 2 side on the side surface defining the recess 5 of the partition wall 3.
- the upper surface of the partition wall 3 means a surface facing the surface (bottom surface) of the partition wall 3 on the side of the substrate 2.
- the region is referred to as the upper surface portion 21.
- a portion where the liquid repellent portion 11 is not provided is a portion having at least a liquid repellency lower than that of the liquid repellent portion 11. That is, in the surface layer part 23 of the partition wall 3, the part where the liquid repellent part 11 is not provided is a part showing lyophilicity.
- a portion where the liquid repellent portion 11 is not provided is referred to as a lyophilic portion 12.
- the liquid repellent part 11 is indicated by a thick line
- the lyophilic part 12 is indicated by a thin line.
- “showing lyophilicity” means that the contact angle with respect to anisole is less than 20 °.
- the contact angle with respect to anisole is 20 ° or more, and preferably 25 ° or more.
- the lyophilic portion 12 of this embodiment has a contact angle with respect to anisole of less than 20 °, and preferably 10 ° or less.
- the partition wall 3 of this embodiment is composed of a single layer member.
- the liquid repellent portion 11 has a two-layer structure in which an organic thin film layer having liquid repellency is further formed on the surface of the partition wall.
- the liquid repellent portion 11 and the lyophilic portion 12 are provided on the side surface defining the concave portion 5 of the partition wall 3, so that the substrate is more disposed on the side surface of the partition wall 3, that is, in the concave portion 5.
- the lower side near 2 shows lyophilicity
- the upper side near the upper surface part 21 shows liquid repellency. Therefore, the partition wall 3 of the present embodiment is configured as a single layer with respect to wettability, but has a two-layer structure in which a single-layer partition wall that exhibits lyophilicity and a single-layer partition wall that exhibits liquid repellency are stacked. The same characteristics can be obtained.
- the upper direction means the thickness direction of the substrate 2, that is, one direction toward the side where the organic EL element 4 is provided with respect to the substrate 2 in the Z direction
- the lower direction means The upper direction means the opposite direction.
- liquid repellent material that imparts liquid repellency is distributed in the liquid repellent portion 11.
- the liquid repellent material will be described later.
- the organic EL element 4 is provided in a section defined by the partition 3 (that is, the recess 5).
- each organic EL element 4 is provided in each recess 5. Therefore, when the grid-like partition 3 is provided, the organic EL elements 4 are arranged in a matrix like the recesses 5. That is, the organic EL elements 4 are arranged on the substrate 2 with a predetermined interval in the X direction and with a predetermined interval in the Y direction.
- the recess 5 is provided with three types of organic EL elements 4. That is, in the recess 5, (1) a red organic EL element 4R that emits red light, (2) a green organic EL element 4G that emits green light, and (3) a blue organic EL element 4B that emits blue light. Is provided. These three types of red organic EL element 4R, green organic EL element 4G, and blue organic EL element 4B have, for example, the following (I), (II), and (III) rows in the Y direction as shown in FIG. Are arranged so as to be repeatedly arranged in this order.
- an organic EL element that emits white light may be further provided in the recess 5.
- a monochromatic display device may be realized by providing only one type of organic EL element in the recess 5.
- the organic EL element 4 includes, for example, a first electrode 6, one or more organic thin film layers, and a second electrode 10 stacked in this order from the substrate 2 side.
- a layer containing an organic substance as a material is referred to as an organic thin film layer.
- the organic EL element 4 includes at least one light emitting layer 9 as an organic thin film layer.
- the organic EL element 4 may further include an organic thin film layer and an inorganic thin film layer different from the light emitting layer as necessary, in addition to at least one light emitting layer 9.
- a hole injection layer, a hole transport layer, an electron block layer, an electron transport layer, an electron injection layer Etc. are provided between the first electrode 6 and the second electrode 10.
- Two or more light emitting layers 9 may be provided between the first electrode 6 and the second electrode 10.
- the organic EL element 4 includes a first electrode 6 and a second electrode 10 as a pair of electrodes including an anode and a cathode.
- One of the first electrode 6 and the second electrode 10 is provided as an anode, and the other electrode is provided as a cathode.
- the first electrode 6 functioning as an anode
- the first organic thin film layer 7 functioning as a hole injection layer
- the second organic thin film layer 9 functioning as a light emitting layer
- the first function functioning as a cathode.
- the organic EL element 4 in which the two electrodes 10 are laminated on the substrate 2 in this order will be described.
- the red organic EL element 4R includes a light emitting layer 9 that emits red light
- the green organic EL element 4G includes a light emitting layer 9 that emits green light
- the blue organic EL element 4B emits a blue light. 9 is provided.
- the first electrode 6 is provided for each organic EL element 4. That is, the same number of first electrodes 6 as the organic EL elements 4, that is, the same number as the number of recesses 5 are provided on the substrate 2.
- the first electrodes 6 are provided corresponding to the arrangement of the organic EL elements 4, and are arranged in a matrix like the organic EL elements 4.
- the partition wall 3 of the present embodiment is formed in a lattice shape mainly in a region excluding the first electrode 6, but the end portion 3 a is formed so as to cover the peripheral edge portion of the first electrode 6. (See FIG. 1).
- the first organic thin film layer 7 corresponding to the hole injection layer is provided on the first electrode 6 in the recess 5.
- the first organic thin film layer 7 can be provided with a different material or thickness depending on the type of the organic EL element 4 as necessary.
- FIG. Furthermore, when forming the organic EL element 4 having a microcavity structure, the thickness of the first organic thin film layer 7 is adjusted for each type of the organic EL element 4 in accordance with the emission wavelength so that optical resonance occurs. Also good.
- the second organic thin film layer 9 functioning as a light emitting layer is provided on the first organic thin film layer 7 in the recess 5.
- the light emitting layer is provided according to the type of the organic EL element. Therefore, the light emitting layer 9 that emits red light is provided in the concave portion 5 in which the red organic EL element 4R is provided, and the light emitting layer 9 that emits green light is provided in the concave portion 5 in which the green organic EL element 4G is provided.
- the light emitting layer 9 that emits the light is provided in the recess 5 in which the blue organic EL element 4B is provided.
- the second electrode 10 is provided on the organic thin film layer 9.
- “provided on the layer” may take either a form provided in contact with the lower layer (lower layer) or a form provided apart from the lower layer.
- a predetermined inorganic layer may be provided between the organic thin film layer 9 and the second electrode 10 provided on the organic thin film layer 9.
- the second electrode 10 is formed on the entire surface in the display region where the organic EL element 4 is provided. That is, the second electrode 10 is formed not only on the second organic thin film layer 9 but also on the partition 3, continuously formed over the plurality of organic EL elements 4, and common to all the organic EL elements 4. It is provided as an electrode.
- FIGS. 4 to 9 are diagrams for explaining a manufacturing process of the display device according to the present embodiment.
- the manufacturing method of a light-emitting device includes the manufacturing method of the board
- the method of manufacturing a substrate with a partition includes a step of forming a thin film comprising a photosensitive resin composition containing a liquid repellent material on a substrate, an exposure step of exposing the thin film, and developing the exposed thin film, A development step for forming a structure to be a single-layer partition wall, and a curing and baking step for forming the single-layer partition wall by heating the structure body.
- the angle formed between the side surface of the structure and the substrate is an obtuse angle.
- the angle formed between the side surface and the substrate is an acute angle.
- a manufacturing method of a light-emitting device includes a step of preparing the above substrate with a partition, a plurality of organic EL elements having a pair of electrodes and one or a plurality of organic thin film layers provided between the pair of electrodes.
- an organic thin film layer is formed by supplying a coating liquid containing a material to be an organic thin film layer to the concave portion and solidifying.
- a substrate 2 provided with a partition wall 3 and a first electrode 6 is prepared.
- the substrate 2 provided with the first electrode 6 in advance may be prepared, or the first electrode 6 may be formed on the substrate 2 in this step.
- a substrate on which circuits for individually driving a plurality of organic EL elements are formed in advance can also be used as the substrate 2 of this embodiment.
- a substrate on which a TFT (Thin Film Transistor), a capacitor, and the like are formed in advance may be used as the substrate 2 of this embodiment.
- the plurality of first electrodes 6 are formed in a matrix on the substrate 2.
- the first electrode 6 can be formed, for example, by forming a conductive thin film on one main surface of the substrate 2 and patterning the conductive thin film in a matrix by a patterning method such as a photolithography method.
- a mask having an opening formed in a predetermined portion is disposed on the substrate 2, and the first electrode 6 is formed by selectively depositing a conductive material on the predetermined portion on the substrate 2 through the mask. A pattern may be formed. The material of the first electrode 6 will be described later.
- the process of forming the partition 3 is implemented.
- the partition walls 3 are formed by patterning by photolithography.
- a photosensitive resin composition containing a liquid repellent material is applied to the substrate 2 to form a thin film 24 made of the photosensitive resin composition containing a liquid repellent material.
- the method for applying the photosensitive resin composition include spin coating and slit coating.
- a pre-baking process is usually performed.
- the solvent is removed by heating the substrate 2 on which the thin film 24 is formed, for example, at a temperature of 70 ° C. to 120 ° C. for 50 seconds to 120 seconds.
- the liquid repellent material is distributed in the surface layer portion 23.
- the liquid repellent material is fixed to the surface layer portion 23.
- an exposure process is performed.
- a negative photosensitive resin composition In the case where a negative photosensitive resin composition is used, light is irradiated to a portion where the partition wall 3 is to be formed.
- a positive photosensitive resin composition In the case where a positive photosensitive resin composition is used, light is irradiated to the portion excluding the portion where the partition 3 is to be formed.
- a mode in which a negative photosensitive resin composition is used will be described.
- a photomask 25 that shields the light L in a predetermined pattern is disposed on the substrate 2 on which the thin film 24 is formed, and the thin film made of the photosensitive resin composition is interposed through the photomask 25. 24 is exposed.
- light is irradiated only to the site
- the irradiated light L is schematically shown using white arrow symbols.
- the exposure amount is set according to a desired tilt angle ⁇ 2.
- the exposure amount for example, 40mJ / m 2 ⁇ 250mJ / m 2, it is preferred more preferably 50mJ / m 2 ⁇ 200mJ / m 2, is 100mJ / m 2 ⁇ 200mJ / m 2.
- the inclination angle ⁇ 2 may depend on the thickness of the thin film 24 made of the photosensitive resin composition.
- the thickness of the thin film 24 made of the photosensitive resin composition is preferably 0.3 ⁇ m to 2.5 ⁇ m, more preferably 0.5 ⁇ m to 2.5 ⁇ m, and 0.5 ⁇ m to 1.0 ⁇ m. More preferably. Since it is difficult for light to reach the substrate 2 during the exposure process, it becomes easy to form the structure 26 that becomes the reverse-tapered one-layer partition wall 3, so that the thickness of the thin film 24 is 0.3 ⁇ m or more. It is preferable that it is 0.5 ⁇ m or more. Further, since the development reproducibility is good and the variation in the line width of the pattern tends to be small, the thickness of the thin film 24 is preferably 2.5 ⁇ m or less, and more preferably 1 ⁇ m or less.
- the inclination angle ⁇ 2 can also be adjusted by adjusting the development time.
- the inclination angle ⁇ 2 tends to increase as the development time increases.
- the inclination angle ⁇ 2 can be adjusted by adjusting the distance between the photomask 25 and the substrate 2.
- the inclination angle ⁇ 2 tends to approach 90 ° as the distance between the photomask 25 and the substrate 2 is shortened.
- the inclination angle ⁇ 2 also depends on the TMAH concentration of the developer.
- development is performed by adjusting the above-described exposure amount and the like so as to form a structure body 26 that is a reverse-tapered partition wall 3 having an obtuse inclination angle ⁇ 2 as shown in FIG. Later, a structure 26 to be a single-layer partition wall 3 is formed.
- the inclination angle ⁇ 2 of the structure 26 that forms the reverse-tapered single-layer partition wall 3 is preferably 100 ° to 175 °, and more preferably 120 ° to 170 °.
- the liquid repellent material is fixed to the surface layer portion 23. Therefore, even in the structure 26 that becomes the one-layer partition wall 3 after exposure and development, The liquid material is distributed in the surface layer portion 23. In FIG. 6 to FIG. 9, portions where the liquid repellent material is distributed are indicated by thick lines. On the other hand, the liquid repellent material is not distributed on the side surface of the structure 26 to be the single-layer partition wall 3.
- the distance in plan view is preferably 0.5 ⁇ m to 3.0 ⁇ m.
- the cure baking process is performed by heating at a temperature of 200 ° C. to 230 ° C. for 15 minutes to 60 minutes, for example. By this cure baking process, the partition walls 3 are formed.
- the liquid repellent material distributed in the surface layer portion 23 also descends along with the deformation of the structure body. It will be distributed in a part of.
- the liquid repellent portion 11 extending from the end portion 15 of the upper surface portion of the partition wall 3 to the midway position 22 between the end portions 16 on the substrate side is formed.
- the photosensitive resin composition used for formation of the partition 3 contains the following component (A), component (B), component (C), component (D), and component (E).
- Component (A) Structure derived from an unsaturated compound having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a cyclic ether structure having 2 to 4 carbon atoms
- a copolymer containing a unit (however, there is no structural unit derived from an unsaturated compound having a perfluoroalkyl group having 4 to 6 carbon atoms) (hereinafter sometimes referred to as “resin (A)”.
- Component (B) A polymer containing a structural unit derived from an unsaturated compound having a perfluoroalkyl group having 4 to 6 carbon atoms (hereinafter sometimes referred to as “resin (B)”) Component (C) Polymerizable compound Component (D) Polymerization initiator Component (E) Solvent
- the photosensitive resin composition includes a resin different from the resin (A) and the resin (B) (hereinafter sometimes referred to as “resin (A1)”), a polymerization initiation assistant (D1), and a polyfunctional thiol compound. It may contain at least one selected from the group consisting of (T).
- the photosensitive resin composition does not contain a surfactant.
- the compound illustrated as each component can be used individually or in combination unless there is particular notice.
- the resin (A) examples include the following resin (A-1) and resin (A-2).
- Resin (A-1) at least one compound (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms (b ) And a copolymer.
- Resin (A-2) Monomer (c) copolymerizable with compound (a) and unsaturated compound (b) (however, it does not have a cyclic ether structure having 2 to 4 carbon atoms), A copolymer obtained by polymerizing the compound (a) and the unsaturated compound (b). However, the compound (a), the unsaturated compound (b) and the monomer (c) do not have a perfluoroalkyl group having 4 to 6 carbon atoms.
- the resin (A) is preferable.
- the compound (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.
- the partition wall 3 of this embodiment is preferably a structure obtained by curing a photosensitive resin composition containing an acrylic resin.
- (meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.
- the unsaturated compound (b) is an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring).
- Monomers having a cyclic ether structure of 2 to 4 and an ethylenically unsaturated double bond are preferred, and monomers having a cyclic ether structure of 2 to 4 carbon atoms and a (meth) acryloyloxy group are more preferred. .
- Examples of the unsaturated compound (b) include an unsaturated compound (b1) having an oxiranyl group, an unsaturated compound (b2) having an oxetanyl group, and an unsaturated compound (b3) having a tetrahydrofuryl group.
- Examples of the unsaturated compound (b1) include an unsaturated compound (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon group is epoxidized, and an unsaturated alicyclic hydrocarbon. And an unsaturated compound (b1-2) having an epoxidized structure.
- the unsaturated compound (b1) is preferably a monomer having an oxiranyl group and a (meth) acryloyloxy group, and has a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and a (meth) acryloyloxy group. Monomers are more preferred. If these monomers are used, the storage stability of the photosensitive resin composition can be further enhanced.
- the unsaturated compound (b1-1) include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, ⁇ -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, ⁇ -methyl-o-vinylbenzyl glycidyl ether, ⁇ -methyl-m-vinylbenzyl glycidyl ether, ⁇ -methyl-p-vinylbenzyl glycidyl ether, 2,3 -Bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styren
- Examples of the unsaturated compound (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), a compound represented by the following formula (I) And compounds represented by the following formula (II).
- vinylcyclohexene monooxide for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.
- 3,4-epoxycyclohexylmethyl acrylate for example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cy
- R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. Also good.
- X 1 and X 2 each represents a single bond, —R 3 —, * —R 3 —O—, * —R 3 —S—, * —R 3 —NH—.
- the bond to which the symbol “*” is attached represents a bond that is bonded to an oxygen atom.
- R 3 represents an alkanediyl group having 1 to 6 carbon atoms.
- alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and a tert-butyl group.
- alkyl group substituted with a hydroxy group include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy- Examples include 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.
- R 1 and R 2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.
- alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
- X 1 and X 2 are preferably a single bond, methylene group, ethylene group, * —CH 2 —O— group, * —CH 2 CH 2 —O— group, more preferably a single bond, * — A CH 2 CH 2 —O— group.
- the symbol “*” represents bonding with an oxygen atom.
- the unsaturated compound (b2) a monomer having an oxetanyl group and a (meth) acryloyloxy group is preferable.
- the unsaturated compound (b2) include 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, and 3-methyl-3- (meth) acryloyloxy. Examples thereof include ethyl oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.
- the unsaturated compound (b3) a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is preferable.
- Specific examples of the unsaturated compound (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.
- Examples of the monomer (c) include (meth) acrylic acid esters, N-substituted maleimides, unsaturated dicarboxylic acid diesters, alicyclic unsaturated compounds, styrenes, and other vinyl compounds. Note that (meth) acrylic acid esters having an ethylenically unsaturated group are excluded from (meth) acrylic acid esters.
- the ratio of the structural units derived from each monomer is preferably in the following range with respect to the total number of moles of the structural units constituting the resin (A-1).
- the ratio of the structural unit of the resin (A-1) is in the above range, the storage stability of the photosensitive resin composition, the developability when forming a pattern from the photosensitive resin composition, and the coating obtained There exists a tendency for the solvent resistance of a film
- the resin (A-1) is preferably a resin (A-1) in which the unsaturated compound (b) is an unsaturated compound (b1), and the unsaturated compound (b) is an unsaturated compound (b1-2). Resin (A-1) is more preferred.
- Resin (A-1) is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) It can manufacture with reference to the cited reference described in the said literature.
- the ratio of the structural units derived from the respective monomers is preferably in the following range with respect to the total number of moles of all the structural units constituting the resin (A-2).
- the ratio of the structural units of the resin (A-2) is in the above range, the storage stability of the photosensitive resin composition, the developability when forming a pattern from the photosensitive resin composition, and the coating obtained There exists a tendency for the solvent resistance of a film
- the resin (A-2) is preferably a resin (A-2) in which the unsaturated compound (b) is an unsaturated compound (b1), and the unsaturated compound (b) is an unsaturated compound (b1-2).
- the resin (A-2) is more preferable.
- the resin (A-2) can be produced by the same method as the resin (A-1).
- the weight average molecular weight in terms of polystyrene of the resin (A) is preferably 3000 to 100,000, more preferably 5000 to 50000.
- the coating property tends to be excellent, the film thickness of the exposed portion is hardly generated during development, and the non-exposed portion is easily removed by development.
- the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above range, the developability tends to be excellent.
- the acid value of the resin (A) is 20 mgKOH / g to 150 mgKOH / g, preferably 40 mgKOH / g to 135 mgKOH / g, more preferably 50 mgKOH / g to 135 mgKOH / g.
- the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titrating with an aqueous potassium hydroxide solution.
- the content of the resin (A) is preferably 5% by mass to 95% by mass, more preferably 20% by mass to the total amount of the resin (A), the resin (A1) and the component (C) polymerizable compound. 80% by mass, particularly preferably 40% by mass to 60% by mass. If the content of the resin (A) is in the above range, the developability of the photosensitive resin composition, the adhesion of the resulting pattern, the solvent resistance and the mechanical properties tend to be good.
- the resin (B) include a polymer containing a structural unit derived from an unsaturated compound (d) having a C 4-6 perfluoroalkyl group.
- Examples of the unsaturated compound (d) include compounds represented by the following formula (d-0).
- R f represents a perfluoroalkyl group having 4 to 6 carbon atoms.
- R d represents a hydrogen atom, a halogen atom, a cyano group, a phenyl group, a benzyl group or an alkyl group having 1 to 21 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a halogen atom or a hydroxy group. May be.
- X d is a single bond, a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a divalent divalent hydrocarbon group having 6 to 12 carbon atoms.
- R e represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- alkyl group having 1 to 4 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group.
- R f is a perfluoroalkyl group having 4 to 6 carbon atoms, preferably a perfluorobutyl group or a perfluorohexyl group.
- alkyl group having 1 to 21 carbon atoms in R d examples include linear groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.
- Alkyl group isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1 -Propylbutyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhe
- Examples of the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms in X d include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1, 4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, Examples include alkanediyl groups such as octane-1,8-diyl group.
- Examples of the divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms in Xd include, for example, a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, and a cyclodecandiyl group.
- Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms in Xd include a phenylene group and a naphthalenediyl group.
- the group represented by —CH 2 — is a group represented by —O—, a group represented by —CO—, a group represented by —NR e —, a group represented by —S— or —SO
- Examples of X d substituted with a group represented by 2 — include groups represented by the following formulas (xd-1) to (xd-10).
- X d is preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an ethylene group.
- the resin (B) is preferably a resin including a structural unit derived from the unsaturated compound (d) and a structural unit derived from the compound (a), and a structural unit derived from the unsaturated compound (d)
- a resin containing a structural unit derived from the compound (a) and a structural unit derived from the unsaturated compound (b) is more preferable.
- the resin (B) contains the structural unit derived from the compound (a), the developability is excellent, and thus the residue and unevenness derived from the development tend to be suppressed.
- the resin (B) contains a structural unit derived from the unsaturated compound (b), the solvent resistance tends to be excellent.
- the resin (B) may contain a structural unit derived from the monomer (c) and does not have an ethylenically unsaturated bond derived from the monomer (c).
- the compound (a), the unsaturated compound (b) and the monomer (c) are as described above.
- the ratio of the structural units derived from each monomer is the sum of the structural units constituting the resin (B). It is preferable to be in the following range with respect to the number of moles.
- Structural unit derived from compound (a) 5% by mass to 40% by mass (more preferably 10% by mass to 30% by mass)
- Structural unit derived from unsaturated compound (d) 60% by mass to 95% by mass (more preferably 70% by mass to 90% by mass)
- the ratio of the structural unit derived from each monomer is the resin (B).
- the total number of moles of the structural units to be formed is preferably in the following range.
- Structural unit derived from compound (a) 5% by mass to 40% by mass (more preferably 10% by mass to 30% by mass) Structural unit derived from unsaturated compound (b); 5% by mass to 80% by mass (more preferably 10% by mass to 70% by mass) Structural unit derived from unsaturated compound (d); 10% by mass to 80% by mass (more preferably 20% by mass to 70% by mass)
- the resin (B) is a copolymer of the compound (a), the unsaturated compound (b), the monomer (c) and the unsaturated compound (d), the ratio of the structural unit derived from each monomer
- the weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3000 to 20000, and more preferably 5000 to 15000.
- the coating property tends to be excellent, the film thickness of the exposed portion is hardly generated during development, and the non-exposed portion is easily removed by development.
- the acid value of the resin (B) is 20 mgKOH / g to 200 mgKOH / g, preferably 40 mgKOH / g to 150 mgKOH / g.
- the content of the resin (B) is preferably 0.001 to 10 parts by mass, more preferably 0 with respect to 100 parts by mass of the total amount of the resin (A), the resin (A1) and the component (C) polymerizable compound. 0.01 to 5 parts by mass.
- the content of the resin (B) is in the above range, the developability during pattern formation and the resulting pattern tend to be excellent in liquid repellency.
- the photosensitive resin composition may contain resin (A1).
- Resin (A1-1) a copolymer obtained by polymerizing compound (a) and monomer (c)
- Resin (A1-2) a resin obtained by reacting the unsaturated compound (b) with a copolymer obtained by polymerizing the compound (a) and the monomer (c)
- Resin (A1-3) examples thereof include a resin obtained by reacting compound (a) with a copolymer obtained by polymerizing unsaturated compound (b) and monomer (c).
- the content of the resin (A1) is preferably 0 to 80% by mass, more preferably 0 to 50% by mass, based on the total amount of the resin (A) and the resin (A1). When content of resin (A1) exists in the said range, a pattern can be formed with high sensitivity and it is excellent in developability.
- the photosensitive resin composition contains a component (C) polymerizable compound.
- the component (C) polymerizable compound is a compound that can be polymerized by active radicals generated from the component (D) polymerization initiator and is, for example, a compound having an ethylenically unsaturated bond, preferably (meth) acrylic. It is an acid ester compound.
- the component (C) polymerizable compound having one ethylenically unsaturated bond is the same as the compound (a), unsaturated compound (b) and monomer (c) already described, and among them, (meth) acrylic Acid esters are preferred.
- component (C) polymerizable compound having two ethylenically unsaturated bonds examples include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol diester.
- (Meth) acrylate ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl Koruji (meth) acrylate, 3-methyl-pentanediol di (meth) acrylate.
- component (C) polymerizable compound having three or more ethylenically unsaturated bonds examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meta).
- component (C) polymerizable compound having three or more ethylenically unsaturated bonds a tri- or higher functional photopolymerizable compound is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.
- the content of the component (C) polymerizable compound is preferably 5% by mass to 95% by mass, more preferably based on the total amount of the resin (A), the resin (A1) and the component (C) polymerizable compound. Is 20% by mass to 80% by mass. When the content of the component (C) polymerizable compound is in the above range, the sensitivity, the strength of the pattern obtained, smoothness, and reliability tend to be good.
- the photosensitive resin composition contains a component (D) polymerization initiator.
- the component (D) polymerization initiator is not particularly limited as long as it is a compound capable of initiating polymerization by the action of light or heat, and a known polymerization initiator can be used.
- component (D) polymerization initiator examples include alkylphenone compounds, biimidazole compounds, triazine compounds, acylphosphine oxide compounds, and oxime compounds.
- a light and / or thermal cationic polymerization initiator for example, a polymerization initiator composed of an onium cation and an anion derived from a Lewis acid
- a polymerization initiator containing these compounds is particularly preferred because it tends to be highly sensitive.
- the polymerization initiation assistant (D1) can be used together with the component (D) polymerization initiator described above.
- the polymerization initiation assistant (D1) is a compound or sensitizer that is used in combination with the component (D) polymerization initiator, and is used to accelerate the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. is there.
- Examples of the polymerization initiation aid (D1) include thioxanthone compounds, amine compounds, and carboxylic acid compounds.
- Examples of the combination of the component (D) polymerization initiator and the polymerization initiator assistant (D1) include a combination of an acetophenone compound and a thioxanthone compound, and a combination of an acetophenone compound and an aromatic amine compound.
- the content of the component (D) polymerization initiator is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (A), the resin (A1) and the component (C) polymerizable compound. More preferably, it is 1 to 20 parts by mass, and still more preferably 1 to 10 parts by mass. When the content of the component (D) polymerization initiator is in the above range, a pattern can be obtained with high sensitivity.
- the amount of the polymerization initiation aid (D1) used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the resin (A), the resin (A1) and the component (C) polymerizable compound. More preferably, it is 0.3 to 7 parts by mass.
- the amount of the polymerization initiation assistant (D1) is in the above range, a pattern can be obtained with high sensitivity, and the resulting pattern has a good shape.
- the photosensitive resin composition contains a component (E) solvent.
- the solvent examples include an ester solvent (a solvent containing a group represented by —COO— in the molecule and not containing a group represented by —O—), an ether solvent (represented by —O— in the molecule).
- Solvent containing a group and not containing a group represented by —COO— an ether ester solvent (a solvent containing a group represented by —COO— and a group represented by —O— in the molecule), a ketone solvent (A solvent containing a group represented by —CO— in the molecule and not a group represented by —COO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, etc. Can be used.
- the content of the component (E) solvent in the photosensitive resin composition is preferably 60% by mass to 95% by mass, more preferably 70% by mass to 90% by mass with respect to the total amount of the photosensitive resin composition. is there.
- the solid content of the photosensitive resin composition is preferably 5% by mass to 40% by mass, and more preferably 10% by mass to 30% by mass.
- solid content means the quantity remove
- the polyfunctional thiol compound (T) that can be contained in the photosensitive resin composition refers to a compound having two or more sulfanyl groups (—SH) in the molecule.
- —SH sulfanyl groups
- polyfunctional thiol compound (T) examples include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3- Sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), Trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydride Carboxyethyl tris (3-sulfanyl)
- the content of the polyfunctional thiol compound (T) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass with respect to 100 parts by mass of the component (D) polymerization initiator. Part by mass.
- the content of the polyfunctional thiol compound (T) is in the above range, the sensitivity of the photosensitive resin composition is increased and the developability tends to be favorable, which is preferable.
- the light (irradiation light) irradiated to the layer of the photosensitive resin composition is absorbed by an ultraviolet absorber or the like, and therefore becomes weaker as it is separated from the surface side of the layer. Therefore, the photosensitive resin composition of the present embodiment is characterized in that the light irradiation side (surface side) is more easily cured and is harder to be cured as it is separated from the surface side. For this reason, when the exposure amount is small, it is difficult to cure near the bottom of the layer where the irradiated light is difficult to reach. Therefore, when exposed to the developer, the shape of the end including the side surface facing the recess 5 of the partition wall 3 is inversely tapered. It becomes a shape.
- the exposure amount is preferably 100 mJ / cm 2 or more because the adhesion between the partition walls 3 and the substrate tends to be improved. Further, the exposure amount is preferably 250 mJ / cm 2 or less because it tends to easily form the structure 26 that becomes the one-layer partition wall 3 having a reverse taper shape.
- the developer used for development examples include an aqueous potassium chloride solution and an aqueous tetramethylammonium hydroxide (TMAH) solution. Since it becomes easy to develop and it becomes easy to form the structure 26 which becomes the reverse-tapered one-layer partition wall 3 with good reproducibility, the concentration of the developer in terms of TMAH is preferably 0.5% by weight or more.
- concentration of TMAH conversion of a developing solution means the TMAH density
- the shape of the partition 3 and the arrangement thereof are appropriately set according to the specifications of the display device such as the number of pixels and the resolution, the ease of manufacturing, and the like.
- the width in the X direction or Y direction of the partition walls 3 in the display area is about 5 ⁇ m to 50 ⁇ m
- the height of the partition walls 3 is about 0.3 ⁇ m to 5 ⁇ m
- the width of the recess 5 in the X direction or Y direction is about 10 ⁇ m to 200 ⁇ m.
- the width of the first electrode 6 in the X direction or Y direction is about 10 ⁇ m to 200 ⁇ m, respectively.
- the step of providing the organic EL element further includes a step of surface-treating the substrate with partition walls before supplying the coating liquid for forming the organic thin film layer. That is, in order to improve the wettability of the first electrode 6 after the formation of the partition wall 3 and before the step of forming the organic thin film layer, that is, before supplying the coating liquid for forming the organic thin film layer.
- the surface treatment include oxygen plasma treatment, UV ozone treatment, alkaline solvent treatment, ozone water treatment (treatment using ozone water), and among these, surface treatment by ozone water treatment is preferable.
- the method of ozone water treatment is not particularly limited as long as wettability is improved.
- the ozone water treatment includes, for example, a treatment in which ozone water in which ozone is dissolved is supplied to the substrate 2 provided with the partition walls 3 by shower from the upper surface, and is swung for a predetermined time to perform cleaning.
- the ozone concentration of the ozone water is usually 1 ppm to 20 ppm, and preferably 1 ppm to 10 ppm.
- the rocking time is usually 1 minute to 30 minutes, and preferably 1 minute to 10 minutes.
- the liquid repellency of the partition wall may be lowered, and if the ozone water concentration is too low or the oscillation time is too short, There is a possibility that sufficient wettability of one electrode 6 cannot be ensured.
- the first organic thin film layer 7 is formed.
- at least one organic thin film layer may be formed by a coating method.
- a mode in which the first organic thin film layer 7 and the second organic thin film layer 9 are formed by a coating method will be described.
- the ink 13 containing the material to be the first organic thin film layer 7 is supplied to the region surrounded by the partition wall 3 (the recess 5 defined in the partition wall 3).
- the method for supplying the ink 13 is not particularly limited.
- a method for supplying ink for example, an ink jet printing method, a nozzle coating method, a relief printing method, and an intaglio printing method are used.
- the ink 13 supplied to the recess 5 surrounded by the partition wall 3 is repelled by the surface portion 23 of the partition wall 3 and the liquid repellent portion 11 extending to a part of the side surface, the ink 13 overflows to the adjacent recess 5 beyond the partition wall 3. Without leaving, it is held in a region (concave portion 5) surrounded by the partition walls 3.
- the first organic thin film layer 7 is formed by solidifying the ink 13 supplied to the recess 5.
- the ink 13 can be solidified by, for example, natural drying, heat drying, or vacuum drying.
- the ink 13 includes a material that is polymerized by applying energy
- the material constituting the organic thin film layer is polymerized by heating or irradiating light after the ink 13 is supplied. May be formed.
- the first organic thin film layer 7 can be hardly soluble.
- the upper surface portion side of the side walls of the partition walls 3 exhibits liquid repellency, but the lower side of the side surfaces of the partition walls 3, that is, the main surface side of the substrate 2 exhibits lyophilic properties. 13 is repelled on the upper surface side of the side wall of the partition wall 3 and in contact with the liquid on the lower side of the side surface of the partition wall 3 while the ink 13 is held, the solvent is vaporized and a thin film is formed. Therefore, in the process of vaporizing the solvent, the portion where the liquid surface of the ink 13 and the partition wall 3 are gradually lowered, but the descent stops near the boundary between the liquid repellent portion and the lyophilic portion, and remains as it is. dry. Therefore, as shown in FIG.
- the position P2 in contact with the partition wall 3 on the upper surface of the first organic thin film layer 7 exists in the vicinity of the boundary between the liquid repellent part and the lyophilic part.
- the position P2 in contact with the partition wall 3 on the upper surface side of the organic thin film layer may be referred to as a pinning point P2.
- the organic thin film layer formed by the coating method has a position on the surface opposite to the substrate side at the center (the thickness of the organic thin film layer is the largest in plan view).
- the height of P1 from the main surface of the substrate 2, that is, the thickness (nm) of the organic thin film layer and the organic The relationship between the height (nm) of the upper end portion (pinning point) P2 of the interface between the thin film layer and the side wall of the partition wall from the main surface of the substrate 2 in the thickness direction of the substrate is expressed by the following formula (1). It is preferable to satisfy.
- the height difference is small and flatter between the central portion where the thickness is the thinnest and the end portion in the vicinity of the partition wall.
- the position P2 of the upper end portion of the interface between the organic thin film layer and the side wall of the partition wall 3 exists in the vicinity of the boundary position (midway position) between the liquid repellent part and the lyophilic part on the side surface of the partition wall.
- the pinning point is higher than the pinning point P2 of the present embodiment. As a whole, the flatness may be lower than that of the organic thin film layer.
- the second organic thin film layer 9 that functions as a light emitting layer is formed.
- the second organic thin film layer 9 can be formed in the same manner as the first organic thin film layer 7. That is, it is a region surrounded by the partition 3 with three types of ink including a light emitting layer 9 that emits red light, a light emitting layer 9 that emits green light, and a light emitting layer 9 that emits blue light.
- the light emitting layer 9 can be formed by supplying each to the recess 5 and further solidifying it.
- the second organic thin film layer 9 also preferably satisfies the relationship of the above formula (1), and more preferably satisfies the relationship of the formula (2).
- the second electrode 10 is formed on the organic thin film layer.
- the second electrode 10 is formed on the entire surface in the display region where the organic EL element 4 is provided. That is, the second electrode 10 is formed not only on the second organic thin film layer 9 but also on the partition 3 and continuously formed over the plurality of organic EL elements 4.
- the second electrode 10 functions as an electrode common to all the organic EL elements 4.
- the organic EL element 4 has at least one light emitting layer as an organic thin film layer.
- a hole injection layer, a hole transport layer, an electron block layer, a hole block layer, an electron transport layer, and an electron injection layer are provided as an organic thin film layer between the pair of electrodes.
- anode / light emitting layer / cathode b) anode / hole injection layer / light emitting layer / cathode c) anode / hole injection layer / light emitting layer / electron injection layer / cathode d) anode / hole injection layer / light emitting layer / Electron transport layer / electron injection layer / cathode e) anode / hole injection layer / hole transport layer / light emitting layer / cathode f) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode g ) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode h) Anode / light emitting layer / electron injection layer / cathode i) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cath
- the organic EL element 4 having the above-described configuration is formed by laminating each layer in order from the anode on the main surface of the substrate 2 and finally forming the cathode, and conversely, laminating each layer in order from the cathode on the main surface of the substrate 2. Finally, an anode can be formed.
- a flexible substrate or a rigid substrate is used, and examples thereof include a glass substrate and a plastic substrate.
- a thin film made of metal oxide, metal sulfide, metal, or the like can be used for the anode 6.
- indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (Indium Zinc Oxide: IZO) A thin film made of gold, platinum, silver, copper and the like.
- an electrode exhibiting optical transparency is used for the anode.
- a known hole injection material can be used for the hole injection layer.
- hole injection materials include oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, phenylamines, starburst amines, phthalocyanines, amorphous carbon, polyaniline, and polythiophene derivatives. Can do.
- a known hole transport material can be used for the hole transport layer.
- a hole transport material polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, a polyaniline or Derivatives thereof, polythiophene or derivatives thereof, polyarylamine or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof it can.
- the light emitting layer is usually formed from an organic substance that mainly emits fluorescence and / or phosphorescence, or an organic substance and a dopant that assists the organic substance.
- the dopant is added, for example, in order to improve the luminous efficiency and change the emission wavelength.
- the organic substance contained in the light emitting layer may be a low molecular compound or a high molecular compound.
- Examples of the light emitting material constituting the light emitting layer include known pigment materials, metal complex materials, polymer materials, and dopant materials.
- the dye material examples include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds, Examples thereof include a pyridine ring compound, a perinone derivative, a perylene derivative, an oligothiophene derivative, an oxadiazole dimer, a pyrazoline dimer, a quinacridone derivative, and a coumarin derivative.
- the metal complex material examples include rare earth metals such as Tb, Eu and Dy, or Al, Zn, Be, Ir, Pt, etc. as a central metal, and an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure And the like.
- polymer materials include polymerizing polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinyl carbazole derivatives, and the above dye materials and metal complex materials. And the like.
- examples of materials that emit blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives.
- examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, and polymers thereof, polyparaphenylene vinylene derivatives, polyfluorene derivatives, and the like.
- Examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, and polymers thereof, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyfluorene derivatives, and the like.
- the material that emits white light can be realized by mixing the material that emits blue light, the material that emits green light, and the material that emits red light.
- Examples of the dopant material include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squarylium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, and phenoxazone.
- a known electron transport material can be used for the electron transport layer.
- electron transport materials include oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyano. Mention may be made of ethylene or a derivative thereof, a diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or a derivative thereof, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof.
- a known electron injection material can be used for the electron injection layer.
- the electron injection material include alkali metals, alkaline earth metals, alloys containing one or more of alkali metals and alkaline earth metals, alkali metal or alkaline earth metal oxides, halides, carbonates, or A mixture of these substances can be mentioned.
- the cathode material is preferably a material having a low work function, easy electron injection into the light emitting layer, and high electrical conductivity.
- the material with a high visible light reflectance is preferable as a material of a cathode.
- the cathode for example, an alkali metal, an alkaline earth metal, a transition metal, a Group 13 metal of the periodic table, or the like can be used.
- a transparent conductive electrode made of a conductive metal oxide, a conductive organic material, or the like can be used.
- the above layers and electrodes can be formed by vapor deposition or coating.
- each layer by the coating method it is preferable to form by the method of forming the organic thin film layer of this embodiment mentioned above.
- the display device (light emitting device) of the present invention is manufactured.
- Example 1 First, a TFT substrate was prepared in which a first electrode (anode) made of an ITO thin film and wiring connected to the electrode were patterned in advance.
- the photosensitive resin A is a photosensitive resin containing a negative acrylic material, and can be produced by the method described in Example 2 of JP 2012-73603 A.
- a photosensitive resin composition containing a prepared liquid repellent material is applied and formed on the surface of the TFT substrate by a spin coater, and further, a prebaking process is performed by heating at 110 ° C. for 90 seconds on a hot plate. The solvent was evaporated.
- region of the thin film which consists of photosensitive resin compositions was exposed using the proximity exposure machine (Hitachi Ltd. LE4000A) (exposure amount: 100 mJ / cm ⁇ 2 >). Subsequently, a developer (SD-1 (TMAH 2.0% by weight) manufactured by Tokuyama Corporation) was showered and developed for 45 seconds to remove the photosensitive resin composition in the unexposed area, thereby obtaining a structure having a predetermined pattern. Obtained.
- SD-1 TMAH 2.0% by weight
- the side surface (corresponding to the side surface of the recess) defined by patterning the structure after this development process was processed into a thin film with an FIB apparatus (XVision 200DB manufactured by Seiko Instruments Inc.), and SEM observation revealed that the side surface and the main surface of the substrate It was confirmed that the structure is an inversely tapered structure with an obtuse angle.
- the angle ⁇ 2 formed between the side surface of the structure and the main surface of the substrate was 148 °.
- connects the 1st electrode 1 was 1.5 micrometers.
- the photosensitive resin composition was cured by heating at 230 ° C. for 20 minutes.
- the inversely tapered portion on the side surface of the partition wall descended toward the surface of the substrate, and the lowered tip contacted the surface of the substrate and was cured.
- a partition wall having a forward tapered shape on the side surface defining the recess is formed.
- the side face of the partition wall after the curing and baking process was thin-film processed with an FIB apparatus (XVision 200DB manufactured by Seiko Instruments Inc.) and observed with a STEM. As a result, it was confirmed that the partition wall had a forward taper shape.
- the angle ⁇ 1 formed between the side wall of the partition wall and the surface of the substrate was 38 °.
- the partition wall thickness was 1.0 ⁇ m.
- the contact angle between the upper surface of the partition wall and the anisole after the curing baking process was about 37 °.
- the contact angle between the surface of the first electrode (ITO thin film) and pure water was about 26 °.
- the surface of the substrate was washed with ozone water (concentration: 2 ppm, treatment time: 10 minutes) using an ozone water production apparatus (FA-1000ZW12-5C manufactured by Loki Techno Co., Ltd.) as a surface treatment process.
- ozone water production apparatus FA-1000ZW12-5C manufactured by Loki Techno Co., Ltd.
- the organic thin film layer As the organic thin film layer, a hole injection layer, a hole transport layer, and a light emitting layer were laminated in this order.
- an ink was prepared by mixing an organic solvent and a hole injection material so that the solid content concentration was 1.0% by weight, the viscosity was 8 cp, and the surface tension was 34.7 mN / m.
- This ink was applied in a predetermined recess using an inkjet apparatus (Lilex 142P manufactured by ULVAC).
- the substrate was placed on a temperature control stage in a vacuum drying chamber connected to a dry pump, the temperature of the temperature control stage was set to 10 ° C., the pressure was reduced to about 2.0E-1 Pa, and vacuum drying was performed. .
- the temperature of the temperature control stage was set to 230 ° C., and baking was performed in an atmospheric pressure environment for 15 minutes to form a hole injection layer (thickness: 45 nm) having a uniform thickness.
- the thickness is the thickness of the center of the concave portion in a plan view and means the smallest thickness.
- a hole transport layer was formed in the same manner as the hole injection layer.
- an ink was prepared by mixing an organic solvent and a hole transport material so that the solid content concentration was 0.45 wt%, the viscosity was 3.4 cp, and the surface tension was 34.2 mN / m.
- This ink was applied in a predetermined recess using an inkjet device (Litrex142P manufactured by ULVAC). Since the ink applied to each recess was repelled by the upper surface of the partition wall having high liquid repellency, the ink was prevented from overflowing to the adjacent recess through the upper surface of the partition wall, and contained in the recess.
- the substrate was placed on a temperature control stage in a vacuum drying chamber connected to a dry pump, the temperature of the temperature control stage was set to 25 ° C., the pressure was reduced to about 2.0E-1 Pa, and vacuum drying was performed. .
- the temperature of the temperature control stage was set to 190 ° C., and firing was performed in an atmospheric pressure environment for 60 minutes, thereby forming an intermediate layer (thickness 15 nm) having a uniform thickness.
- the thickness here is the thickness of the center of the concave portion in a plan view and means the smallest thickness.
- polymer light-emitting material 1 that emits red light is mixed with an organic solvent so that the solid content concentration is 2.0% by weight, the viscosity is 8.5 cp, and the surface tension is 34.3 mN / m.
- a red ink was prepared.
- the polymer light-emitting material 2 that emits green light is used as an organic solvent so that its solid content concentration is 1.8 wt%, its viscosity is 6.2 cp, and its surface tension is 34.6 mN / m.
- the green ink was prepared by mixing.
- the polymer light-emitting material 3 that emits blue light is used as an organic solvent so that its solid content concentration is 0.8% by weight, its viscosity is 8.2 cp, and its surface tension is 34.1 mN / m.
- a blue ink was prepared by mixing. Each of these inks was applied in a predetermined recess using an inkjet apparatus (Litrex142P manufactured by ULVAC). Since the ink applied to each recess was repelled by the upper surface of the partition wall having high liquid repellency, the ink was prevented from overflowing to the adjacent recess through the upper surface of the partition wall, and contained in the recess.
- the substrate was placed on a temperature control stage in a vacuum drying chamber connected to a dry pump, the temperature of the temperature control stage was set to 10 ° C., the pressure was reduced to about 2.0E-1 Pa, and vacuum drying was performed. .
- the temperature of the temperature control stage was set to 230 ° C., and firing was performed in an atmospheric pressure environment for 10 minutes to form a light emitting layer (thickness 74 nm) having a uniform thickness.
- the thickness is the thickness of the center of the concave portion in a plan view and means the smallest thickness.
- a layer made of NaF (thickness 2 nm), a layer made of Mg (thickness 2 nm), and a layer made of Al (thickness 200 nm) are sequentially formed by vacuum deposition to form a second electrode (cathode). did. Then, the sealing substrate was bonded together, the organic EL element was sealed, and the display apparatus was produced.
- Example 2 First, the same TFT substrate as in Example 1 was prepared.
- a photosensitive resin Aa was produced.
- An appropriate amount of nitrogen gas was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to create a nitrogen gas atmosphere.
- 166 parts of propylene glycol monomethyl ether acetate and 52 parts of methoxypropanol were added and heated to 85 ° C. with stirring.
- the obtained photosensitive resin Aa had a weight average molecular weight Mw of 7.7 ⁇ 103 and a molecular weight distribution of 1.90.
- the photosensitive resin Aa has the following structural units.
- Component (A) 55 parts by mass as a resin, component (C) 45 parts by mass as a polymerizable compound, component (D) 6 parts by mass as a polymerization initiator, and polymerization initiator aid (D1) 12 parts by mass are mixed.
- a component (E) solvent is added so that the solid content concentration becomes 21%, and a liquid repellent material (Liquid repellent Opt-Ace (registered trademark) HP series, manufactured by Daikin) is further mixed to obtain a photosensitive resin containing the liquid repellent material.
- a composition was prepared.
- the solid content concentration ratio of the liquid repellent material to the photosensitive resin Aa was 0.3% (weight).
- the photosensitive resin composition containing the obtained liquid repellent material is applied and formed on the surface of the prepared TFT substrate by a spin coater, and further prebaked by heating at 105 ° C. for 110 seconds on a hot plate. Treatment was performed and the solvent was evaporated.
- region of the thin film which consists of photosensitive resin compositions was exposed using the proximity exposure machine (Hitachi Ltd. LE4000A) (exposure amount: 200 mJ / cm ⁇ 2 >). Subsequently, the developer (SD-1 (TMAH 2.38 wt%) manufactured by Tokuyama Corporation) was showered and developed for 60 seconds to remove the photosensitive resin in the unexposed areas.
- SD-1 TMAH 2.38 wt%) manufactured by Tokuyama Corporation
- the side surface of the structure after the development process was thin-film processed with an FIB apparatus (XVision 200DB manufactured by Seiko Instruments Inc.) and observed with an SEM. As a result, an inversely tapered structure was confirmed as in Example 1.
- the angle ⁇ 2 formed between the side surface of the structure and the substrate surface was 148 °.
- connects the 1st electrode 1 was 2.5 micrometers. .
- the photosensitive resin composition was cured by heating at 230 ° C. for 20 minutes.
- the tip portion of the reverse tapered shape on the side surface of the partition wall was lowered to the main surface of the substrate by heat, and was cured while the tip portion was in contact with the main surface of the substrate. In this way, a forward tapered partition is formed.
- the side face of the partition wall after the curing and baking process was thin-film processed with an FIB apparatus (XVision 200DB manufactured by Seiko Instruments Inc.) and observed with a STEM. As a result, it was confirmed that the partition wall had a forward taper shape.
- the angle ⁇ 1 formed between the side wall of the partition wall and the main surface of the substrate was 39 °.
- the partition wall thickness was 1.0 ⁇ m as in Example 1.
- the contact angle between the upper surface of the partition wall and the anisole after the curing baking process was 36 ° to 37 °.
- the contact angle between the surface of the first electrode (ITO thin film) and pure water was about 27 °.
- a TFT substrate was prepared in the same manner as in Example 1.
- a solution of the photosensitive resin B (ZPN 2464, manufactured by Nippon Zeon Co., Ltd.) and a liquid repellent material (a liquid repellent Optace (registered trademark) HP series, manufactured by Daikin) are mixed to form a photosensitive resin containing a liquid repellent material.
- a composition was prepared.
- the solid content concentration ratio of the liquid repellent material with respect to the photosensitive resin was set to 0.2% by weight so that the liquid repellency of the upper surface of the partition wall after the partition wall formation was approximately the same as that in Example 1 (37 °). .
- a photosensitive resin composition containing a liquid repellent material is applied and formed on the surface of the prepared TFT substrate by a spin coater, and a pre-baking step is performed by heating at 110 ° C. for 60 seconds on a hot plate, The solvent was evaporated.
- region of the thin film which consists of photosensitive resin compositions was exposed using the proximity exposure machine (Hitachi Ltd. LE4000A) (exposure amount: 100 mJ / cm ⁇ 2 >). Subsequently, a developer (SD-1 (TMAH 0.8% by weight) manufactured by Tokuyama Corporation) was showered and developed for 60 seconds to remove the photosensitive resin composition in the unexposed area.
- SD-1 TMAH 0.8% by weight
- the side surface of the structure after this development step was thin-film processed with an FIB apparatus (XVision 200DB manufactured by Seiko Instruments Inc.) and observed with an SEM, and it was confirmed that the structure was a forward tapered structure.
- the angle ⁇ 2 formed between the side surface of the structure and the main surface of the substrate was 38 °.
- the photosensitive resin composition was cured by heating at 230 ° C. for 30 minutes.
- the side wall of the partition wall after the curing and baking process was thin-film processed with an FIB apparatus (XVision 200DB manufactured by Seiko Instruments Inc.) and observed with a STEM. As a result, it was confirmed that the partition wall had a forward taper shape.
- the angle ⁇ 1 formed between the side wall of the partition wall and the main surface of the substrate was 38 °.
- the partition wall thickness was 1.0 ⁇ m.
- the contact angle between the upper surface of the partition wall and the anisole after the curing baking process was 36 to 37 °.
- the contact angle between the surface of the first electrode (ITO thin film) and pure water was about 27 °.
- the pinning point P2 can be set lower, and in the embodiment in which the position of the pinning point P2 is close to the top of the recess, It is possible to reduce the thickness of the organic thin film layer in the vicinity of the side surface.
Abstract
Description
前記1層の隔壁は、撥液性を示す撥液部位を有し、
前記撥液部位は、前記凹部外である隔壁の上面部に延在しており、かつ前記隔壁の前記凹部を画成する側面であって、前記上面部の端部から、前記基板側の端部までの間の中途位置まで延在している、隔壁付基板に関する。
前記1層または複数層の有機薄膜層のうち、塗布法によって形成される有機薄膜層は、平面視での前記凹部の中央部の位置P1における前記有機薄膜層の厚さと、当該有機薄膜層と前記隔壁の側面との界面の上端部の位置P2の基板からの高さとが、下記式(1)の関係を満たす、前記発光装置に関する。
P1+500≧P2・・・(1)
撥液性材料を含む感光性樹脂組成物からなる薄膜を前記基板上に形成する工程と、
前記薄膜を露光する露光工程と、
露光された前記薄膜を現像することによって、前記1層の隔壁となる構造体を形成する現像工程と、
前記構造体を加熱することによって前記1層の隔壁を形成するキュアベーク工程とを含み、
前記構造体の側面と基板とのなす角は、鈍角であり、
前記キュアベーク工程において形成される前記1層の隔壁は、その側面と基板とのなす角が、鋭角である、隔壁付基板の製造方法に関する。
一対の電極と、当該一対の電極間に設けられる1層または複数層の有機薄膜層とを有する複数の有機EL素子を、それぞれ前記凹部に形成する工程とを有し、
前記有機EL素子を形成する工程では、前記有機薄膜層となる材料を含む塗布液を前記凹部に供給し、固化することにより前記有機薄膜層を形成する、発光装置の製造方法に関する。
図1および図2を参照して、本実施形態の表示装置の構成について説明する。図1は本実施形態の表示装置の一部を拡大して模式的に示す断面図である。図2は本実施形態の表示装置の一部を拡大して模式的に示す平面図である。
図1および図2に示されるように、表示装置1は、基板2と、この基板2に予め設定された区画である凹部を画成する隔壁3と、隔壁3によって画成される複数の凹部に設けられる複数の有機EL素子4とを含む。
なお図2に示される一実施形態では、格子状の隔壁3が設けられた表示装置1を示している。
なお他の実施形態の隔壁3として、隔壁3の側面と基板2の主表面とのなす角が鈍角に設定される、いわゆる逆テーパ形状の隔壁3を用いてもよい。以下では、隔壁3の側面、または後述の構造体の側面と、基板2の主表面とのなす角を隔壁3の傾斜角または構造体の傾斜角という場合がある。
(I)赤色有機EL素子4RがX方向に所定の間隔をあけて配置される行
(II)緑色有機EL素子4GがX方向に所定の間隔をあけて配置される行
(III)青色有機EL素子4BがX方向に所定の間隔をあけて配置される行
以下、図4~図9を参照しつつ、表示装置(発光装置)の製造方法について説明する。図4~図9は、本実施形態の表示装置の製造工程を説明するための図である。
発光装置の製造方法は、上記の構成を有する隔壁付基板の製造方法を含む。隔壁付基板の製造方法は、撥液性材料を含む感光性樹脂組成物からなる薄膜を基板上に形成する工程と、薄膜を露光する露光工程と、露光された前記薄膜を現像することによって、1層の隔壁となる構造体を形成する現像工程と、構造体を加熱することによって前記1層の隔壁を形成するキュアベーク工程とを含み、構造体の側面と基板とのなす角は、鈍角であり、キュアベーク工程において形成される1層の隔壁は、その側面と基板とのなす角が、鋭角とされる。
本工程では、隔壁3と第1の電極6とが設けられた基板2を用意する。なお本工程では、あらかじめ第1の電極6が設けられた基板2を用意してもよく、また本工程において基板2に第1の電極6を形成してもよい。なおアクティブマトリクス型の表示装置の場合、複数の有機EL素子を個別に駆動するための回路が予め形成された基板を、本実施形態の基板2として用いることもできる。たとえばTFT(Thin Film Transistor)やキャパシタなどがあらかじめ形成された基板を本実施形態の基板2として用いてもよい。
図4に示されるように、本実施形態では、まず撥液性材料を含む感光性樹脂組成物を基板2に塗布し、撥液性材料を含む感光性樹脂組成物からなる薄膜24を形成する。感光性樹脂組成物の塗布方法としては、たとえばスピンコート法、スリットコート法などをあげることができる。
成分(A)不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも1種に由来する構造単位と、炭素原子数2~4の環状エーテル構造を有する不飽和化合物に由来する構造単位とを含む共重合体(ただし、炭素原子数4~6のペルフルオロアルキル基を有する不飽和化合物に由来する構造単位は有さない。)(以下、「樹脂(A)」という場合がある。)
成分(B)炭素原子数4~6のペルフルオロアルキル基を有する不飽和化合物に由来する構造単位を含む重合体(以下、「樹脂(B)」という場合がある。)
成分(C)重合性化合物
成分(D)重合開始剤
成分(E)溶剤
なお、本明細書においては、各成分として例示する化合物は、特に断りのない限り、単独で又は組合せて使用することができる。
樹脂(A-1):不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも1種の化合物(a)と炭素原子数2~4の環状エーテル構造を有する不飽和化合物(b)とを重合してなる共重合体。
樹脂(A-2):化合物(a)及び不飽和化合物(b)と共重合可能な単量体(c)(ただし、炭素原子数2~4の環状エーテル構造は有さない。)と、化合物(a)と、不飽和化合物(b)とを重合してなる共重合体。
ただし、化合物(a)、不飽和化合物(b)及び単量体(c)は、炭素原子数4~6のペルフルオロアルキル基を有さない。
樹脂(A)としては、樹脂(A-1)が好ましい。
マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、3‐ビニルフタル酸、4-ビニルフタル酸、3,4,5,6-テトラヒドロフタル酸、1,2,3,6-テトラヒドロフタル酸、ジメチルテトラヒドロフタル酸、1,4-シクロヘキセンジカルボン酸等の不飽和ジカルボン酸類;
メチル-5-ノルボルネン-2,3-ジカルボン酸、5-カルボキシビシクロ[2.2.1]ヘプト-2-エン、5,6-ジカルボキシビシクロ[2.2.1]ヘプト-2-エン、5-カルボキシ-5-メチルビシクロ[2.2.1]ヘプト-2-エン、5-カルボキシ-5-エチルビシクロ[2.2.1]ヘプト-2-エン、5-カルボキシ-6-メチルビシクロ[2.2.1]ヘプト-2-エン、5-カルボキシ-6-エチルビシクロ[2.2.1]ヘプト-2-エン等のカルボキシ基を含有するビシクロ不飽和化合物類;
無水マレイン酸、シトラコン酸無水物、イタコン酸無水物、3-ビニルフタル酸無水物、4-ビニルフタル酸無水物、3,4,5,6-テトラヒドロフタル酸無水物、1,2,3,6-テトラヒドロフタル酸無水物、ジメチルテトラヒドロフタル酸無水物、5,6-ジカルボキシビシクロ[2.2.1]ヘプト-2-エン無水物(ハイミック酸無水物)等の不飽和ジカルボン酸類無水物;
こはく酸モノ〔2-(メタ)アクリロイルオキシエチル〕、フタル酸モノ〔2-(メタ)アクリロイルオキシエチル〕等の2価以上の多価カルボン酸の不飽和モノ〔(メタ)アクリロイルオキシアルキル〕エステル類;
α-(ヒドロキシメチル)アクリル酸のような、同一分子中にヒドロキシ基及びカルボキシ基を含有する不飽和アクリレート類等が挙げられる。
これらのうち、アクリル酸、メタクリル酸、無水マレイン酸等が共重合反応性、アルカリ溶解性の観点から好ましく用いられる。すなわち、本実施形態の隔壁3は、アクリル樹脂を含む感光性樹脂組成物を硬化させた構造体であることが好ましい。
本明細書において、「(メタ)アクリル酸」とは、アクリル酸及びメタクリル酸からなる群から選ばれる少なくとも1種を表す。「(メタ)アクリロイル」及び「(メタ)アクリレート」等の表記も同様の意味を有する。
不飽和化合物(b)は、炭素原子数2~4の環状エーテル構造(例えば、オキシラン環、オキセタン環およびテトラヒドロフラン環からなる群から選ばれる少なくとも1種)を有する不飽和化合物であり、炭素原子数2~4の環状エーテル構造とエチレン性不飽和二重結合とを有する単量体が好ましく、炭素原子数2~4の環状エーテル構造と(メタ)アクリロイルオキシ基とを有する単量体がより好ましい。
不飽和化合物(b1)としては、オキシラニル基と(メタ)アクリロイルオキシ基とを有する単量体が好ましく、不飽和脂環式炭化水素がエポキシ化された構造と(メタ)アクリロイルオキシ基とを有する単量体がより好ましい。これらの単量体を用いれば、感光性樹脂組成物の保存安定性をより高めることができる。
X1及びX2は、単結合、-R3-、*-R3-O-、*-R3-S-、*-R3-NH-を表す。ここで記号「*」が付された結合手は、酸素原子と結合する結合手を表す。
R3は、炭素原子数1~6のアルカンジイル基を表す。
炭素原子数1~4のアルキル基としては、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、sec-ブチル基、tert-ブチル基等が挙げられる。
ヒドロキシ基で置換されているアルキル基としては、ヒドロキシメチル基、1-ヒドロキシエチル基、2-ヒドロキシエチル基、1-ヒドロキシプロピル基、2-ヒドロキシプロピル基、3-ヒドロキシプロピル基、1-ヒドロキシ-1-メチルエチル基、2-ヒドロキシ-1-メチルエチル基、1-ヒドロキシブチル基、2-ヒドロキシブチル基、3-ヒドロキシブチル基、4-ヒドロキシブチル基等が挙げられる。
R1及びR2としては、好ましくは水素原子、メチル基、ヒドロキシメチル基、1-ヒドロキシエチル基、2-ヒドロキシエチル基が挙げられ、より好ましくは水素原子、メチル基が挙げられる。
X1及びX2としては、好ましくは単結合、メチレン基、エチレン基、*-CH2-O-基、*-CH2CH2-O-基が挙げられ、より好ましくは単結合、*-CH2CH2-O-基が挙げられる。ここで記号「*」は酸素原子と結合することを表す。
不飽和化合物(b2)としては、オキセタニル基と(メタ)アクリロイルオキシ基とを有する単量体が好ましい。不飽和化合物(b2)としては、例えば、3-メチル-3-(メタ)アクリロイルオキシメチルオキセタン、3-エチル-3-(メタ)アクリロイルオキシメチルオキセタン、3-メチル-3-(メタ)アクリロイルオキシエチルオキセタン、3-エチル-3-(メタ)アクリロイルオキシエチルオキセタン等が挙げられる。
不飽和化合物(b3)としては、具体的には、テトラヒドロフルフリルアクリレート(例えば、ビスコートV#150、大阪有機化学工業(株)製)、テトラヒドロフルフリルメタクリレート等が挙げられる。
化合物(a)に由来する構造単位;5モル%~60モル%(より好ましくは10モル%~50モル%)
不飽和化合物(b)に由来する構造単位;40モル%~95モル%(より好ましくは50モル%~90モル%)
樹脂(A-1)の構造単位の比率が、上記の範囲にあると、感光性樹脂組成物の保存安定性、感光性樹脂組成物からパターンを形成する際の現像性、並びに、得られる塗膜及びパターンの耐溶剤性、耐熱性および機械強度が良好になる傾向がある。
樹脂(A-1)としては、不飽和化合物(b)が不飽和化合物(b1)である樹脂(A-1)が好ましく、不飽和化合物(b)が不飽和化合物(b1-2)である樹脂(A-1)がより好ましい。
化合物(a)に由来する構造単位;2モル%~40モル%(より好ましくは5モル%~35モル%)
単量体(c)に由来する構造単位;1モル%~65モル%(より好ましくは1モル%~60モル%)
不飽和化合物(b)に由来する構造単位;2モル%~95モル%(より好ましくは5モル%~80モル%)
樹脂(A-2)の構造単位の比率が、上記の範囲にあると、感光性樹脂組成物の保存安定性、感光性樹脂組成物からパターンを形成する際の現像性、並びに、得られる塗膜及びパターンの耐溶剤性、耐熱性及び機械強度が良好になる傾向がある。
樹脂(A-2)としては、不飽和化合物(b)が不飽和化合物(b1)である樹脂(A-2)が好ましく、不飽和化合物(b)が不飽和化合物(b1-2)である樹脂(A-2)がより好ましい。
樹脂(A-2)は、樹脂(A-1)と同様の方法により製造することができる。
樹脂(B)としては、たとえば炭素原子数4~6のペルフルオロアルキル基を有する不飽和化合物(d)に由来する構造単位を含む重合体が挙げられる。
Rdは、水素原子、ハロゲン原子、シアノ基、フェニル基、ベンジル基又は炭素原子数1~21のアルキル基を表し、該アルキル基に含まれる水素原子は、ハロゲン原子又はヒドロキシ基で置換されていてもよい。
Rdとしては、水素原子、ハロゲン原子及びメチル基が好ましい。
Xdにおける炭素原子数6~12の2価の芳香族炭化水素基としては、たとえばフェニレン基、ナフタレンジイル基等が挙げられる。
化合物(a)に由来する構造単位;5質量%~40質量%(より好ましくは10質量%~30質量%)
不飽和化合物(d)に由来する構造単位;60質量%~95質量%(より好ましくは70質量%~90質量%)
化合物(a)に由来する構造単位;5質量%~40質量%(より好ましくは10質量%~30質量%)
不飽和化合物(b)に由来する構造単位;5質量%~80質量%(より好ましくは10質量%~70質量%)
不飽和化合物(d)に由来する構造単位;10質量%~80質量%(より好ましくは20質量%~70質量%)
化合物(a)に由来する構造単位;5質量%~40質量%(より好ましくは10質量%~30質量%)
不飽和化合物(b)に由来する構造単位;5質量%~70質量%(より好ましくは10質量%~60質量%)
単量体(c)に由来する構造単位;10質量%~50質量%(より好ましくは20質量%~40質量%)
不飽和化合物(d)に由来する構造単位;10質量%~80質量%(より好ましくは20質量%~70質量%)
樹脂(A1-1):化合物(a)と単量体(c)とを重合してなる共重合体、
樹脂(A1-2):化合物(a)と単量体(c)とを重合してなる共重合体に不飽和化合物(b)を反応させて得られる樹脂、
樹脂(A1-3):不飽和化合物(b)と単量体(c)とを重合してなる共重合体に化合物(a)を反応させて得られる樹脂等が挙げられる。
樹脂(A1)の含有量は、樹脂(A)及び樹脂(A1)の合計量に対して、好ましくは0~80質量%、より好ましくは0~50質量%である。樹脂(A1)の含有量が、前記の範囲にあると、パターンを高感度で形成することができ、かつ現像性に優れる。
感光性樹脂組成物は、成分(C)重合性化合物を含む。
成分(C)重合性化合物の含有量が、前記の範囲にあると、感度、得られるパターンの強度、平滑性、信頼性が良好になる傾向がある。
有機EL素子を設ける工程は、有機薄膜層を形成するための塗布液を供給する前に、隔壁付基板を表面処理する工程をさらに含む。すなわち、隔壁3の形成後であって、有機薄膜層を形成する工程の前、すなわち有機薄膜層を形成するための塗布液を供給する前に、第1の電極6のぬれ性を向上させるために、隔壁3が設けられた基板2(隔壁付基板)に対して表面処理工程を行うことが好ましい。表面処理としては、酸素プラズマ処理、UVオゾン処理、アルカリ溶剤処理、オゾン水処理(オゾン水を用いて洗浄する処理)等が挙げられ、これらの中でもオゾン水処理による表面処理が好ましい。
次に第1の有機薄膜層7を形成する。有機薄膜層が複数層ある場合、少なくとも1層の有機薄膜層を塗布法によって形成すればよい。本実施形態では、第1の有機薄膜層7および第2の有機薄膜層9を塗布法によって形成する形態について説明する。
P1+500≧P2 ・・・(1)
さらには、下記式(2)の関係を満たすことが好ましい。
P2≧P1 ・・・(2)
すなわち、最小厚さ部P1(nm)と有機薄膜層と隔壁の側面との界面の上端部の位置P2の基板2の主表面からの高さ(nm)との差が500nm以下であることが好ましい。このように本実施形態の有機薄膜層では、その厚さが最も薄くなる中央部と隔壁近傍の端部とで、高低差が小さく、より平坦となる。
本工程では有機薄膜層上に第2の電極10を形成する。本実施形態では第2の電極10は、有機EL素子4が設けられる表示領域において全面に形成する。すなわち第2の電極10は、第2の有機薄膜層9上だけでなく、隔壁3上にも形成し、複数の有機EL素子4にわたって連続して形成する。このように第2の電極10を形成することにより、第2の電極10は全ての有機EL素子4に共通の電極として機能する。
以下、有機EL素子4の構成例についてさらに詳しく説明する。有機EL素子4は、有機薄膜層として少なくとも1層の発光層を有する。上述したように一対の電極間には有機薄膜層として、たとえば正孔注入層、正孔輸送層、電子ブロック層、正孔ブロック層、電子輸送層、および電子注入層などを有する。
a)陽極/発光層/陰極
b)陽極/正孔注入層/発光層/陰極
c)陽極/正孔注入層/発光層/電子注入層/陰極
d)陽極/正孔注入層/発光層/電子輸送層/電子注入層/陰極
e)陽極/正孔注入層/正孔輸送層/発光層/陰極
f)陽極/正孔注入層/正孔輸送層/発光層/電子注入層/陰極
g)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
h)陽極/発光層/電子注入層/陰極
i)陽極/発光層/電子輸送層/電子注入層/陰極
(ここで、記号「/」は、記号「/」を挟む各層が互いに接合されていることを示す。以下同じ。)
まずITO薄膜からなる第1の電極(陽極)および電極に接続される配線等が予めパターン形成されたTFT基板を用意した。
まず実施例1と同じTFT基板を用意した。
成分(C)重合性化合物:トリメチロールプロパントリアクリレート(新中村化学工業(株)製 A-TMPT)
成分(D)重合開始剤:2-メチル-2-モルホリノ-1-(4-メチルスルファニルフェニル)プロパン-1-オン(BASF社製 イルガキュア(登録商標)907)
重合開始助剤(D1):4,4’-ビス(ジエチルアミノ)ベンゾフェノン(保土ヶ谷化学工業(株)製 EAB-F)
成分(E)溶剤:下記(Ea)~(Ed)の混合溶媒
(Ea):プロピレングリコールモノメチルエーテルアセテート;25質量%
(Eb):3-エトキシプロピオン酸エチル;25質量%
(Ec):3-メトキシ1-ブタノール;25質量%
(Ed):3-メトキシブチルアセテート;25質量%
まず実施例1と同様にしてTFT基板を用意した。
このキュアベーク工程後の隔壁の側面をFIB装置(セイコーインスツルメンツ製 XVision 200DB)にて薄膜加工し、STEM観察したところ、順テーパ形状の隔壁であることが確認された。隔壁の側面と基板の主表面とのなす角度θ1は38°であった。隔壁の厚さは1.0μmとした。
実施例1、2と比較例とのピニングポイントP2、有機薄膜層の最小厚さ部P1、図9に2点鎖線で示した隔壁の側面の基板側の端部における基板の主表面からのZ方向の有機薄膜層の厚さ(端部厚さ)を表1に示す。
2 基板
3 隔壁
3a 端部
4 有機EL素子
5 凹部
6 第1の電極(陽極)
7 第1の有機薄膜層(正孔注入層)
9 第2の有機薄膜層(発光層)
10 第2の電極(陰極)
11 撥液部位
12 親液部位
13 インキ
15 上面部の端部
16 基板側の端部
21 上面部
22 中途位置
23 表層部
24 感光性樹脂組成物からなる薄膜
25 フォトマスク
26 構造体
27 上端部
Claims (9)
- 基板と、この基板上において凹部を画成する1層の隔壁とを含む隔壁付基板であって、
前記1層の隔壁は、撥液性を示す撥液部位を有し、
前記撥液部位は、前記凹部外である隔壁の上面部に延在しており、かつ前記隔壁の前記凹部を画成する側面であって、前記上面部の端部から、前記基板側の端部までの間の中途位置まで延在している、隔壁付基板。 - 前記撥液部位には、撥液性を付与する撥液性材料が分布している、請求項1に記載の隔壁付基板。
- 前記1層の隔壁は、前記側面と前記基板とのなす角が、鋭角である、請求項1または2に記載の隔壁付基板。
- 前記隔壁は、アクリル樹脂を含む感光性樹脂組成物を硬化させた構造体である、請求項1~3のいずれか1項に記載の隔壁付基板。
- 請求項1~4のいずれか1項に記載の隔壁付基板と、
前記隔壁によって画成される前記凹部にそれぞれ設けられる複数の有機エレクトロルミネッセンス素子とを含む発光装置。 - 前記有機エレクトロルミネッセンス素子は、一対の電極と、当該一対の電極間に設けられる1層または複数層の有機薄膜層とを有し、
前記1層または複数層の有機薄膜層のうち、塗布法によって形成される有機薄膜層は、平面視での前記凹部の中央部の位置P1における前記有機薄膜層の厚さと、当該有機薄膜層と前記隔壁の側面との界面の上端部の位置P2の基板からの高さとが、下記式(1)の関係を満たす、請求項5に記載の発光装置。
P1+500≧P2・・・(1) - 請求項3に記載の隔壁付基板の製造方法であって、
撥液性材料を含む感光性樹脂組成物からなる薄膜を前記基板上に形成する工程と、
前記薄膜を露光する露光工程と、
露光された前記薄膜を現像することによって、前記1層の隔壁となる構造体を形成する現像工程と、
前記構造体を加熱することによって前記1層の隔壁を形成するキュアベーク工程とを含み、
前記構造体の側面と基板とのなす角は、鈍角であり、
前記キュアベーク工程において形成される前記1層の隔壁は、その側面と基板とのなす角が、鋭角である、隔壁付基板の製造方法。 - 請求項1~4のいずれか1項に記載の隔壁付基板を用意する工程と、
一対の電極と、当該一対の電極間に設けられる1層または複数層の有機薄膜層とを有する複数の有機エレクトロルミネッセンス素子を、それぞれ前記凹部に設ける工程とを有し、
前記有機エレクトロルミネッセンス素子を設ける工程では、前記有機薄膜層となる材料を含む塗布液を前記凹部に供給し、固化することにより前記有機薄膜層を形成する、発光装置の製造方法。 - 前記有機エレクトロルミネッセンス素子を設ける工程は、前記塗布液を供給する前に、前記隔壁付基板をオゾン水を用いて表面処理する工程をさらに含む、請求項8に記載の発光装置の製造方法。
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- 2015-03-27 JP JP2016511636A patent/JP6557216B2/ja active Active
- 2015-03-27 CN CN201580013074.1A patent/CN106105398B/zh not_active Expired - Fee Related
- 2015-03-27 WO PCT/JP2015/059751 patent/WO2015152085A1/ja active Application Filing
- 2015-03-27 KR KR1020167026485A patent/KR20160138058A/ko not_active Application Discontinuation
- 2015-03-31 TW TW104110411A patent/TWI668890B/zh not_active IP Right Cessation
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WO2019080510A1 (en) | 2017-10-23 | 2019-05-02 | Boe Technology Group Co., Ltd. | NETWORK SUBSTRATE, METHOD FOR MANUFACTURING SAME, AND DISPLAY APPARATUS |
EP3701565A4 (en) * | 2017-10-23 | 2021-08-04 | BOE Technology Group Co., Ltd. | NETWORK SUBSTRATE, ITS MANUFACTURING PROCESS AND DISPLAY APPARATUS |
US11302755B2 (en) | 2017-10-23 | 2022-04-12 | Hefei Xinsheng Optoelectronics Technology Co., Ltd. | Array substrate, manufacturing method thereof, and display apparatus |
EP3509109A3 (en) * | 2017-12-14 | 2019-10-23 | LG Display Co., Ltd. | Electroluminescence display apparatus |
US10943962B2 (en) | 2017-12-14 | 2021-03-09 | Lg Display Co., Ltd. | Electroluminescence display apparatus |
Also Published As
Publication number | Publication date |
---|---|
TWI668890B (zh) | 2019-08-11 |
JPWO2015152085A1 (ja) | 2017-04-13 |
CN106105398A (zh) | 2016-11-09 |
CN106105398B (zh) | 2018-06-29 |
KR20160138058A (ko) | 2016-12-02 |
JP6557216B2 (ja) | 2019-08-07 |
TW201603347A (zh) | 2016-01-16 |
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